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Sample records for solution state ligand

  1. 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.

  2. 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.

  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. Ligands Exchange Process on Gold Nanoparticles in Acetone Solution

    Science.gov (United States)

    Hu, C. L.; Mu, Y. Y.; Bian, Z. C.; Luo, Z. H.; Luo, K.; Huang, A. Z.

    2018-05-01

    The ligands exchange process on gold nanoparticles (GNPs) was proceeded by using hydrophobic group (PPh3) and hydrophilic group (THPO) in acetone solution. The FTIR and XPS results demonstrated that part of THPO was replaced by PPh3 which was dissolved in polar solution (acetone); the results were in accordance with the electrochemical analysis where the differential capacity decreased with increasing exchange time. After 12 h, the exchange process terminated and the final ratio of PPh3 and THPO was about 1.4: 1. This ratio remained unchanged although the PPh3 and THPO modified GNPs re-dispersed in the PPh3 acetone solution demonstrating the stable adsorption of both ligands after exchanging for 12 h. The TEM images showed that the gold nanoparticles were self-assembled from scattered to arranged morphology due to the existence of hydrophilic and hydrophobic ligands and led to Janus gold nanoparticles.

  5. Mixed ligand chelates of rare earths in aqueous solution

    International Nuclear Information System (INIS)

    Lakhani, S.U.; Thakur, G.S.; Sangal, S.P.

    1981-01-01

    Mixed ligand chelates of the 1:1 trivalent lanthanoids-EDTA, HEDTA and NTA chelates-1, 2-Dihydroxybenzene (Pyrocatechol) have been investigated at 35degC and 0.2 M ionic strength maintained by NaC10 4 . The formation of mixed ligand chelates has been found in all cases. The formation of mixed ligand chelates with EDTA shows the coordination number of lanthanoids to be eight, while the mixed ligand chelates with HEDTA and NTA shows the coordination number to be seven and six respectively. The stability constants of mixed ligand chelates are smaller than the binary complexes. The order of stability constants with respect to primary ligands follows the order NTA>HEDTA>EDTA. With respect to metal ions the stability constants increases with the decrease in ionic radii such as Gd< Er< Yb. (author)

  6. Solution structure of the twelfth cysteine-rich ligand-binding repeat in rat megalin

    International Nuclear Information System (INIS)

    Wolf, Christian A.; Dancea, Felician; Shi Meichen; Bade-Noskova, Veronika; Rueterjans, Heinz; Kerjaschki, Dontscho; Luecke, Christian

    2007-01-01

    Megalin, an approx. 600 kDa transmembrane glycoprotein that acts as multi-ligand transporter, is a member of the low density lipoprotein receptor gene family. Several cysteine-rich repeats, each consisting of about 40 residues, are responsible for the multispecific binding of ligands. The solution structure of the twelfth cysteine-rich ligand-binding repeat with class A motif found in megalin features two short β-strands and two helical turns, yielding the typical fold with a I-III, II-V and IV-VI disulfide bridge connectivity pattern and a calcium coordination site at the C-terminal end. The resulting differences in electrostatic surface potential compared to other ligand-binding modules of this gene family, however, may be responsible for the functional divergence

  7. Long-lived charge-separated states in ligand-stabilized silver clusters

    KAUST Repository

    Pelton, Matthew; Tang, Yun; Bakr, Osman; Stellacci, Francesco

    2012-01-01

    Recently developed synthesis methods allow for the production of atomically monodisperse clusters of silver atoms stabilized in solution by aromatic thiol ligands, which exhibit intense absorption peaks throughout the visible and near-IR spectral regions. Here we investigated the time-dependent optical properties of these clusters. We observed two kinetic processes following ultrafast laser excitation of any of the absorption peaks: a rapid decay, with a time constant of 1 ps or less, and a slow decay, with a time constant that can be longer than 300 ns. Both time constants decrease as the polarity of the solvent increases, indicating that the two processes correspond to the formation and recombination, respectively, of a charge-separated state. The long lifetime of this state and the broad optical absorption spectrum mean that the ligand-stabilized silver clusters are promising materials for solar energy harvesting. © 2012 American Chemical Society.

  8. Long-lived charge-separated states in ligand-stabilized silver clusters

    KAUST Repository

    Pelton, Matthew

    2012-07-25

    Recently developed synthesis methods allow for the production of atomically monodisperse clusters of silver atoms stabilized in solution by aromatic thiol ligands, which exhibit intense absorption peaks throughout the visible and near-IR spectral regions. Here we investigated the time-dependent optical properties of these clusters. We observed two kinetic processes following ultrafast laser excitation of any of the absorption peaks: a rapid decay, with a time constant of 1 ps or less, and a slow decay, with a time constant that can be longer than 300 ns. Both time constants decrease as the polarity of the solvent increases, indicating that the two processes correspond to the formation and recombination, respectively, of a charge-separated state. The long lifetime of this state and the broad optical absorption spectrum mean that the ligand-stabilized silver clusters are promising materials for solar energy harvesting. © 2012 American Chemical Society.

  9. Rapid and Efficient Collection of Platinum from Karstedt's Catalyst Solution via Ligands-Exchange-Induced Assembly.

    Science.gov (United States)

    Yang, Gonghua; Wei, Yanlong; Huang, Zhenzhu; Hu, Jiwen; Liu, Guojun; Ou, Ming; Lin, Shudong; Tu, Yuanyuan

    2018-02-21

    Reported herein is a novel strategy for the rapid and efficient collection of platinum from Karstedt's catalyst solution. By taking advantage of a ligand-exchange reaction between alkynols and the 1,3-divinyltetramethyldisiloxane ligand (M Vi M Vi ) that coordinated with platinum (Pt(0)), the Karstedt's catalyst particles with a size of approximately 2.5 ± 0.7 nm could be reconstructed and assembled into larger particles with a size of 150 ± 35 nm due to the hydrogen bonding between the hydroxyl groups of the alkynol. In addition, because the silicone-soluble M Vi M Vi ligand of the Karstedt's catalyst was replaced by water-soluble alkynol ligands, the resultant large particles were readily dispersed in water, resulting in rapid, efficient, and complete collection of platinum from the Karstedt's catalyst solutions with platinum concentrations in the range from ∼20 000 to 0.05 ppm. Our current strategy not only was used for the rapid and efficient collection of platinum from the Karstedt's catalyst solutions, but it also enabled the precise evaluation of the platinum content in the Karstedt's catalysts, even if this platinum content was extremely low (i.e., 0.05 ppm). Moreover, these platinum specimens that were efficiently collected from the Karstedt's catalyst solutions could be directly used for the evaluation of platinum without the need for pretreatment processes, such as calcination and digestion with hydrofluoric acid, that were traditionally used prior to testing via inductively coupled plasma mass spectrometry in conventional methods.

  10. Transition state structures in solution

    International Nuclear Information System (INIS)

    Bertran, J.; Lluch, J. M.; Gonzalez-Lafont, A.; Dillet, V.; Perez, V.

    1995-01-01

    In the present paper the location of transition state structures for reactions in solution has been studied. Continuum model calculations have been carried out on the Friedel-Crafts alkylation reaction and a proton transfer through a water molecule between two oxygen atoms in formic acid. In this model the separation between the chemical system and the solvent has been introduced. On the other hand, the discrete Monte Carlo methodology has also been used to simulate the solvent effect on dissociative electron transfer processes. In this model, the hypothesis of separability is not assumed. Finally, the validity of both approaches is discussed

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

    International Nuclear Information System (INIS)

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

    2013-01-01

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

  12. Deciphering ligands' interaction with Cu and Cu2O nanocrystal surfaces by NMR solution tools.

    Science.gov (United States)

    Glaria, Arnaud; Cure, Jérémy; Piettre, Kilian; Coppel, Yannick; Turrin, Cédric-Olivier; Chaudret, Bruno; Fau, Pierre

    2015-01-12

    The hydrogenolysis of [Cu2{(iPrN)2(CCH3)}2] in the presence of hexadecylamine (HDA) or tetradecylphosphonic acid (TDPA) in toluene leads to 6-9 nm copper nanocrystals. Solution NMR spectroscopy has been used to describe the nanoparticle surface chemistry during the dynamic phenomenon of air oxidation. The ligands are organized as multilayered shells around the nanoparticles. The shell of ligands is controlled by both their intermolecular interactions and their bonding strength on the nanocrystals. Under ambient atmosphere, the oxidation rate of colloidal copper nanocrystals closely relies on the chemical nature of the employed ligands (base or acid). Primary amine molecules behave as soft ligands for Cu atoms, but are even more strongly coordinated on surface Cu(I) sites, thus allowing a very efficient corrosion protection of the copper core. On the contrary, the TDPA ligands lead to a rapid oxidation rate of Cu nanoparticles and eventually to the re-dissolution of Cu(II) species at the expense of the nanocrystals. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Dynamics of ligand exchange and association processes in solutions of transition 3d-metal fluorides

    International Nuclear Information System (INIS)

    Nazmutdinova, G.A.; Shtyrlin, V.G.; Zakharov, A.V.; Sal'nikov, Yu.I.

    1993-01-01

    By 19 NMR in combination with ESR spectroscopy rate constants and activation parameters of fluoride-ion exchange reactions in solutions of VOF 5 3- and FeF 6 3- complexes were determined. Associative character of the studied reactions of ligand exchange is shown. Dependence of fluoride complex reactivity on the charge, electron structure of the central ion and formation of hydrogen bonds of coordinated F - ions with solvent molecules was demonstrated. Stability constants, rates of formation and dissociation of intercomplex associates in fluoride solutions were ascertained

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-10-01

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

  15. Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution

    DEFF Research Database (Denmark)

    Zhang, Wenkai; Kjær, Kasper Skov; Alonso-Mori, Roberto

    2017-01-01

    iron complexes with four cyanide (CN-;) ligands and one 2,2′-bipyridine (bpy) ligand. This enables MLCT excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL...... state lifetime of iron based complexes due to spin crossover-the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand...

  16. 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

  17. 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.

  18. Ligand binding and thermostability of different allosteric states of the insulin zinc-hexamer

    DEFF Research Database (Denmark)

    Huus, Kasper; Havelund, Svend; Olsen, Helle B

    2006-01-01

    The influence of ligand binding and conformation state on the thermostability of hexameric zinc-insulin was studied by differential scanning calorimetry (DSC). The insulin hexamer exists in equilibrium between the forms T6, T3R3, and R6. Phenolic ligands induce and stabilize the T3R3- and R6-stat...

  19. Equilibrium Speciation of Select Lanthanides in the Presence of Acidic Ligands in Homo- and Heterogeneous Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, Troy A [Univ. of Nevada, Las Vegas, NV (United States)

    2011-08-01

    This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd3+), sodium (Na+), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd3+ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, 22Na and 13C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution of Nd3+, Na+, lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logKNd and logKNa extraction constants under selected conditions. Results showed that high Nd3+ loading of the HDEHP led to Nd3+ speciation that departs from the ion exchange mechanism and includes formation of highly aggregated, polynuclear [NdLactate(DEHP)2]x; (with x > 1). By substituting lanthanum (La3+) for Nd3+ in this system, NMR scoping experiments using 23Na, 31P nuclei and 13C labeled lactate were performed. Results indicated that this technique is sensitive to changes in system speciation, and that further experiments are warranted. In a homogeneous system representing the TALSPEAK aqueous phase, Lactate protonation behavior at various temperatures was characterized using a combination of potentiometric titration and modeling with the Hyperquad computer program. The temperature dependent deprotonation behavior of lactate showed little change with temperature at 2.0 M NaCl ionic strength. Cloud point extraction is a non-traditional separation technique that starts with a homogeneous

  20. Computing UV/vis spectra using a combined molecular dynamics and quantum chemistry approach: bis-triazin-pyridine (BTP) ligands studied in solution.

    Science.gov (United States)

    Höfener, Sebastian; Trumm, Michael; Koke, Carsten; Heuser, Johannes; Ekström, Ulf; Skerencak-Frech, Andrej; Schimmelpfennig, Bernd; Panak, Petra J

    2016-03-21

    We report a combined computational and experimental study to investigate the UV/vis spectra of 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine (BTP) ligands in solution. In order to study molecules in solution using theoretical methods, force-field parameters for the ligand-water interaction are adjusted to ab initio quantum chemical calculations. Based on these parameters, molecular dynamics (MD) simulations are carried out from which snapshots are extracted as input to quantum chemical excitation-energy calculations to obtain UV/vis spectra of BTP ligands in solution using time-dependent density functional theory (TDDFT) employing the Tamm-Dancoff approximation (TDA). The range-separated CAM-B3LYP functional is used to avoid large errors for charge-transfer states occurring in the electronic spectra. In order to study environment effects with theoretical methods, the frozen-density embedding scheme is applied. This computational procedure allows to obtain electronic spectra calculated at the (range-separated) DFT level of theory in solution, revealing solvatochromic shifts upon solvation of up to about 0.6 eV. Comparison to experimental data shows a significantly improved agreement compared to vacuum calculations and enables the analysis of relevant excitations for the line shape in solution.

  1. Ligand adsorption on an activated carbon for the removal of chromate ions from aqueous solutions.

    Science.gov (United States)

    García-Martín, J; López-Garzón, R; Godino-Salido, M Luz; Gutiérrez-Valero, M Dolores; Arranz-Mascarós, P; Cuesta, R; Carrasco-Marín, F

    2005-07-19

    The results presented in this work are related to the design of a guideline to develop specific properties at the surface of an activated carbon (AC). For this, two model aromatic compounds have been synthesized and their electrolytic behavior in aqueous solutions was studied by a potentiometric method. The textural characteristics of the activated carbon were determined by porosimetry methods. The nature of oxygen-carrying functions and the acid-base behavior of the AC surface were characterized by TPD and potentiometric titration methods, respectively. The adsorption and desorption equilibria of the aromatic compounds on activated carbon were measured in aqueous solutions, and the hysteresis between adsorption and desorption, which reveals irreversible adsorption, was discussed on the basis of the frontier orbital theory. HOMO and LUMO orbitals of the adsorbent and adsorbates were calculated, and irreversible adsorption was attributed to the small energy difference between HOMO and LUMO of the aromatic adsorbates and the adsorbent. Adsorption equilibria of K2CrO4 in aqueous solution on the AC alone and on the AC-aromatic ligand adsorbents, respectively, prove the efficient development of specific chemical functions at the carbon surface provided by the adsorbed aromatic compounds.

  2. Solution stabilities of some mixed ligand complexes of UO22+ and Th4+ with complexones and salicylic acids

    International Nuclear Information System (INIS)

    Singh, R.K.; Saxena, M.C.

    1991-01-01

    Formation constants (log Ksub(MAL)sup(MA)) of mixed ligands complexes (MAL), where M = UO 2 2+ or Th 4+ , A = IMDA, NTA, HEDTA, EDTA, CDTA or DTPA, L = salicylic acid (SA) or 5-sulphosalicylic acid (SSA), have been determined by pH titrations using Irving-Rossotti approach at 25 o C and at I =0.2 (mol dm -3 , KNO 3 ). The solution stabilities exhibit the sequence (i) Th 4+ >UO 2 2+ , (ii) IMDA>NTA>HEDTA>EDTA>CDTA>DTPA, and (iii) SA>SSA with respect to metal ions, primary ligands and secondary ligands, respectively. The formation constants log Ksub(ML)sup(M) and log Ksub(ML 2 )sup(ML) have also been determined. The Δlog K values have been found to be negative-increasing numerically with the negative charge on the deprotonated primary ligand (A n- ). (author). 17 refs., 1 tab

  3. Photophysical investigation of energy transfer luminescence of lanthanide chelates with aromatic polyaminocarboxylate ligands in aqueous solutions

    International Nuclear Information System (INIS)

    Hoshino, Hitoshi; Saitoh, Takashi; Yotsuyanagi, Takao

    1995-01-01

    Some photophysical data including emission lifetimes (τ), total emission quantum yields (Φ), and ligand phosphorescence data are reported for the energy-transfer luminescence of the Eu(III) chelate of Quin 2 and the Tb(III) chelate of BAPTA: Quin 2 means 2-[(2-amino-5-methylphenoxy)methyl]-6-methoxy-8-aminoquinoline-N,N,N',N'-tetraacetic acid; BAPTA means 1,2-bis(2-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid. The energy diagrams for the ligand T 1 and the metal-center f-f levels are proposed. The τ values of Tb(III)-BAPTA chelates are 1.73 ms in H 2 O and 3.44 ms in D 2 O. The Eu(III)-Quin 2 chelate system shows a bi-exponential decay of emission; τ=0.048 and 0.20 ms in H 2 O and 0.066 and 1.44 ms in D 2 O. The Quin 2 chelate is kinetically inert, so that the interchange of these two conformer structures are very slow at room temperature. The number of water molecules in the primary coordination sphere is calculated from the lifetime data to be 1.9-2.4 for Eu-Quin 2 and 0.5 for Tb-BAPTA. The Φ values in aqueous solutions are rather small in these systems; 0.009 for Tb-BAPTA and 0.0023 for Eu-Quin 2, but these are enough counterbalanced by the large molar absorptivities giving the great sensitization factors for the ions; the sensitization factors against each aqua ion are 1380 for Eu-Quin 2 and 1600 for Tb-BAPTA. (author)

  4. 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

  5. The Effect of Precursor Ligands and Oxidation State in the Synthesis of Bimetallic Nano-Alloys

    KAUST Repository

    LaGrow, Alec P.

    2015-05-12

    The characteristics of bimetallic nanomaterials are dictated by their size, shape and elemental distribution. Solution synthesis is widely utilized to form nanomaterials, such as nanoparticles, with controlled size and shape. However, the effects of variables on the characteristics of bimetallic nanomaterials are not completely understood. In this study, we used a continuous-flow synthetic strategy to explore the effects of the ligands and the oxidation state of a metal precursor in a shape-controlled synthesis on the final shape of the nanomaterials and the elemental distribution within the alloy. We demonstrate that this strategy can tune the size of monodisperse PtM (M=Ni or Cu) alloy nanocrystals ranging from 3 to 16 nm with an octahedral shape using acetylacetonate or halide precursors of Pt(II), Pt(IV) and Ni or Cu (II). The nanoparticles formed from halide precursors showed an enrichment of platinum on their surfaces, and the bromides could oxidatively etch the nanoparticles during synthesis with the O2/Br- pair. The two nanocrystal precursors can be uti-lized independently and can control the size with a trend of Pt(acac)2ligand shell of a precursor during the synthesis of alloy nanoparticles as well as to control, in a scalable manner, the nanomaterial size and surface chemistry.

  6. Development of Novel Method for Rapid Extract of Radionuclides from Solution Using Polymer Ligand Film

    Science.gov (United States)

    Rim, Jung H.

    Accurate and fast determination of the activity of radionuclides in a sample is critical for nuclear forensics and emergency response. Radioanalytical techniques are well established for radionuclides measurement, however, they are slow and labor intensive, requiring extensive radiochemical separations and purification prior to analysis. With these limitations of current methods, there is great interest for a new technique to rapidly process samples. This dissertation describes a new analyte extraction medium called Polymer Ligand Film (PLF) developed to rapidly extract radionuclides. Polymer Ligand Film is a polymer medium with ligands incorporated in its matrix that selectively and rapidly extract analytes from a solution. The main focus of the new technique is to shorten and simplify the procedure necessary to chemically isolate radionuclides for determination by alpha spectrometry or beta counting. Five different ligands were tested for plutonium extraction: bis(2-ethylhexyl) methanediphosphonic acid (H2DEH[MDP]), di(2-ethyl hexyl) phosphoric acid (HDEHP), trialkyl methylammonium chloride (Aliquat-336), 4,4'(5')-di-t-butylcyclohexano 18-crown-6 (DtBuCH18C6), and 2-ethylhexyl 2-ethylhexylphosphonic acid (HEH[EHP]). The ligands that were effective for plutonium extraction further studied for uranium extraction. The plutonium recovery by PLFs has shown dependency on nitric acid concentration and ligand to total mass ratio. H2DEH[MDP] PLFs performed best with 1:10 and 1:20 ratio PLFs. 50.44% and 47.61% of plutonium were extracted on the surface of PLFs with 1M nitric acid for 1:10 and 1:20 PLF, respectively. HDEHP PLF provided the best combination of alpha spectroscopy resolution and plutonium recovery with 1:5 PLF when used with 0.1M nitric acid. The overall analyte recovery was lower than electrodeposited samples, which typically has recovery above 80%. However, PLF is designed to be a rapid field deployable screening technique and consistency is more important

  7. Solution structure of human intestinal fatty acid binding protein: Implications for ligand entry and exit

    International Nuclear Information System (INIS)

    Zhang Fengli; Luecke, Christian; Baier, Leslie J.; Sacchettini, James C.; Hamilton, James A.

    1997-01-01

    The human intestinal fatty acid binding protein (I-FABP) is a small (131 amino acids) protein which binds dietary long-chain fatty acids in the cytosol of enterocytes. Recently, an alanine to threonine substitution at position 54 in I-FABP has been identified which affects fatty acid binding and transport, and is associated with the development of insulin resistance in several populations including Mexican-Americans and Pima Indians. To investigate the molecular basis of the binding properties of I-FABP, the 3D solution structure of the more common form of human I-FABP (Ala54) was studied by multidimensional NMR spectroscopy.Recombinant I-FABP was expressed from E. coli in the presence and absence of 15N-enriched media. The sequential assignments for non-delipidated I-FABP were completed by using 2D homonuclear spectra (COSY, TOCSY and NOESY) and 3D heteronuclear spectra(NOESY-HMQC and TOCSY-HMQC). The tertiary structure of human I-FABP was calculated by using the distance geometry program DIANA based on 2519 distance constraints obtained from the NMR data. Subsequent energy minimization was carried out by using the program SYBYL in the presence of distance constraints. The conformation of human I-FABP consists of 10 antiparallel β-strands which form two nearly orthogonal β-sheets of five strands each, and two short α-helices that connect the β-strands A and B. The interior of the protein consists of a water-filled cavity between the two β-sheets. The NMR solution structure of human I-FABP is similar to the crystal structure of rat I-FABP.The NMR results show significant conformational variability of certain backbone segments around the postulated portal region for the entry and exit of fatty acid ligand

  8. Solution structure of human intestinal fatty acid binding protein: Implications for ligand entry and exit

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Fengli [Boston University School of Medicine, Department of Biophysics (United States); Luecke, Christian [Johann Wolfgang Goethe-Universitaet (Germany); Baier, Leslie J. [NIDDK, NIH, Phoenix Epidemiology and Clinical Research Branch (United States); Sacchettini, James C. [Texas A and M University, Department of Biochemistry and Biophysics (United States); Hamilton, James A. [Boston University School of Medicine, Department of Biophysics (United States)

    1997-04-15

    The human intestinal fatty acid binding protein (I-FABP) is a small (131 amino acids) protein which binds dietary long-chain fatty acids in the cytosol of enterocytes. Recently, an alanine to threonine substitution at position 54 in I-FABP has been identified which affects fatty acid binding and transport, and is associated with the development of insulin resistance in several populations including Mexican-Americans and Pima Indians. To investigate the molecular basis of the binding properties of I-FABP, the 3D solution structure of the more common form of human I-FABP (Ala54) was studied by multidimensional NMR spectroscopy.Recombinant I-FABP was expressed from E. coli in the presence and absence of 15N-enriched media. The sequential assignments for non-delipidated I-FABP were completed by using 2D homonuclear spectra (COSY, TOCSY and NOESY) and 3D heteronuclear spectra(NOESY-HMQC and TOCSY-HMQC). The tertiary structure of human I-FABP was calculated by using the distance geometry program DIANA based on 2519 distance constraints obtained from the NMR data. Subsequent energy minimization was carried out by using the program SYBYL in the presence of distance constraints. The conformation of human I-FABP consists of 10 antiparallel {beta}-strands which form two nearly orthogonal {beta}-sheets of five strands each, and two short {alpha}-helices that connect the {beta}-strands A and B. The interior of the protein consists of a water-filled cavity between the two {beta}-sheets. The NMR solution structure of human I-FABP is similar to the crystal structure of rat I-FABP.The NMR results show significant conformational variability of certain backbone segments around the postulated portal region for the entry and exit of fatty acid ligand.

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

    NARCIS (Netherlands)

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

    2005-01-01

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

  10. Distribution of the ligand field at the Fe2+ ion in frozen aqueous solutions of Fe(ClO4)2

    International Nuclear Information System (INIS)

    Nagy, D.L.; Horvath, D.; Szuecs, I.S.; Spiering, H.

    1981-01-01

    Moessbauer spectra of eutectic frozen aqueous solutions of Fe(ClO 4 ) 2 have been measured at 4.2 K in applied longitudinal magnetic fields up to 5 T. The spectra are interpreted in terms of a model accounting for the random distribution of the ligand field at the Fe 2+ ion owing to the amorphity of the environment. The equilibrium state of the Fe(H 2 O) 6 2+ complex is determined by a static Jahn-Teller calculation. The main features of all spectra can be well reproduced by choosing Esub(JT)(tau)=140 cm -1 and ωsub(tau)=150 cm -1 . (author)

  11. The Effect of Precursor Ligands and Oxidation State in the Synthesis of Bimetallic Nano-Alloys

    KAUST Repository

    LaGrow, Alec P.; Knudsen, Kristian; AlYami, Noktan; Anjum, Dalaver H.; Bakr, Osman

    2015-01-01

    of variables on the characteristics of bimetallic nanomaterials are not completely understood. In this study, we used a continuous-flow synthetic strategy to explore the effects of the ligands and the oxidation state of a metal precursor in a shape

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

    International Nuclear Information System (INIS)

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

    1976-01-01

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

  13. Enhanced Open-Circuit Voltage in Colloidal Quantum Dot Photovoltaics via Reactivity-Controlled Solution-Phase Ligand Exchange

    KAUST Repository

    Jo, Jea Woong; Kim, Younghoon; Choi, Jongmin; de Arquer, F. Pelayo Garcí a; Walters, Grant; Sun, Bin; Ouellette, Olivier; Kim, Junghwan; Proppe, Andrew H.; Quintero-Bermudez, Rafael; Fan, James; Xu, Jixian; Tan, Chih Shan; Voznyy, Oleksandr; Sargent, Edward H.

    2017-01-01

    The energy disorder that arises from colloidal quantum dot (CQD) polydispersity limits the open-circuit voltage (VOC) and efficiency of CQD photovoltaics. This energy broadening is significantly deteriorated today during CQD ligand exchange and film assembly. Here, a new solution-phase ligand exchange that, via judicious incorporation of reactivity-engineered additives, provides improved monodispersity in final CQD films is reported. It has been found that increasing the concentration of the less reactive species prevents CQD fusion and etching. As a result, CQD solar cells with a VOC of 0.7 V (vs 0.61 V for the control) for CQD films with exciton peak at 1.28 eV and a power conversion efficiency of 10.9% (vs 10.1% for the control) is achieved.

  14. Enhanced Open-Circuit Voltage in Colloidal Quantum Dot Photovoltaics via Reactivity-Controlled Solution-Phase Ligand Exchange

    KAUST Repository

    Jo, Jea Woong

    2017-10-09

    The energy disorder that arises from colloidal quantum dot (CQD) polydispersity limits the open-circuit voltage (VOC) and efficiency of CQD photovoltaics. This energy broadening is significantly deteriorated today during CQD ligand exchange and film assembly. Here, a new solution-phase ligand exchange that, via judicious incorporation of reactivity-engineered additives, provides improved monodispersity in final CQD films is reported. It has been found that increasing the concentration of the less reactive species prevents CQD fusion and etching. As a result, CQD solar cells with a VOC of 0.7 V (vs 0.61 V for the control) for CQD films with exciton peak at 1.28 eV and a power conversion efficiency of 10.9% (vs 10.1% for the control) is achieved.

  15. State memory in solution gated epitaxial graphene

    Science.gov (United States)

    Butko, A. V.; Butko, V. Y.; Lebedev, S. P.; Lebedev, A. A.; Davydov, V. Y.; Smirnov, A. N.; Eliseyev, I. A.; Dunaevskiy, M. S.; Kumzerov, Y. A.

    2018-06-01

    We studied electrical transport in transistors fabricated on a surface of high quality epitaxial graphene with density of defects as low as 5·1010 cm-2 and observed quasistatic hysteresis with a time constant in a scale of hours. This constant is in a few orders of magnitude greater than the constant previously reported in CVD graphene. The hysteresis observed here can be described as a shift of ∼+2V of the Dirac point measured during a gate voltage increase from the position of the Dirac point measured during a gate voltage decrease. This hysteresis can be characterized as a nonvolatile quasistatic state memory effect in which the state of the gated graphene is determined by its initial state prior to entering the hysteretic region. Due to this effect the difference in resistance of the gated graphene measured in the hysteretic region at the same applied voltages can be as high as 70%. The observed effect can be explained by assuming that charge carriers in graphene and oppositely charged molecular ions from the solution form quasistable interfacial complexes at the graphene interface. These complexes likely preserve the initial state by preventing charge carriers in graphene from discharging in the hysteretic region.

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

    International Nuclear Information System (INIS)

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

    1983-01-01

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

  17. Docking of flexible ligands to flexible receptors in solution by molecular dynamics simulation

    NARCIS (Netherlands)

    Mangoni, R; Roccatano, D; Di Nola, A

    1999-01-01

    In this paper, a method of simulating the docking of small flexible ligands to flexible receptors in water is reported. The method is based on molecular dynamics simulations and is an extension of an algorithm previously reported by Di Nola et al, (Di Nola et al,, Proteins 1994;19:174-182), The

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

    International Nuclear Information System (INIS)

    Ribokaite, Kristina

    2013-01-01

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

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

    International Nuclear Information System (INIS)

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

    1987-01-01

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

  20. Effects of ligand substitution on the excited state dynamics of the Ru(dcbpy)(CO) 2I 2 complex

    Science.gov (United States)

    Lehtovuori, Viivi; Kallioinen, Jani; Myllyperkiö, Pasi; Haukka, Matti; Korppi-Tommola, Jouko

    2003-11-01

    Spectroscopic evidence suggest [PCCP 3 (2001) 1992] that illumination with visible light of the [ trans-I-Ru(dcbpy)(CO) 2I 2] (dcbpy= 4,4 '-dicarboxy-2,2 '-bipyridine) complex in solution induces dissociation of a CO group followed by reorganization of the ligands and attachment of a solvent molecule. In the present study, we report results on excited state dynamics of this ruthenium complex and its photoproduct. Femtosecond transient absorption measurements reveal dominance of excited state absorption of the reactant and the photoproduct [ cis-I-Ru(dcbpy)(CO)(Sol)I 2] (Sol=ethanol or acetonitrile) in the visible spectral region. The time-resolved measurements for the reactant at 77 K indicate interligand charge transfer from mixed Ru-I states to empty dcbpy orbitals. For the photoproduct, no such transfer was observed. In both complexes recovery from the lowest energy excited triplet state to the ground state occurs via two channels: radiative relaxation and a parallel barrier controlled non-radiative relaxation. The barrier is much higher in the reactant (about 850 cm -1) than in the product. A combination of DFT and ZINDO/CI calculations was used to estimate excited singlet and triplet spectra of the reactant and the product molecules. Calculated singlet-triplet difference spectra qualitatively match the observed transient spectra 500 fs after excitation supporting the idea that observed excited state relaxation occurs from the triplet states in both complexes.

  1. Effects of ligand substitution on the excited state dynamics of the Ru(dcbpy)(CO)2I2 complex

    International Nuclear Information System (INIS)

    Lehtovuori, Viivi; Kallioinen, Jani; Myllyperkioe, Pasi; Haukka, Matti; Korppi-Tommola, Jouko

    2003-01-01

    Spectroscopic evidence suggest [PCCP 3 (2001) 1992] that illumination with visible light of the [trans-I-Ru(dcbpy)(CO) 2 I 2 ] (dcbpy4,4 ' -dicarboxy-2,2 ' -bipyridine) complex in solution induces dissociation of a CO group followed by reorganization of the ligands and attachment of a solvent molecule. In the present study, we report results on excited state dynamics of this ruthenium complex and its photoproduct. Femtosecond transient absorption measurements reveal dominance of excited state absorption of the reactant and the photoproduct [cis-I-Ru(dcbpy)(CO)(Sol)I 2 ] (Sol=ethanol or acetonitrile) in the visible spectral region. The time-resolved measurements for the reactant at 77 K indicate interligand charge transfer from mixed Ru-I states to empty dcbpy orbitals. For the photoproduct, no such transfer was observed. In both complexes recovery from the lowest energy excited triplet state to the ground state occurs via two channels: radiative relaxation and a parallel barrier controlled non-radiative relaxation. The barrier is much higher in the reactant (about 850 cm -1 ) than in the product. A combination of DFT and ZINDO/CI calculations was used to estimate excited singlet and triplet spectra of the reactant and the product molecules. Calculated singlet-triplet difference spectra qualitatively match the observed transient spectra 500 fs after excitation supporting the idea that observed excited state relaxation occurs from the triplet states in both complexes

  2. 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

  3. 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.

  4. Isotopic studies on ligand exchange between complex and simple cyanides in water medium and in liquid hydrogen cyanide. Part 2. Radiocyanide ligand exchange study between hydrogen cyanide and octacyanotungstate(4) in water solutions of mineral acids

    International Nuclear Information System (INIS)

    Zielinski, M.

    1979-01-01

    Radiocyanide ligand exchange between potassium octacyanotungstate(4) and hydrogen cyanide in aqueous solutions of sulfuric acid and between octacyanotungstic(4) acid and hydrogen cyanide in aqueous solutions have been investigated experimentally. The observed enhancement of the rate of ligand exchange in acidic medium has been rationalized in terms of the proposed new general reaction scheme taking into account the reversible decomposition of complex cyanide at low pH, and irreversible one at high pH. The discussion on the results obtained has been carried out within the framework of derived formal kinetic equations. (author)

  5. Fringe proteins modulate Notch-ligand cis and trans interactions to specify signaling states.

    Science.gov (United States)

    LeBon, Lauren; Lee, Tom V; Sprinzak, David; Jafar-Nejad, Hamed; Elowitz, Michael B

    2014-09-25

    The Notch signaling pathway consists of multiple types of receptors and ligands, whose interactions can be tuned by Fringe glycosyltransferases. A major challenge is to determine how these components control the specificity and directionality of Notch signaling in developmental contexts. Here, we analyzed same-cell (cis) Notch-ligand interactions for Notch1, Dll1, and Jag1, and their dependence on Fringe protein expression in mammalian cells. We found that Dll1 and Jag1 can cis-inhibit Notch1, and Fringe proteins modulate these interactions in a way that parallels their effects on trans interactions. Fringe similarly modulated Notch-ligand cis interactions during Drosophila development. Based on these and previously identified interactions, we show how the design of the Notch signaling pathway leads to a restricted repertoire of signaling states that promote heterotypic signaling between distinct cell types, providing insight into the design principles of the Notch signaling system, and the specific developmental process of Drosophila dorsal-ventral boundary formation.

  6. 5f state interaction with inner coordination sphere ligands: einsteinium 3+ ion fluorescence in aqueous and organic phases

    International Nuclear Information System (INIS)

    Beitz, J.V.; Wester, D.W.; Williams, C.W.

    1983-01-01

    The interaction between 5f electron states of einsteinium 3+ ion and coordinated ligands in solution has been probed using laser-induced fluorescence. Aquo einsteinium 3+ ion was observed to fluoresce from its first excited J = 5 state in a broad-band peaking at 9260 wavenumbers. The observed fluorescence lifetimes were 1.05 microseconds and 2.78 microseconds in H 2 O and D 2 O (99+ % D atom), respectively. The non-radiative decay rates derived from the lifetime data are compared with previously reported data for Cm, Sm, Eu, Tb, and Dy aquo 3+ ions. The 5f actinide states exhibit substantially greater non-radiative decay rates than do lanthanide 4f states of similar energy gap. This provides evidence that actinide 5f electrons interact more strongly with their inner coordination sphere than do lanthanide ion 4f electrons. The fluorescence lifetime of einsteinium 3+ ion complexed with 1 formal di(2-ethylhexyl)orthophosphoric acid in h-heptane was 2.34 microseconds. 3 figures, 1 table

  7. 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

  8. Solution characterization of the extracellular region of CD147 and its interaction with its enzyme ligand cyclophilin-A

    Energy Technology Data Exchange (ETDEWEB)

    Schlegel, Jennifer; Redzic, Jasmina S.; Porter, Christopher; Yurchenko, Vyacheslav; Bukrinsky, Michael; Labeikovsky, Wladimir; Armstrong, Geoffrey S.; Zhang, Fengli; Isern, Nancy G.; Degregori, James; Hodges, Robert; Eisenmesser, Elan Z.

    2009-08-21

    The CD147 receptor plays an integral role in numerous diseases by stimulating the expression of several protein families and serving as the receptor for extracellular cyclophilins, however, neither CD147 nor its interactions with its cyclophilin ligands have been well characterized in solution. CD147 is a unique protein in that it can function both at the cell membrane and after being released from cells where it continues to retain activity. Thus, the CD147 receptor functions through at least two mechanisms that include both cyclophilin-independent and cyclophilin-dependent modes of action. In regard to CD147 cyclophilin-independent activity, CD147 homophilic interactions are thought to underlie its activity. In regard to CD147 cyclophilin-dependent activity, cyclophilin/CD147 interactions may represent a novel means of signaling since cyclophilins are also peptidyl-prolyl isomerases.

  9. 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

  10. Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2′-bipyridine2(CN2

    Directory of Open Access Journals (Sweden)

    Kasper S. Kjær

    2017-07-01

    Full Text Available We have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy2(CN2], where bpy=2,2′-bipyridine, initiated by metal-to-ligand charge transfer (MLCT excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2′-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy2(CN2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a short lived metal-centered triplet transient species. These measurements of [Fe(bpy2(CN2] complement prior measurement performed on [Fe(bpy3]2+ and [Fe(bpy(CN4]2− in dimethylsulfoxide solution and help complete the chemical series [Fe(bpyN(CN6–2N]2N-4, where N = 1–3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3d transition metal complexes.

  11. 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

  12. Four-state solution of the Yang-Baxter equation

    International Nuclear Information System (INIS)

    Kashaev, R.M.; Mangazeev, V.V.

    1990-01-01

    A new four-state solution of the Yang-Baxter equation is constructed with the help of the lowest dimensional cyclic L-operator related to a 3-state R-matrix. Some special choice of parameters which this solution depends on, leads to the exactly solvable spin model on the chain with Hermitian Hamiltonian. 8 refs

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

    Digital Repository Service at National Institute of Oceanography (India)

    Vudamala, K.; Chakraborty, P.

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

  14. Pharmacophore searching: A potential solution for correcting unknown ligands (UNK) labelling errors in Protein Data Bank (PDB'S).

    Science.gov (United States)

    Ibrahim, Musadiq; Lapthorn, Adrian Jonathan; Ibrahim, Mohammad

    2017-08-01

    The Protein Data Bank (PDB) is the single most important repository of structural data for proteins and other biologically relevant molecules. Therefore, it is critically important to keep the PDB data, error-free as much as possible. In this study, we have critically examined PDB structures of 292 protein molecules which have been deposited in the repository along with potentially incorrect ligands labelled as Unknown ligands (UNK). Pharmacophores were generated for all the protein structures by using Discovery Studio Visualizer (DSV) and Accelrys, Catalyst ® . The generated pharmacophores were subjected to the database search containing the reported ligand. Ligands obtained through Pharmacophore searching were then checked for fitting the observed electron density map by using Coot ® . The predicted ligands obtained via Pharmacophore searching fitted well with the observed electron density map, in comparison to the ligands reported in the PDB's. Based on our study we have learned that till may 2016, among 292 submitted structures in the PDB, at least 20 structures have ligands with a clear electron density but have been incorrectly labelled as unknown ligands (UNK). We have demonstrated that Pharmacophore searching and Coot ® can provide potential help to find suitable known ligands for these protein structures, the former for ligand search and the latter for electron density analysis. The use of these two techniques can facilitate the quick and reliable labelling of ligands where the electron density map serves as a reference. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. 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.

  16. An improvement to the ligand optimisation method (LOM) for measuring the apparent dissociation constant and ligand purity in Ca2+ and Mg2+ buffer solutions.

    Science.gov (United States)

    McGuigan, John A S; Kay, James W; Elder, Hugh Y

    2014-01-01

    In Ca(2+)/Mg(2+) buffers the calculated ionised concentrations ([X(2+)]) can vary by up to a factor of seven. Since there are no defined standards it is impossible to check calculated [X(2+)], making measurement essential. The ligand optimisation method (LOM) is an accurate method to measure [X(2+)] in Ca(2+)/Mg(2+) buffers; independent estimation of ligand purity extends the method to pK(/) buffers, to calculate electrode and buffer characteristics as a function of Σ. Ca(2+)-electrodes have a Σ buffers. These results demonstrated that it is pK(/) that is normally distributed. Until defined standards are available, [X(2+)] in Ca(2+)/Mg(2+) buffers have to be measured. The most appropriate method is to use Ca(2+)/Mg(2) electrodes combined with the Excel programs SALE or AEC. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Steady state solution of the Poisson-Nernst-Planck equations

    International Nuclear Information System (INIS)

    Golovnev, A.; Trimper, S.

    2010-01-01

    The exact steady state solution of the Poisson-Nernst-Planck equations (PNP) is given in terms of Jacobi elliptic functions. A more tractable approximate solution is derived which can be used to compare the results with experimental observations in binary electrolytes. The breakdown of the PNP for high concentration and high applied voltage is discussed.

  18. Hot 56Mn reactions in permanganate solutions: a quasi solution state study [Paper No. NC-6

    International Nuclear Information System (INIS)

    Dedgaonkar, V.G.; Mitra, S.

    1982-01-01

    Neutron activation of aqueous solutions of transition metal and ammonium permanganates over the concentration range 1-10 -3 M has been performed. Retentions for concentrated solutions were much higher than the solid state values, and upon dilution, a limiting value of approx. 4 per cent was attained. Activation of 1-10 -1 M permanganate quasi solutions containing either alumina or a polystyrene cation exchanger allowed continuous extraction of the recoil species before their recombination. (author)

  19. Role of solution conformation and flexibility of short peptide ligands that bind to the p56(lck) SH2 domain

    NARCIS (Netherlands)

    Dekker, Frank J; de Mol, Nico J; Bultinck, Patrick; Kemmink, Johan; Hilbers, Hans W; Liskamp, Rob M J; Dekker, Frank

    2003-01-01

    A general approach in drug design is making ligands more rigid in order to avoid loss in conformational entropy (deltaS(conf)) upon receptor binding. We hypothesized that in the high affinity binding of pYEEI peptide ligands to the p56(lck) SH2 domain this loss in deltaS(conf) might be diminished

  20. 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.

  1. The role of ligands on the equilibria between functional states of a G protein-coupled receptor.

    Science.gov (United States)

    Kim, Tae Hun; Chung, Ka Young; Manglik, Aashish; Hansen, Alexandar L; Dror, Ron O; Mildorf, Thomas J; Shaw, David E; Kobilka, Brian K; Prosser, R Scott

    2013-06-26

    G protein-coupled receptors exhibit a wide variety of signaling behaviors in response to different ligands. When a small label was incorporated on the cytosolic interface of transmembrane helix 6 (Cys-265), (19)F NMR spectra of the β2 adrenergic receptor (β2AR) reconstituted in maltose/neopentyl glycol detergent micelles revealed two distinct inactive states, an activation intermediate state en route to activation, and, in the presence of a G protein mimic, a predominant active state. Analysis of the spectra as a function of temperature revealed that for all ligands, the activation intermediate is entropically favored and enthalpically disfavored. β2AR enthalpy changes toward activation are notably lower than those observed with rhodopsin, a likely consequence of basal activity and the fact that the ionic lock and other interactions stabilizing the inactive state of β2AR are weaker. Positive entropy changes toward activation likely reflect greater mobility (configurational entropy) in the cytoplasmic domain, as confirmed through an order parameter analysis. Ligands greatly influence the overall changes in enthalpy and entropy of the system and the corresponding changes in population and amplitude of motion of given states, suggesting a complex landscape of states and substates.

  2. Dynamic translocation of ligand-complexed DNA through solid-state nanopores with optical tweezers

    International Nuclear Information System (INIS)

    Sischka, Andy; Spiering, Andre; Anselmetti, Dario; Khaksar, Maryam; Laxa, Miriam; Koenig, Janine; Dietz, Karl-Josef

    2010-01-01

    We investigated the threading and controlled translocation of individual lambda-DNA (λ-DNA) molecules through solid-state nanopores with piconewton force sensitivity, millisecond time resolution and picoampere ionic current sensitivity with a set-up combining quantitative 3D optical tweezers (OT) with electrophysiology. With our virtually interference-free OT set-up the binding of RecA and single peroxiredoxin protein molecules to λ-DNA was quantitatively investigated during dynamic translocation experiments where effective forces and respective ionic currents of the threaded DNA molecule through the nanopore were measured during inward and outward sliding. Membrane voltage-dependent experiments of reversible single protein/DNA translocation scans yield hysteresis-free, asymmetric single-molecule fingerprints in the measured force and conductance signals that can be attributed to the interplay of optical trap and electrostatic nanopore potentials. These experiments allow an exact localization of the bound protein along the DNA strand and open fascinating applications for label-free detection of DNA-binding ligands, where structural and positional binding phenomena can be investigated at a single-molecule level.

  3. Exact solutions of continuous states for Hartmann potential

    International Nuclear Information System (INIS)

    Chen Changyuan; Lu Falin; Sun Dongsheng

    2004-01-01

    In this Letter, we obtain the exact solutions of continuous states for the Hartmann potential. The normalized wave functions of continuous states on the 'k/2π scale' and the calculation formula of phase shifts are presented. Analytical properties of the scattering amplitude are discussed

  4. Technical Solution for Improved Safeguards/State Cooperation

    International Nuclear Information System (INIS)

    Miller, S.

    2015-01-01

    This paper will discuss an information technology solution to allow the IAEA Safeguards Department to improve cooperation with States. The solution will be a portal or hub to integrate the information, processes, and people between Safeguards and States. It will allow for two-way communication and collaboration between Safeguards staff and State representatives. This paper discusses the information security challenges inherent in building such a system. It proposes technical architectures that might allow the existing integration approach (e.g., encrypted email exchange) to be kept, while expanding it to include modern integration technologies (e.g., web services), as well explorer new collaborative web technologies. It looks at current Safeguards processes and approaches to cooperation and discusses efficiencies that could be achieved through the adoption of this technology solution. Example process areas for improvement include: a) Safeguards Agreements: States are obligated to submit data on their nuclear programme to the IAEA on a periodic basis. Declarations are received through two separate systems using encrypted email. The proposed solution would allow for enhanced exchange of declaration where States can submit any type of declaration using one system. When declarations are received and validated, an acknowledgement would automatically be sent to the State. The solution would provide the Safeguards Department the ability to ask for clarification as well as collaborate on the submitted declarations. Both the question and the response would be recorded in the system. The solution could also integrate tools allowing declarations to be added directly and validated before submission. b) Other areas that could benefit from this solution include declarations from States with small quantities protocol, facility declarations, as well as systems that support extra-budgetary funding (e.g., SPRICS). (author)

  5. Liquid crystalline states of surfactant solutions of isotropic micelles

    International Nuclear Information System (INIS)

    Bagdassarian, C.; Gelbart, W.M.; Ben-Shaul, A.

    1988-01-01

    We consider micellar solutions whose surfactant molecules prefer strongly to form small, globular aggregates in the absence of intermicellar interactions. At sufficiently high volume fraction of surfactant, the isotropic phase of essentially spherical micelles is shown to be unstable with respect to an orientationally ordered (nematic) state of rodlike aggregates. This behavior is relevant to the phase diagrams reported for important classes of aqueous amphiphilic solutions

  6. A novel signal transduction protein: Combination of solute binding and tandem PAS-like sensor domains in one polypeptide chain: Periplasmic Ligand Binding Protein Dret_0059

    Energy Technology Data Exchange (ETDEWEB)

    Wu, R. [Midwest Center for Structural Genomics, Argonne National Laboratory, Argonne Illinois 60439; Biosciences Division, Argonne National Laboratory, Argonne Illinois 60439; Wilton, R. [Biosciences Division, Argonne National Laboratory, Argonne Illinois 60439; Cuff, M. E. [Midwest Center for Structural Genomics, Argonne National Laboratory, Argonne Illinois 60439; Biosciences Division, Argonne National Laboratory, Argonne Illinois 60439; Structural Biology Center, Argonne National Laboratory, Argonne Illinois 60439; Endres, M. [Midwest Center for Structural Genomics, Argonne National Laboratory, Argonne Illinois 60439; Babnigg, G. [Midwest Center for Structural Genomics, Argonne National Laboratory, Argonne Illinois 60439; Biosciences Division, Argonne National Laboratory, Argonne Illinois 60439; Edirisinghe, J. N. [Mathematics and Computer Science Division, Argonne National Laboratory, Argonne Illinois 60439; Computation Institute, University of Chicago, Chicago Illinois 60637; Henry, C. S. [Mathematics and Computer Science Division, Argonne National Laboratory, Argonne Illinois 60439; Computation Institute, University of Chicago, Chicago Illinois 60637; Joachimiak, A. [Midwest Center for Structural Genomics, Argonne National Laboratory, Argonne Illinois 60439; Biosciences Division, Argonne National Laboratory, Argonne Illinois 60439; Structural Biology Center, Argonne National Laboratory, Argonne Illinois 60439; Department of Biochemistry and Molecular Biology, University of Chicago, Chicago Illinois 60637; Schiffer, M. [Biosciences Division, Argonne National Laboratory, Argonne Illinois 60439; Pokkuluri, P. R. [Biosciences Division, Argonne National Laboratory, Argonne Illinois 60439

    2017-03-06

    We report the structural and biochemical characterization of a novel periplasmic ligand-binding protein, Dret_0059, from Desulfohalobium retbaense DSM 5692, an organism isolated from the Salt Lake Retba in Senegal. The structure of the protein consists of a unique combination of a periplasmic solute binding protein (SBP) domain at the N-terminal and a tandem PAS-like sensor domain at the C-terminal region. SBP domains are found ubiquitously and their best known function is in solute transport across membranes. PAS-like sensor domains are commonly found in signal transduction proteins. These domains are widely observed as parts of many protein architectures and complexes but have not been observed previously within the same polypeptide chain. In the structure of Dret_0059, a ketoleucine moiety is bound to the SBP, whereas a cytosine molecule is bound in the distal PAS-like domain of the tandem PAS-like domain. Differential scanning flourimetry support the binding of ligands observed in the crystal structure. There is significant interaction between the SBP and tandem PAS-like domains, and it is possible that the binding of one ligand could have an effect on the binding of the other. We uncovered three other proteins with this structural architecture in the non-redundant sequence data base, and predict that they too bind the same substrates. The genomic context of this protein did not offer any clues for its function. We did not find any biological process in which the two observed ligands are coupled. The protein Dret_0059 could be involved in either signal transduction or solute transport.

  7. Effects of ligand substitution on the excited state dynamics of the Ru(dcbpy)(CO){sub 2}I{sub 2} complex

    Energy Technology Data Exchange (ETDEWEB)

    Lehtovuori, Viivi; Kallioinen, Jani; Myllyperkioe, Pasi; Haukka, Matti; Korppi-Tommola, Jouko

    2003-11-15

    Spectroscopic evidence suggest [PCCP 3 (2001) 1992] that illumination with visible light of the [trans-I-Ru(dcbpy)(CO){sub 2}I{sub 2}] (dcbpy4,4{sup '}-dicarboxy-2,2{sup '}-bipyridine) complex in solution induces dissociation of a CO group followed by reorganization of the ligands and attachment of a solvent molecule. In the present study, we report results on excited state dynamics of this ruthenium complex and its photoproduct. Femtosecond transient absorption measurements reveal dominance of excited state absorption of the reactant and the photoproduct [cis-I-Ru(dcbpy)(CO)(Sol)I{sub 2}] (Sol=ethanol or acetonitrile) in the visible spectral region. The time-resolved measurements for the reactant at 77 K indicate interligand charge transfer from mixed Ru-I states to empty dcbpy orbitals. For the photoproduct, no such transfer was observed. In both complexes recovery from the lowest energy excited triplet state to the ground state occurs via two channels: radiative relaxation and a parallel barrier controlled non-radiative relaxation. The barrier is much higher in the reactant (about 850 cm{sup -1}) than in the product. A combination of DFT and ZINDO/CI calculations was used to estimate excited singlet and triplet spectra of the reactant and the product molecules. Calculated singlet-triplet difference spectra qualitatively match the observed transient spectra 500 fs after excitation supporting the idea that observed excited state relaxation occurs from the triplet states in both complexes.

  8. Heterogeneous Ferroelectric Solid Solutions Phases and Domain States

    CERN Document Server

    Topolov, Vitaly

    2012-01-01

    The book deals with perovskite-type ferroelectric solid solutions for modern materials science and applications, solving problems of complicated heterophase/domain structures near the morphotropic phase boundary and applications to various systems with morphotropic phases. In this book domain state–interface diagrams are presented for the interpretation of heterophase states in perovskite-type ferroelectric solid solutions. It allows to describe the stress relief in the presence of polydomain phases, the behavior of unit-cell parameters of coexisting phases and the effect of external electric fields. The novelty of the book consists in (i) the first systematization of data about heterophase states and their evolution in ferroelectric solid solutions (ii) the general interpretation of heterophase and domain structures at changing temperature, composition or electric field (iii) the complete analysis of interconnection domain structures, unit-cell parameters changes, heterophase structures and stress relief.

  9. Stabilizing the border steady-state solution of two interacting ...

    African Journals Online (AJOL)

    In this paper, we have successfully developed a feedback control which has been used to stabilize an unstable steady-state solution (0, 3.3534). This convergence has occurred when the values of the final time are 190, 200, 210 and 220 which corresponds to the scenario when the value of the step length of our simulation ...

  10. Solution NMR characterization of magnetic/electronic properties of azide and cyanide-inhibited substrate complexes of human heme oxygenase: implications for steric ligand tilt.

    Science.gov (United States)

    Peng, Dungeng; Ogura, Hiroshi; Ma, Li-Hua; Evans, John P; de Montellano, Paul R Ortiz; La Mar, Gerd N

    2013-04-01

    Solution 2D (1)H NMR was carried out on the azide-ligated substrate complex of human heme oxygenase, hHO, to provide information on the active site molecular structure, chromophore electronic/magnetic properties, and the distal H-bond network linked to the exogenous ligand by catalytically relevant oriented water molecules. While 2D NMR exhibited very similar patterns of two-dimensional nuclear Overhauser spectroscopy cross peaks of residues with substrate and among residues as the previously characterized cyanide complex, significant, broadly distributed chemical shift differences were observed for both labile and non-labile protons. The anisotropy and orientation of the paramagnetic susceptibility tensor, χ, were determined for both the azide and cyanide complexes. The most significant difference observed is the tilt of the major magnetic axes from the heme normal, which is only half as large for the azide than cyanide ligand, with each ligand tilted toward the catalytically cleaved α-meso position. The difference in chemical shifts is quantitatively correlated with differences in dipolar shifts in the respective complexes for all but the distal helix. The necessity of considering dipolar shifts, and hence determination of the orientation/anisotropy of χ, in comparing chemical shifts involving paramagnetic complexes, is emphasized. The analysis shows that the H-bond network cannot detect significant differences in H-bond acceptor properties of cyanide versus azide ligands. Lastly, significant retardation of distal helix labile proton exchange upon replacing cyanide with azide indicates that the dynamic stability of the distal helix is increased upon decreasing the steric interaction of the ligand with the distal helix. Copyright © 2013. Published by Elsevier Inc.

  11. 1,2,4-Triazines in the Synthesis of Bipyridine Bisphenolate ONNO Ligands and Their Highly Luminescent Tetradentate Pt(II) Complexes for Solution-Processable OLEDs.

    Science.gov (United States)

    Pander, Piotr; Bulmer, Rachel; Martinscroft, Ross; Thompson, Stuart; Lewis, Frank W; Penfold, Thomas J; Dias, Fernando B; Kozhevnikov, Valery N

    2018-04-02

    This article describes a convenient method for the synthesis of ONNO-type tetradentate 6,6'-bis(2-phenoxy)-2,2'-bipyridine (bipyridine bisphenolate, BpyBph) ligands and their platinum(II) complexes. The methodology includes the synthesis of 1,2,4-triazine precursors followed by their transformation to functionalized pyridines by the Boger reaction. Two complementary routes employing 3,3'- and 5,5'-bis-triazines allow a modification of the central pyridine rings in different positions, which was exemplified by the introduction of cyclopentene rings. The new ligands were used to prepare highly luminescent ONNO-type Pt(II) complexes. The position of the cyclopentene rings significantly influences the solubility and photophysical properties of these complexes. Derivatives with closely positioned cyclopentene rings are soluble in organic solvents and proved to be the best candidate for solution-processable organic light-emitting devices (OLEDs), showing efficient single-dopant candlelight electroluminescence.

  12. Solid-state thermolysis of a fac-rhenium(I) carbonyl complex with a redox non-innocent pincer ligand.

    Science.gov (United States)

    Jurca, Titel; Chen, Wen-Ching; Michel, Sheila; Korobkov, Ilia; Ong, Tiow-Gan; Richeson, Darrin S

    2013-03-25

    The development of rhenium(I) chemistry has been restricted by the limited structural and electronic variability of the common pseudo-octahedral products fac-[ReX(CO)3L2] (L2 = α-diimine). We address this constraint by first preparing the bidentate bis(imino)pyridine complexes [(2,6-{2,6-Me2C6H3N=CPh}2C5H3N)Re(CO)3X] (X = Cl 2, Br 3), which were characterized by spectroscopic and X-ray crystallographic means, and then converting these species into tridentate pincer ligand compounds, [(2,6-{2,6-Me2C6H3N=CPh}2C5H3N)Re(CO)2X] (X = Cl 4, Br 5). This transformation was performed in the solid-state by controlled heating of 2 or 3 above 200 °C in a tube furnace under a flow of nitrogen gas, giving excellent yields (≥95 %). Compounds 4 and 5 define a new coordination environment for rhenium(I) carbonyl chemistry where the metal center is supported by a planar, tridentate pincer-coordinated bis(imino)pyridine ligand. The basic photophysical features of these compounds show significant elaboration in both number and intensity of the d-π* transitions observed in the UV/Vis spec tra relative to the bidentate starting materials, and these spectra were analyzed using time-dependent DFT computations. The redox nature of the bis(imino)pyridine ligand in compounds 2 and 4 was examined by electrochemical analysis, which showed two ligand reduction events and demonstrated that the ligand reduction shifts to a more positive potential when going from bidentate 2 to tridentate 4 (+160 mV for the first reduction step and +90 mV for the second). These observations indicate an increase in electrostatic stabilization of the reduced ligand in the tridentate conformation. Elaboration on this synthetic methodology documented its generality through the preparation of the pseudo-octahedral rhenium(I) triflate complex [(2,6-{2,6-Me2C6H3N=CPh}2C5H3N)Re(CO)2OTf] (7, 93 % yield). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Complexation study of NpO2+ and UO22+ ions with several organic ligands in aqueous solutions of high ionic strength

    International Nuclear Information System (INIS)

    Borkowski, M.; Lis, S.; Choppin, G.R.

    1995-01-01

    The acid dissociation constants, pK a , and the stability constants for NpO 2 + and UO 2 2+ have been measured for certain organic ligands [acetate, α-hydroxyisobutyrate, lactate, ascorbate, oxalate, citrate, EDTA, 8-hydroxyquinoline, 1, 10-phenanthroline, and thenoyltrifluoroacetone] in 5 m (NaCl) ionic strength solution. The pK a values were determined by potentiometry or spectrometry. These methods, as well as solvent extraction with 233 U and 237 Np radiotracers, were used to measure the stability constants of the 1:1 and 1:2 complexes of dioxo cations. These constants were used to estimate the concentrations required to result in 10 % competition with hydrolysis in the 5 m NaCl solution. Such estimates are of value in assessing the solubility from radioactive waste of AnO 2 + and AnO 2 2+ in brine solutions in contact with nuclear waste in a salt-bed repository

  14. Solution of generalized control system equations at steady state

    International Nuclear Information System (INIS)

    Vilim, R.B.

    1987-01-01

    Although a number of reactor systems codes feature generalized control system models, none of the models offer a steady-state solution finder. Indeed, if a transient is to begin from steady-state conditions, the user must provide estimates for the control system initial conditions and run a null transient until the plant converges to steady state. Several such transients may have to be run before values for control system demand signals are found that produce the desired plant steady state. The intent of this paper is (a) to present the control system equations assumed in the SASSYS reactor systems code and to identify the appropriate set of initial conditions, (b) to describe the generalized block diagram approach used to represent these equations, and (c) to describe a solution method and algorithm for computing these initial conditions from the block diagram. The algorithm has been installed in the SASSYS code for use with the code's generalized control system model. The solution finder greatly enhances the effectiveness of the code and the efficiency of the user in running it

  15. Organic-inorganic hybrid perovskite quantum dots with high PLQY and enhanced carrier mobility through crystallinity control by solvent engineering and solid-state ligand exchange.

    Science.gov (United States)

    Woo Choi, Jin; Woo, Hee Chul; Huang, Xiaoguang; Jung, Wan-Gil; Kim, Bong-Joong; Jeon, Sie-Wook; Yim, Sang-Youp; Lee, Jae-Suk; Lee, Chang-Lyoul

    2018-05-22

    The photoluminescence quantum yield (PLQY) and charge carrier mobility of organic-inorganic perovskite QDs were enhanced by the optimization of crystallinity and surface passivation as well as solid-state ligand exchange. The crystallinity of perovskite QDs was determined by the Effective solvent field (Esol) of various solvents for precipitation. The solvent with high Esol could more quickly countervail the localized field generated by the polar solvent, and it causes fast crystallization of the dissolved precursor, which results in poor crystallinity. The post-ligand adding process (PLAP) and post-ligand exchange process (PLEP) increase the PLQY of perovskite QDs by reducing non-radiative recombination and the density of surface defect states through surface passivation. Particularly, the post ligand exchange process (PLEP) in the solid-state improved the charge carrier mobility of perovskite QDs in addition to the PLQY enhancement. The ligand exchange with short alkyl chain length ligands could improve the packing density of perovskite QDs in films by reducing the inter-particle distance between perovskite QDs. The maximum hole mobility of 6.2 × 10-3 cm2 V-1 s-1, one order higher than that of pristine QDs without the PLEP, is obtained at perovskite QDs with hexyl ligands. By using PLEP treatment, compared to the pristine device, a 2.5 times higher current efficiency in perovskite QD-LEDs was achieved due to the improved charge carrier mobility and PLQY.

  16. Alkali Metal Ion Complexes with Phosphates, Nucleotides, Amino Acids, and Related Ligands of Biological Relevance. Their Properties in Solution.

    Science.gov (United States)

    Crea, Francesco; De Stefano, Concetta; Foti, Claudia; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

    2016-01-01

    Alkali metal ions play very important roles in all biological systems, some of them are essential for life. Their concentration depends on several physiological factors and is very variable. For example, sodium concentrations in human fluids vary from quite low (e.g., 8.2 mmol dm(-3) in mature maternal milk) to high values (0.14 mol dm(-3) in blood plasma). While many data on the concentration of Na(+) and K(+) in various fluids are available, the information on other alkali metal cations is scarce. Since many vital functions depend on the network of interactions occurring in various biofluids, this chapter reviews their complex formation with phosphates, nucleotides, amino acids, and related ligands of biological relevance. Literature data on this topic are quite rare if compared to other cations. Generally, the stability of alkali metal ion complexes of organic and inorganic ligands is rather low (usually log K  Na(+) > K(+) > Rb(+) > Cs(+). For example, for citrate it is: log K ML = 0.88, 0.80, 0.48, 0.38, and 0.13 at 25 °C and infinite dilution. Some considerations are made on the main aspects related to the difficulties in the determination of weak complexes. The importance of the alkali metal ion complexes was also studied in the light of modelling natural fluids and in the use of these cations as probes for different processes. Some empirical relationships are proposed for the dependence of the stability constants of Na(+) complexes on the ligand charge, as well as for correlations among log K values of NaL, KL or LiL species (L = generic ligand).

  17. Solid state structure of thorium(IV) complexes with common aminopoly-carboxylate ligands

    International Nuclear Information System (INIS)

    Thuery, Pierre

    2011-01-01

    The crystal structures of the complexes formed by reaction of thorium(IV) nitrate with iminodiacetic acid (H 2 IDA), nitrilotriacetic acid (H 3 NTA), and ethylenediaminetetraacetic acid (H 4 EDTA) under hydrothermal conditions are reported. In [Th(HIDA) 2 (C 2 O 4 )].H 2 O (1), the metal atom is chelated by two carboxylate groups from two HIDA - anions and by two oxalate ligands formed in situ; two additional oxygen atoms from two more HIDA - anions complete the ten-coordinate environment of bi-capped square anti-prismatic geometry. The uncoordinated nitrogen atom is protonated and involved in hydrogen bonding. Two different ligands are present in [Th(NTA)(H 2 NTA)(H 2 O)].H 2 O (2), one of them being a O 3 ,N-chelating tri-anion which acts also as a bridge toward two neighboring metal ions, and the other being a bis-monodentate bridging species with an uncoordinated carboxylic arm and a central ammonium group. An aqua ligand completes the nine-coordinated, capped square anti-prismatic metal environment. The EDTA 4- anion in [Th(EDTA)(H 2 O)].2H 2 O (3) is chelating through one oxygen atom from each carboxylate group and the two nitrogen atoms, as in a previously reported molecular complex. Two carboxylate groups are bridging, which, with the addition of an aqua ligand, gives a capped square anti-prismatic coordination polyhedron. Aminopoly-carboxylate ligands have been much investigated in relation with actinide decorporation and nuclear wastes management studies, and the present results add to the structural information available on their complexes with thorium(IV), which has mainly been obtained up to now by extended X-ray absorption fine structure (EXAFS) spectroscopy. In particular, the bridging (non-chelating) coordination mode of H 2 NTA - is a novel feature in this context. All three complexes crystallize as two-dimensional assemblies and are thus novel examples of thorium-organic coordination polymers. (author)

  18. On the state of phosphomolybdenovanadic heteropolyblue in aqueous solutions

    International Nuclear Information System (INIS)

    Kuznetsova, L.I.; Yurchenko, Eh.N.; Maksimovskaya, R.I.; Kirik, N.P.; Matveev, K.I.

    1977-01-01

    The effect has been investigated of pH solution on the state of the phosphomolybdenovanadic heteropolyblues of the 12. series, containing n=1,2,3,6 atoms of vanadium (6). It has been shown that the free VO 2+ intrusion into the sphere of heteropolyanions takes place alongside with pH increasing from 1 to 3. At the some time the rate of oxidation of the heteropolyblue solutions by oxygen and the optical density of solutions increase too. The dissociation constants of the heteropolyblue molecule in acid medium increase with increasing of the quantity of vanadium atoms. It has been shown that stability of heteropolyblue in relation to molybdenum decreases with increasing of its quantity in the heteropolyblue molecule. Using precipitation of the heteropolyanions by the cation of tetraethyl ammonium, it has been shown that heteropolyanions can consist of 1,2,3 and 6 atoms of V(6). The state of heteropolyblues in an aqueous solution is characterized by electron absorption spectra

  19. 50-Fold EQE Improvement up to 6.27% of Solution-Processed All-Inorganic Perovskite CsPbBr3 QLEDs via Surface Ligand Density Control.

    Science.gov (United States)

    Li, Jianhai; Xu, Leimeng; Wang, Tao; Song, Jizhong; Chen, Jiawei; Xue, Jie; Dong, Yuhui; Cai, Bo; Shan, Qingsong; Han, Boning; Zeng, Haibo

    2017-02-01

    Solution-processed CsPbBr 3 quantum-dot light-emitting diodes with a 50-fold external quantum efficiency improvement (up to 6.27%) are achieved through balancing surface passivation and carrier injection via ligand density control (treating with hexane/ethyl acetate mixed solvent), which induces the coexistence of high levels of ink stability, photoluminescence quantum yields, thin-film uniformity, and carrier-injection efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Ground state solutions for non-local fractional Schrodinger equations

    Directory of Open Access Journals (Sweden)

    Yang Pu

    2015-08-01

    Full Text Available In this article, we study a time-independent fractional Schrodinger equation with non-local (regional diffusion $$ (-\\Delta^{\\alpha}_{\\rho}u + V(xu = f(x,u \\quad \\text{in }\\mathbb{R}^{N}, $$ where $\\alpha \\in (0,1$, $N > 2\\alpha$. We establish the existence of a non-negative ground state solution by variational methods.

  1. State of bivalent cobalt in solution at microconcentration

    International Nuclear Information System (INIS)

    Vdovina, E.D.; Davydov, Yu.P.; Radyuk, R.I.

    1983-01-01

    The first stage of investigations of the state of microamounts of radioactive Co(2) in the 1.0-11.0 pH range by adsorption methods on glass and silica gel, centrifuging, Co (2) migration in the electric field, is performed. 57 Co is used in experiments. It is shown that in the investigated pH range the possibility of formation of pseudocallories is small, Co (2) is in solution in the form of dissolved forms with the positive charge

  2. Ground state solutions for diffusion system with superlinear nonlinearity

    Directory of Open Access Journals (Sweden)

    Zhiming Luo

    2015-03-01

    where $z=(u,v\\colon\\mathbb{R}\\times\\mathbb{R}^{N}\\rightarrow\\mathbb{R}^{2}$, $b\\in C^{1}(\\mathbb{R}\\times\\mathbb{R}^{N}, \\mathbb{R}^{N}$ and $V(x\\in C(\\mathbb{R}^{N},\\mathbb{R}$. Under suitable assumptions on the nonlinearity, we establish the existence of ground state solutions by the generalized Nehari manifold method developed recently by Szulkin and Weth.

  3. Parabolic partial differential equations with discrete state-dependent delay: Classical solutions and solution manifold

    Czech Academy of Sciences Publication Activity Database

    Krisztin, T.; Rezunenko, Oleksandr

    2016-01-01

    Roč. 260, č. 5 (2016), s. 4454-4472 ISSN 0022-0396 R&D Projects: GA ČR GAP103/12/2431 Institutional support: RVO:67985556 Keywords : Parabolic partial differential equations * State dependent delay * Solution manifold Subject RIV: BC - Control Systems Theory Impact factor: 1.988, year: 2016 http://library.utia.cas.cz/separaty/2016/AS/rezunenko-0457879.pdf

  4. Formation of Mixed-Ligand Complexes of Metals(II) with Monoamine Complexones and Amino Acids in Solution

    Science.gov (United States)

    Pyreu, D. F.; Gridchin, S. N.

    2018-05-01

    The formation of mixed-ligand complexes in the M(II)-Nta, Ida-L (M = Cu(II), Ni, Zn, Co(II), L = Ser, Thr, Asp, Arg, Asn) systems, where Ida and Nta are the residues of iminodiacetic and nitrilotriacetic acids, respectively, is studied using pH measurements, calorimetry and spectrophotometry. The thermodynamic parameters (log K, Δr G 0, Δr H, Δr S) of their formation at 298.15 K and ionic strength I = 0.5 (KNO3) are determined. The most likely scenario of amino acid residue coordination in the composition of mixed complexes is discussed.

  5. Do All X-ray Structures of Protein-Ligand Complexes Represent Functional States? EPOR, a Case Study.

    Science.gov (United States)

    Corbett, Michael S P; Mark, Alan E; Poger, David

    2017-02-28

    Based on differences between the x-ray crystal structures of ligand-bound and unbound forms, the activation of the erythropoietin receptor (EPOR) was initially proposed to involve a cross-action scissorlike motion. However, the validity of the motions involved in the scissorlike model has been recently challenged. Here, atomistic molecular dynamics simulations are used to examine the structure of the extracellular domain of the EPOR dimer in the presence and absence of erythropoietin and a series of agonistic or antagonistic mimetic peptides free in solution. The simulations suggest that in the absence of crystal packing effects, the EPOR chains in the different dimers adopt very similar conformations with no clear distinction between the agonist and antagonist-bound complexes. This questions whether the available x-ray crystal structures of EPOR truly represent active or inactive conformations. The study demonstrates the difficulty in using such structures to infer a mechanism of action, especially in the case of membrane receptors where just part of the structure has been considered in addition to potential confounding effects that arise from the comparison of structures in a crystal as opposed to a membrane environment. The work highlights the danger of assigning functional significance to small differences between structures of proteins bound to different ligands in a crystal environment without consideration of the effects of the crystal lattice and thermal motion. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  6. Studies of the Tc oxidation states in humic acid solutions

    International Nuclear Information System (INIS)

    Wang Bo; Liu Dejun; Yao Jun

    2010-01-01

    The oxidation state is an important aspect of the speciation of Tc in groundwater that contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg L -1 and the Tc (Ⅶ) concentration range is about 10 -8 mol l -1 . The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation methods were carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (IPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (Ⅳ) and Tc (Ⅶ) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentrations are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (Ⅶ) is very stable in the Tc (Ⅶ)-humic acid system during a 350 days experimental period, and the Tc (Ⅳ) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (Ⅶ) in aqueous solutions under anaerobic conditions. That is means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

  7. Studies of Tc oxidation states in humic acid solutions

    International Nuclear Information System (INIS)

    Wang Bo; Liu Dejun; Yao Jun

    2011-01-01

    The oxidation state of Tc is an important aspect of the speciation in groundwater which contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg/L and the Tc (VII) concentration is about 10 -8 mol/L. The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation method was carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (TPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (IV) and Tc (VII) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentration are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (VII) is very stable in the Tc (VII)-humic acid system during a 350 days experimental period, and the Tc (IV) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (VII) in aqueous solutions under anaerobic conditions. That means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

  8. Room temperature synthesis of PbSe quantum dots in aqueous solution: Stabilization by interactions with ligands

    Science.gov (United States)

    Primera-Pedrozo, Oliva M.; Arslan, Zikri; Rasulev, Bakhtiyor; Leszczynski, Jerzy

    2011-01-01

    An aqueous route of synthesis is described for rapid synthesis of lead selenide quantum dots (PbSe QDs) at room temperature in an attempt to produce water-soluble and stable nanocrystals. Several thiol-ligands, including thioglycolic acid (TGA), thioglycerol (TGC), 3-mercaptopropionic acid (MPA), 2-mercaptoethyleamine hydrochloride (MEA), 6-mercaptohexanoic acid (MHA), and L-cysteine (L-cys), were used for capping/stabilization of PbSe QDs. The effects of the ligands on the stability of PbSe QDs were evaluated for a period of two months at room temperature under normal light conditions and at 4 °C in dark. The TGA- and MEA-capped QDs exhibited the highest stability prior to purification, almost two months when kept in dark at 4 °C. However, the stability of TGA-capped QDs was reduced substantially after purification to about 5 days under same conditions, while MEA-capped QDs did not show any significant instability. The stabilization energies of Pb-thiolate complexes determined by theoretical DFT simulations supported the experimental results. The PbSe QDs capped with TGA, MPA and MEA were successfully purified and re-dispersed in water, while those stabilized with TGC, MHA and L-cys aggregated during purification attempts. The purified PbSe QDs possess very susceptible surface resulting in poor stability for about 30 – 45 min after re-dispersion in water. In the presence of an excess of free ligand, the stability increased up to 5 days for TGA-capped QDs at pH 7.19, 9 –12 days for MPA-capped QDs at pH 7.3–7.5 and 45–47 days for MEA-capped QDs at pH 7.35. X-Ray Diffraction (XRD) results showed that the QDs possess a cubic rock salt structure with the most intense peaks located at 2θ = 25.3° (200) and 2θ = 29.2° (100). TEM images showed that the size of the QDs ranges between 5 and 10 nm. ICP-MS results revealed that Pb:Se ratio was 1.26, 1.28, 3.85, 1.18, and 1.31 for the QDs capped with TGA, MPA, MEA, L-Cys, and TGC, respectively. The proposed method

  9. Dissipative dark matter halos: The steady state solution

    Science.gov (United States)

    Foot, R.

    2018-02-01

    Dissipative dark matter, where dark matter particle properties closely resemble familiar baryonic matter, is considered. Mirror dark matter, which arises from an isomorphic hidden sector, is a specific and theoretically constrained scenario. Other possibilities include models with more generic hidden sectors that contain massless dark photons [unbroken U (1 ) gauge interactions]. Such dark matter not only features dissipative cooling processes but also is assumed to have nontrivial heating sourced by ordinary supernovae (facilitated by the kinetic mixing interaction). The dynamics of dissipative dark matter halos around rotationally supported galaxies, influenced by heating as well as cooling processes, can be modeled by fluid equations. For a sufficiently isolated galaxy with a stable star formation rate, the dissipative dark matter halos are expected to evolve to a steady state configuration which is in hydrostatic equilibrium and where heating and cooling rates locally balance. Here, we take into account the major cooling and heating processes, and numerically solve for the steady state solution under the assumptions of spherical symmetry, negligible dark magnetic fields, and that supernova sourced energy is transported to the halo via dark radiation. For the parameters considered, and assumptions made, we were unable to find a physically realistic solution for the constrained case of mirror dark matter halos. Halo cooling generally exceeds heating at realistic halo mass densities. This problem can be rectified in more generic dissipative dark matter models, and we discuss a specific example in some detail.

  10. Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2′-bipyridine)2(CN)2

    DEFF Research Database (Denmark)

    Kjær, Kasper Skov; Zhang, Wenkai; Alonso-Mori, Roberto

    2017-01-01

    We have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy)2(CN)2], where bpy=2,2′-bipyridine, initiated by metal-to-ligand charge transfer (MLCT) excitation. The excited-state absorption in the transient UV-visible...

  11. Limitations and Extensions of the Lock-and-Key Principle: Differences between Gas State, Solution and Solid State Structures

    Directory of Open Access Journals (Sweden)

    Hans-Jörg Schneider

    2015-03-01

    Full Text Available The lock-and-key concept is discussed with respect to necessary extensions. Formation of supramolecular complexes depends not only, and often not even primarily on an optimal geometric fit between host and guest. Induced fit and allosteric interactions have long been known as important modifications. Different binding mechanisms, the medium used and pH effects can exert a major influence on the affinity. Stereoelectronic effects due to lone pair orientation can lead to variation of binding constants by orders of magnitude. Hydrophobic interactions due to high-energy water inside cavities modify the mechanical lock-and-key picture. That optimal affinities are observed if the cavity is only partially filled by the ligand can be in conflict with the lock-and-key principle. In crystals other forces than those between host and guest often dominate, leading to differences between solid state and solution structures. This is exemplified in particular with calixarene complexes, which by X-ray analysis more often than other hosts show guest molecules outside their cavity. In view of this the particular problems with the identification of weak interactions in crystals is discussed.

  12. Effect of pH and uranium concentration on interaction of uranium(VI) and uranium(IV) with organic ligands in aqueous solutions

    International Nuclear Information System (INIS)

    Li, W.C.; Victor, D.M.; Chakrabarti, C.L.

    1980-01-01

    The effect of pH and uranium concentration on the interactions of uranium(VI) and uranium(IV) with organic ligands was studied by employing dialysis and ultrafiltration techniques. The interactions of U(VI) and U(IV) with organic ligands in nitrate or chloride aqueous solution have been found to be pH-dependent. The stability constants of uranium-organic complexes decrease in the order: fulvic acid>humic acid>tannic acid for U(VI) and humic acid>tannic acid>fulvic acid for U(IV). Scatchard plots for the uranium-organic acid systems indicate two types of binding sites with a difference in stability constants of about 10 2 . Ultrafiltration of uranium-humic acid complexes indicates that U(VI) and U(IV) ions are concentrated in larger molecular size fractions (>5.1 nm) at pH less than or equal to 3 and in smaller molecular size fractions (in the range 5.1 to 3.1 nm and 2.4 to 1.9 nm) at pH greater than or equal to 5. 7 figures, 4 tables

  13. Dissipative dark matter halos: The steady state solution. II.

    Science.gov (United States)

    Foot, R.

    2018-05-01

    Within the mirror dark matter model and dissipative dark matter models in general, halos around galaxies with active star formation (including spirals and gas-rich dwarfs) are dynamical: they expand and contract in response to heating and cooling processes. Ordinary type II supernovae (SNe) can provide the dominant heat source, which is possible if kinetic mixing interaction exists with strength ɛ ˜10-9- 10-10 . Dissipative dark matter halos can be modeled as a fluid governed by Euler's equations. Around sufficiently isolated and unperturbed galaxies the halo can relax to a steady state configuration, where heating and cooling rates locally balance and hydrostatic equilibrium prevails. These steady state conditions can be solved to derive the physical properties, including the halo density and temperature profiles, for model galaxies. Here, we consider idealized spherically symmetric galaxies within the mirror dark particle model, as in our earlier paper [Phys. Rev. D 97, 043012 (2018), 10.1103/PhysRevD.97.043012], but we assume that the local halo heating in the SN vicinity dominates over radiative sources. With this assumption, physically interesting steady state solutions arise which we compute for a representative range of model galaxies. The end result is a rather simple description of the dark matter halo around idealized spherically symmetric systems, characterized in principle by only one parameter, with physical properties that closely resemble the empirical properties of disk galaxies.

  14. Electronic states of graphene nanoribbons and analytical solutions

    Directory of Open Access Journals (Sweden)

    Katsunori Wakabayashi, Ken-ichi Sasaki, Takeshi Nakanishi and Toshiaki Enoki

    2010-01-01

    Full Text Available Graphene is a one-atom-thick layer of graphite, where low-energy electronic states are described by the massless Dirac fermion. The orientation of the graphene edge determines the energy spectrum of π-electrons. For example, zigzag edges possess localized edge states with energies close to the Fermi level. In this review, we investigate nanoscale effects on the physical properties of graphene nanoribbons and clarify the role of edge boundaries. We also provide analytical solutions for electronic dispersion and the corresponding wavefunction in graphene nanoribbons with their detailed derivation using wave mechanics based on the tight-binding model. The energy band structures of armchair nanoribbons can be obtained by making the transverse wavenumber discrete, in accordance with the edge boundary condition, as in the case of carbon nanotubes. However, zigzag nanoribbons are not analogous to carbon nanotubes, because in zigzag nanoribbons the transverse wavenumber depends not only on the ribbon width but also on the longitudinal wavenumber. The quantization rule of electronic conductance as well as the magnetic instability of edge states due to the electron–electron interaction are briefly discussed.

  15. Highly Efficient Interception and Precipitation of Uranium(VI) from Aqueous Solution by Iron-Electrocoagulation Combined with Cooperative Chelation by Organic Ligands.

    Science.gov (United States)

    Li, Peng; Zhun, Bao; Wang, Xuegang; Liao, PingPing; Wang, Guanghui; Wang, Lizhang; Guo, Yadan; Zhang, Weimin

    2017-12-19

    A new strategy combining iron-electrocoagulation and organic ligands (OGLs) cooperative chelation was proposed to screen and precipitate low concentrations (0-18.52 μmol/L) of uranium contaminant in aqueous solution. We hypothesized that OGLs with amino, hydroxyl, and carboxyl groups hydrophobically/hydrophilically would realize precuring of uranyl ion at pH electrocoagulation would achieve faster and more efficient uranium precipitation. Experimentally, the strategy demonstrated highly efficient uranium(VI) precipitation efficiency, especially with hydrophilic macromolecular OGLs. The uranium removal efficiency at optimized experimental condition reached 99.65%. The decrease of zeta potential and the lattice enwrapping between U-OGLs chelates and flocculation precursor were ascribed to the enhanced uranium precipitation activity. Uranium was precipitated as oxides of U(VI) or higher valences that were easily captured in aggregated micelles under low operation current potential. The actual uranium tailing wastewater was treated, and a satisfied uranium removal efficiency of 99.02% was discovered. After elution of the precipitated flocs, a concentrated uranium solution (up to 106.52 μmol/L) with very few other metallic impurities was obtained. Therefore, the proposed strategy could remove uranium and concentrate it concurrently. This work could provide new insights into the purification and recovery of uranium from aqueous solutions in a cost-effective and environmentally friendly process.

  16. Positive energy Weinberg states for the solution of scattering problems

    International Nuclear Information System (INIS)

    Rawitscher, G.

    1982-01-01

    Positive energy Weinberg states are defined and numerically calculated in the presence of a general complex Woods-Saxon potential. The numerical procedure is checked for the limit of a square well potential for which the Weinberg states and the corresponding eigenvalues are known. A finite number M of these (auxiliary) positive energy Weinberg states are then use as a set of basis functions in order to provide a separable approximation of rank M, V/sub M/, to a potential V, and also to the scattering matrix element S which obtains as a result of the presence of V, S/sub M/. Both V/sub M/ and S/sub M/ are obtained by means of algebraic manipulations which involve the matrix elements of V calculated in terms of the auxiliary postive energy Weinberg states Next, expressions are derived which enable one to iteratively correct for the error in V--V/sub M/. These expressions are a modified version of the quasi-particle method of Weinberg. The convergence of S/sub M/ to S, as well as the first order interation of the error in S/sub M/ is examined as a function M for a numerical example which uses a complex Woods-Saxon potential for V and assumes zero angular momentum. With M = 5 and one iteration an error of less than 10% in S is achieved; for M = 8 the error is less than 1%. The method is expected to be useful for the solution of large systems of coupled equations by matrix techniques or when a part of the potential is non-local

  17. X-ray structures of progesterone receptor ligand binding domain in its agonist state reveal differing mechanisms for mixed profiles of 11beta-substituted steroids.

    NARCIS (Netherlands)

    Lusher, S.J.; Raaijmakers, H.C.A.; Vu-Pham, D.; Kazemier, B.; Bosch, R.; McGuire, R.; Azevedo, R.; Hamersma, H.; Dechering, K.; Oubrie, A.; Duin, M. van; Vlieg, J. de

    2012-01-01

    We present here the x-ray structures of the progesterone receptor (PR) in complex with two mixed profile PR modulators whose functional activity results from two differing molecular mechanisms. The structure of Asoprisnil bound to the agonist state of PR demonstrates the contribution of the ligand

  18. Modelling of Octahedral Manganese II Complexes with Inorganic Ligands: A Problem with Spin-States

    Directory of Open Access Journals (Sweden)

    Ludwik Adamowicz

    2003-08-01

    Full Text Available Abstract: Quantum mechanical ab initio UHF, MP2, MC-SCF and DFT calculations with moderate Gaussian basis sets were performed for MnX6, X = H2O, F-, CN-, manganese octahedral complexes. The correct spin-state of the complexes was obtained only when the counter ions neutralizing the entire complexes were used in the modelling at the B3LYP level of theory.

  19. Flt3 ligand-receptor interaction is important for maintenance of early thymic progenitor numbers in steady-state thymopoiesis.

    Science.gov (United States)

    Kenins, Linda; Gill, Jason W; Holländer, Georg A; Wodnar-Filipowicz, Aleksandra

    2010-01-01

    T-cell production throughout life depends on efficient colonization and intrathymic expansion of BM-derived hematopoietic precursors. After irradiation-induced thymic damage, thymic recovery is facilitated by Flt3 ligand (FL), expressed by perivascular fibroblasts surrounding the thymic entry site of Flt3 receptor-positive progenitor cells. Whether intrathymic FL-Flt3 interactions play a role in steady-state replenishment of T cells remains unknown. Here, using competitive BM transplantation studies and fetal thymic organ cultures we demonstrated the continued numerical advantage of Flt3+ intrathymic T-cell precursors. Sub-kidney capsule thymic transplantation experiments, in which WT and FL-/- thymic lobes were grafted into FL-/- recipients, revealed that FL expression by the thymic microenvironment plays a role in steady-state thymopoiesis. The deficiency of the most immature thymic T-cell precursors correlated to upregulation of FL by thymic MTS15+ fibroblasts, suggesting that the number of Flt3+ progenitor cells may regulate the thymic expression of this cytokine. Together, these results show that FL expression by thymic stromal fibroblasts interacting with Flt3+ T-cell progenitors is important for the physiological maintenance of early T-cell development.

  20. Ligand modeling and design

    Energy Technology Data Exchange (ETDEWEB)

    Hay, B.P. [Pacific Northwest National Lab., Richland, WA (United States)

    1997-10-01

    The purpose of this work is to develop and implement a molecular design basis for selecting organic ligands that would be used in the cost-effective removal of specific radionuclides from nuclear waste streams. Organic ligands with metal ion specificity are critical components in the development of solvent extraction and ion exchange processes that are highly selective for targeted radionuclides. The traditional approach to the development of such ligands involves lengthy programs of organic synthesis and testing, which in the absence of reliable methods for screening compounds before synthesis, results in wasted research effort. The author`s approach breaks down and simplifies this costly process with the aid of computer-based molecular modeling techniques. Commercial software for organic molecular modeling is being configured to examine the interactions between organic ligands and metal ions, yielding an inexpensive, commercially or readily available computational tool that can be used to predict the structures and energies of ligand-metal complexes. Users will be able to correlate the large body of existing experimental data on structure, solution binding affinity, and metal ion selectivity to develop structural design criteria. These criteria will provide a basis for selecting ligands that can be implemented in separations technologies through collaboration with other DOE national laboratories and private industry. The initial focus will be to select ether-based ligands that can be applied to the recovery and concentration of the alkali and alkaline earth metal ions including cesium, strontium, and radium.

  1. Pulse radiolysis of porphyrin and ferriporphyrin solutions in 2-propanol-carbon tetrachloride systems. Protonation and ligand exchange kinetics

    International Nuclear Information System (INIS)

    Brault, D.; Neta, P.

    1983-01-01

    Pulse radiolysis of aqueous and nonaqueous 2-propanol-acetone-carbon tetrachloride mixtures has been investigated by means of conductivity measurements and spectrophotometry. In these solvent mixtures, a pulse of hydrochloric acid originating from either primary events of solvent radiolysis or from further reactions of carbon tetrachloride with radicals derived from 2-propanol and acetone, is produced within ca 100 nanoseconds. Further production of hydrochloric acid occurs as a result of chain reactions involving hydrogen abstraction by CCl 3 or CCl 3 O 2 radicals. These latter radicals appear to be much more reactive and are likely to be involved in the reaction unless the solutions have been thoroughly deoxygenated. Protonation Reactions of porphyrins and ferriporphyrins, which do not react rapidly with the above radicals, were followed by means of spectrophotometric measurements. In turn, these reactions may be used to monitor hydrochloric acid formation. Spectrophotometric measurements on porphyrins corroborate conductivity results, although a quantitative comparison is not feasible because of differences in solvent properties. 6 figures

  2. Structure-dependent photophysical properties of singlet and triplet metal-to-ligand charge transfer states in copper(I) bis(diimine) compounds.

    Science.gov (United States)

    Siddique, Zainul Abedin; Yamamoto, Yuichi; Ohno, Takeshi; Nozaki, Koichi

    2003-10-06

    The photophysical properties of singlet and triplet metal-to-ligand charge transfer (MLCT) states of [Cu(I)(diimine)(2)](+), where diimine is 2,9-dimethyl-1,10-phenanthroline (dmphen), 2,9-dibutyl-1,10-phenanthroline (dbphen), or 6,6'-dimethyl-2,2'-bipyridine (dmbpy), were studied. On 400 nm laser excitation of [Cu(dmphen)(2)](+) in CH(2)Cl(2) solution, prompt (1)MLCT fluorescence with a quantum yield of (2.8 +/- 0.8) x 10(-5) was observed using a picosecond time-correlated single photon counting technique. The quantum yield was dependent on the excitation wavelength, suggesting that relaxation of the Franck-Condon state to the lowest (1)MLCT competes with rapid intersystem crossing (ISC). The fluorescence lifetime of the copper(I) compound was 13-16 ps, unexpectedly long despite a large spin-orbit coupling constant of 3d electrons in copper (829 cm(-1) ). Quantum chemical calculations using a density functional theory revealed that the structure of the lowest (1)MLCT in [Cu(dmphen)(2)](+) (1(1)B(1)) was flattened due to the Jahn-Teller effect in 3d(9) electronic configuration, and the dihedral angle between the two phenanthroline planes (dha) was about 75 degrees with the dha around 90 degrees in the ground state. Intramolecular reorganization energy for the radiative transition of 1(1)B(1) was calculated as 2.1 x 10(3) cm(-1), which is responsible for the large Stokes shift of the fluorescence observed (5.4 x 10(3) cm(-1)). To understand the sluggishness of the intersystem crossing (ISC) of (1)MLCT of the copper(I) compounds, the strength of the spin-orbit interaction between the lowest (1)MLCT (1(1)B(1)) and all (3)MLCT states was calculated. The ISC channels induced by strong spin-orbit interactions (ca. 300 cm(-1)) between the metal-centered HOMO and HOMO - 1 were shown to be energetically unfavorable in the copper(I) compounds because the flattening distortion caused large splitting (6.9 x 10(3) cm(-1)) between these orbitals. The possible ISC is therefore

  3. pH-Dependent spin state population and 19F NMR chemical shift via remote ligand protonation in an iron(ii) complex.

    Science.gov (United States)

    Gaudette, Alexandra I; Thorarinsdottir, Agnes E; Harris, T David

    2017-11-30

    An Fe II complex that features a pH-dependent spin state population, by virtue of a variable ligand protonation state, is described. This behavior leads to a highly pH-dependent 19 F NMR chemical shift with a sensitivity of 13.9(5) ppm per pH unit at 37 °C, thereby demonstrating the potential utility of the complex as a 19 F chemical shift-based pH sensor.

  4. Crystal structure and dynamics of a lipid-induced potential desensitized-state of a pentameric ligand-gated channel

    Energy Technology Data Exchange (ETDEWEB)

    Basak, Sandip [Department of Physiology and Biophysics, School of Medicine, Case Western Reserve University, Cleveland, United States; Schmandt, Nicolaus [Department of Neuroscience, School of Medicine, Case Western Reserve University, Cleveland, United States; Gicheru, Yvonne [Department of Physiology and Biophysics, School of Medicine, Case Western Reserve University, Cleveland, United States; Chakrapani, Sudha [Department of Physiology and Biophysics, School of Medicine, Case Western Reserve University, Cleveland, United States

    2017-03-06

    Desensitization in pentameric ligand-gated ion channels plays an important role in regulating neuronal excitability. Here, we show that docosahexaenoic acid (DHA), a key ω-3 polyunsaturated fatty acid in synaptic membranes, enhances the agonist-induced transition to the desensitized state in the prokaryotic channel GLIC. We determined a 3.25 Å crystal structure of the GLIC-DHA complex in a potentially desensitized conformation. The DHA molecule is bound at the channel-periphery near the M4 helix and exerts a long-range allosteric effect on the pore across domain-interfaces. In this previously unobserved conformation, the extracellular-half of the pore-lining M2 is splayed open, reminiscent of the open conformation, while the intracellular-half is constricted, leading to a loss of both water and permeant ions. These findings, in combination with spin-labeling/EPR spectroscopic measurements in reconstituted-membranes, provide novel mechanistic details of desensitization in pentameric channels.

  5. Effect of solution saturation state and temperature on diopside dissolution

    Directory of Open Access Journals (Sweden)

    Carroll Susan A

    2007-03-01

    Full Text Available Abstract Steady-state dissolution rates of diopside are measured as a function of solution saturation state using a titanium flow-through reactor at pH 7.5 and temperature ranging from 125 to 175°C. Diopside dissolved stoichiometrically under all experimental conditions and rates were not dependent on sample history. At each temperature, rates continuously decreased by two orders of magnitude as equilibrium was approached and did not exhibit a dissolution plateau of constant rates at high degrees of undersaturation. The variation of diopside dissolution rates with solution saturation can be described equally well with a ion exchange model based on transition state theory or pit nucleation model based on crystal growth/dissolution theory from 125 to 175°C. At 175°C, both models over predict dissolution rates by two orders of magnitude indicating that a secondary phase precipitated in the experiments. The ion exchange model assumes the formation of a Si-rich, Mg-deficient precursor complex. Lack of dependence of rates on steady-state aqueous calcium concentration supports the formation of such a complex, which is formed by exchange of protons for magnesium ions at the surface. Fit to the experimental data yields Rate (moldiopsidecm−2s−1=k×10−Ea/2.303RT(aH+2aMg2+n MathType@MTEF@5@5@+=feaafiart1ev1aaatCvAUfKttLearuWrP9MDH5MBPbIqV92AaeXatLxBI9gBaebbnrfifHhDYfgasaacH8akY=wiFfYdH8Gipec8Eeeu0xXdbba9frFj0=OqFfea0dXdd9vqai=hGuQ8kuc9pgc9s8qqaq=dirpe0xb9q8qiLsFr0=vr0=vr0dc8meaabaqaciaacaGaaeqabaqabeGadaaakeaaieaacqWFsbGucqWFHbqycqWF0baDcqWFLbqzcqqGGaaicqGGOaakcqWFTbqBcqWFVbWBcqWFSbaBcqWFGaaicqWFKbazcqWFPbqAcqWFVbWBcqWFWbaCcqWFZbWCcqWFPbqAcqWFKbazcqWFLbqzcqWFGaaicqWFJbWycqWFTbqBdaahaaWcbeqaaiabgkHiTiabikdaYaaakiab=bcaGiab=nhaZnaaCaaaleqabaGaeyOeI0IaeGymaedaaOGaeiykaKIaeyypa0Jaem4AaSMaey41aqRaeeymaeJaeeimaaZaaWbaaSqabeaacqGHsislcqWGfbqrdaWgaaadbaGaemyyaegabeaaliabc+caViabikdaYiabc6caUiabioda

  6. On the accuracy of DFT methods in reproducing ligand substitution energies for transition metal complexes in solution: The role of dispersive interactions

    KAUST Repository

    Jacobsen, Heiko

    2011-12-23

    The performance of a series of density functionals when tested on the prediction of the phosphane substitution energy of transition metal complexes is evaluated. The complexes Fe-BDA and Ru-COD (BDA=benzylideneacetone, COD=cyclooctadiene) serve as reference systems, and calculated values are compared with the experimental values in THF as obtained from calorimetry. Results clearly indicate that functionals specifically developed to include dispersion interactions usually outperform other functionals when BDA or COD substitution is considered. However, when phosphanes of different sizes are compared, functionals including dispersion interactions, at odd with experimental evidence, predict that larger phosphanes bind more strongly than smaller phosphanes, while functionals not including dispersion interaction reproduce the experimental trends with reasonable accuracy. In case of the DFT-D functionals, inclusion of a cut-off distance on the dispersive term resolves this issue, and results in a rather robust behavior whatever ligand substitution reaction is considered. Ne quid nimis: Describing chemical reactions in solution by computational techniques developed for gas-phase scenarios might produce erroneous results (see histogram). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. 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)

  8. Solutions of the Noh Problem for Various Equations of State Using Lie Groups

    International Nuclear Information System (INIS)

    Axford, R.A.

    1998-01-01

    A method for developing invariant equations of state for which solutions of the Noh problem will exist is developed. The ideal gas equation of state is shown to be a special case of the general method. Explicit solutions of the Noh problem in planar, cylindrical and spherical geometry are determined for a Mie-Gruneisen and the stiff gas equation of state

  9. Effects of Ligands on a Ternary Hydroxo Complex Formation with Eu(III) in a Aqueous Solution: Comparison of a Pyridine-2,6-dicarboxylate with a Phthalate

    International Nuclear Information System (INIS)

    Park, K. K.; Cho, H. R.; Kim, W. H.; Jung, E. C.

    2008-01-01

    The interaction of a radionuclide with ligands in a groundwater influences its migration through a hydrogeological system due to a change in the characteristics of a dissolution and a sorption. Actinide ions are classified as a hard acid and strongly interact with ligands having an oxygen donor atom of a hard base such as a hydroxide, carbonate and carboxylate. These ligands reveal a large ionic bonding character. A number of experimental results on a binary complex formation of actinides have been reported. However, actinides may easily form a ternary complex by interacting simultaneously with two different ligands, since an ionic bonding does not restrict the spatial orientation of a ligand. In previous studies, a ternary hydroxo complex formation was investigated by using pyridine-2,6-dicarboxylate (PDA) or phthalate as an organic ligand and Eu(III) as an analogue of an actinide(III) ion. Although these organic ligands equally contain two carboxylate groups that interact with an Eu(III) ion, their stabilities reveal big differences. PDA is a tridentate ligand forming two 5-membered chelates, while phthalate is a bidentate ligand forming a 7-membered chelate. The latter reveals a lower stability than the former due to an angle strain. This is one of the reasons for the lower stability of the Eu(III)-phthalate than that of the Eu(III)- PDA. The difference in the stabilities of binary complexes, EuL + (L=organic ligand), influences the stabilities of the ternary hydroxo complexes, Eu(OH)L. The coordination of a phenylic or pyridine ligand can greatly enhance the fluorescence of an Eu(III) ion due to the high absorbance of a ligand by a π → π * transition and the transfer of this energy to an Eu(III) ion. These fluorescence characteristics in a binary complex system could be changed in a ternary complex. In this study, the effect of a ligand on the stability of a ternary hydroxo complex is reported by comparing the stabilities of Eu-PDA with Eu-phthalate systems

  10. A Concise Equation of State for Aqueous Solutions of Electrolytes Incorporating Thermodynamic Laws and Entropy

    Directory of Open Access Journals (Sweden)

    Raji Heyrovská

    2004-03-01

    Full Text Available Abstract: Recently, the author suggested a simple and composite equation of state by incorporating fundamental thermodynamic properties like heat capacities into her earlier concise equation of state for gases based on free volume and molecular association / dissociation. This work brings new results for aqueous solutions, based on the analogy of the equation of state for gases and solutions over wide ranges of pressures (for gases and concentrations (for solutions. The definitions of entropy and heat energy through the equation of state for gases, also holds for solutions.

  11. Ground state solutions for asymptotically periodic Schrodinger equations with critical growth

    Directory of Open Access Journals (Sweden)

    Hui Zhang

    2013-10-01

    Full Text Available Using the Nehari manifold and the concentration compactness principle, we study the existence of ground state solutions for asymptotically periodic Schrodinger equations with critical growth.

  12. Synthesis, spectroscopic characterization, solid state d.c. electrical conductivity and biological studies of some lanthanide(III chloride complexes with a heterocyclic Schiff base ligand

    Directory of Open Access Journals (Sweden)

    K. Mohanan

    2016-07-01

    Full Text Available Condensation of 2-hydroxy-1-naphthaldehyde with 2-amino-3-carboxyethyl-4,5-dimethylthiophene in 1:1 molar ratio, yielded a potentially tridentate Schiff base viz. 2-[N-(2′-hydroxy-1-naphthylideneamino]-3-carboxyethyl-4,5-dimethylthiophene (HNAT. This ligand formed complexes with lanthanum(III, cerium(III, praseodymium(III, neodymium(III, samarium(III, europium(III and gadolinium(III chloride under well defined conditions. These complexes were characterized through elemental analysis, molar conductance, magnetic moment measurements, IR, UV–Vis, FAB mass and 1H NMR spectral studies. Analytical data showed that all the metal complexes exhibited 1:1 metal–ligand ratio. Molar conductance values adequately confirmed the non-electrolytic nature of the metal complexes. The proton NMR spectral observations supplement the IR spectral assignments. The spectral data revealed that the ligand acted as neutral tridentate, coordinating to the metal ion through azomethine nitrogen, ester carbonyl and naphtholate oxygen without deprotonation. The ligand and its lanthanum(III chloride complex were subjected to XRD studies. The lanthanum(III chloride complex has undergone a facile transesterification reaction. The solid state d.c. electrical conductivity of some selected complexes were measured as a function of temperature, indicating the semiconducting nature of the metal complexes. The antimicrobial activities were examined by disk diffusion method against some pathogenic bacterial and fungal species.

  13. Variations of structures and solid-state conductivity of isomeric silver(I) coordination polymers having linear and V-shaped thiophene-centered ditriazole ligands

    International Nuclear Information System (INIS)

    Hu, Bin; Geng, Jiao; Zhang, Lie; Huang, Wei

    2014-01-01

    A pair of new linear and V-shaped acceptor–donor–acceptor (A−D−A) thiophene-centered ditriazole structural isomers, i.e., 2,5-di(1H-1,2,4-triazol-1-yl)thiophene (L 1 ) and 3,4-di(1H-1,2,4-triazol-1-yl)thiophene (L 2 ), has been synthesized and characterized. They are used as μ 2 -bridging ligands to prepare a pair of silver(I) coordination polymers formulated as [Ag(L 1 )(NO 3 )] n (1) and [Ag(L 2 )(NO 3 )] n (2), which are also structural isomers at the supramolecular level. X-ray single-crystal diffraction analyses for 1 and 2 reveal that they exhibit the same one-dimensional (1D) coordination polymers but different structural architectures because of the distinguishable shape and configuration of isomeric ligands (L 1 and L 2 ) and the alterations of the coordination numbers. More interestingly, compared with the free ligands, 1D silver(I) polymeric isomers 1 and 2 show significant enhancement of solid-state conductivity to different extents (1.42×10 4 and 2.17×10 3 times), where 6.96 times' enhancement of solid-state conductivity from 1 to 2 has been observed. The formation of Ag–N coordinative bonds and the configurational discrepancy of L 1 and L 2 are believed to play important roles in facilitating the electron transport between molecules, which can also be supported by Density Function Theory calculations of their band gaps. - Graphical abstract: A pair of linear and V-shaped isomeric thiophene-centered ditriazole ligands (L 1 ) and L 2 are used to prepare a pair of silver(I) polymeric isomers (1 and 2), where significant enhancement of solid-state conductivity to different extents are observed originating from the distinguishable shape and configuration of isomeric ligands. - Highlights: • A pair of linear and V-shaped thiophene-centered ditriazole structural isomers is prepared. • They are used as µ 2 -bridging ligands to prepare a pair of silver(I) polymeric isomers. • Significant enhancement of solid-state conductivity is observed

  14. Separation of different valency states of neptunium from processing solutions

    International Nuclear Information System (INIS)

    Shabana, R.; EL-Naggar, H.A.

    1990-01-01

    The three main oxidation states of neptunium (Np(IV),Np(V) and Np(V I)) have been separated from each other by solvent extraction and extraction chromatographic techniques. The separation procedure is based on a systematic study of the extraction behaviour of each oxidation state using TBP as an extractant. The purity of separated species is identified using spectrophotometry

  15. State estimation of chemical engineering systems tending to multiple solutions

    Directory of Open Access Journals (Sweden)

    N. P. G. Salau

    2014-09-01

    Full Text Available A well-evaluated state covariance matrix avoids error propagation due to divergence issues and, thereby, it is crucial for a successful state estimator design. In this paper we investigate the performance of the state covariance matrices used in three unconstrained Extended Kalman Filter (EKF formulations and one constrained EKF formulation (CEKF. As benchmark case studies we have chosen: a a batch chemical reactor with reversible reactions whose system model and measurement are such that multiple states satisfy the equilibrium condition and b a CSTR with exothermic irreversible reactions and cooling jacket energy balance whose nonlinear behavior includes multiple steady-states and limit cycles. The results have shown that CEKF is in general the best choice of EKF formulations (even if they are constrained with an ad hoc clipping strategy which avoids undesired states for such case studies. Contrary to a clipped EKF formulation, CEKF incorporates constraints into an optimization problem, which minimizes the noise in a least square sense preventing a bad noise distribution. It is also shown that, although the Moving Horizon Estimation (MHE provides greater robustness to a poor guess of the initial state, converging in less steps to the actual states, it is not justified for our examples due to the high additional computational effort.

  16. Is State-Mandated Redesign an Effective and Sustainable Solution?

    Science.gov (United States)

    Young, Michelle D.

    2013-01-01

    There is a pervasive and ongoing perception that leadership preparation is a problem. Important questions remain about the intentions, capacity, and impact of state departments of education engaged in leadership preparation program redesign. In this essay, I take up several issues concerning this state policy work, including whether a one size…

  17. Np(V) carbonates in solid state and aqueous solution

    International Nuclear Information System (INIS)

    Meinrath, G.

    1994-01-01

    The solubility of NaNpO 2 CO 3 (s) in 0.1M perchlorate solution at 25 deg C in equilibrium with 1.0% CO 2 /N 2 atmosphere has been investigated as a function of pH/lg [CO 3 2- ]. The solid phase was found hexagonal with a=1008.1±0.3 pm and c=991.1±0.2 pm. A solubility product of lg Ksp(NaNpO 2 CO 3 ) = -10.22±0.02 and a formation constant of the first Np(V) carbonato species of lg β 01 = 4.52±0.02 was evaluated. For the dicarbonato species an upper limit of lg lg β 02 2 partial pressure gave evidence that carbonato species are prevailing in solutions at both 1% and 0.03% CO 2 partial pressures. (author) 26 refs.; 4 figs.; 3 tabs

  18. Trendy solutions: Why do states adopt Sustainable Energy Portfolio Standards?

    Energy Technology Data Exchange (ETDEWEB)

    Chandler, Jess [Georgia Institute of Technology, 685 Cherry Street, Atlanta, GA 30332-0345 (United States)], E-mail: jess.chandler@gatech.edu

    2009-08-15

    Thirty-four states had adopted Sustainable Energy Portfolio Standards (SEPS) or similar goals by the end of 2008, with 14 adoptions since 2006. There appears to be something trendy about SEPS and states may adopt SEPS when internal variables would indicate otherwise. This analysis extends the current discussion of SEPS adoption beyond internal variables, relying on innovation and diffusion theory. Logistic regression with SEPS adoption as the dependent variable is used to test internal determinants and diffusion measures for the years 1997-2008. Of the internal determinants variables, affluence and government ideology were found to be positive and significant. The results show that regional and neighbor diffusion variables are significant in SEPS adoption decisions-even when accounting for ideological distance from previous adopters.

  19. Trendy solutions. Why do states adopt Sustainable Energy Portfolio Standards?

    Energy Technology Data Exchange (ETDEWEB)

    Chandler, Jess [Georgia Institute of Technology, 685 Cherry Street, Atlanta, GA 30332-0345 (United States)

    2009-08-15

    Thirty-four states had adopted Sustainable Energy Portfolio Standards (SEPS) or similar goals by the end of 2008, with 14 adoptions since 2006. There appears to be something trendy about SEPS and states may adopt SEPS when internal variables would indicate otherwise. This analysis extends the current discussion of SEPS adoption beyond internal variables, relying on innovation and diffusion theory. Logistic regression with SEPS adoption as the dependent variable is used to test internal determinants and diffusion measures for the years 1997-2008. Of the internal determinants variables, affluence and government ideology were found to be positive and significant. The results show that regional and neighbor diffusion variables are significant in SEPS adoption decisions - even when accounting for ideological distance from previous adopters. (author)

  20. Trendy solutions: Why do states adopt Sustainable Energy Portfolio Standards?

    International Nuclear Information System (INIS)

    Chandler, Jess

    2009-01-01

    Thirty-four states had adopted Sustainable Energy Portfolio Standards (SEPS) or similar goals by the end of 2008, with 14 adoptions since 2006. There appears to be something trendy about SEPS and states may adopt SEPS when internal variables would indicate otherwise. This analysis extends the current discussion of SEPS adoption beyond internal variables, relying on innovation and diffusion theory. Logistic regression with SEPS adoption as the dependent variable is used to test internal determinants and diffusion measures for the years 1997-2008. Of the internal determinants variables, affluence and government ideology were found to be positive and significant. The results show that regional and neighbor diffusion variables are significant in SEPS adoption decisions-even when accounting for ideological distance from previous adopters.

  1. Experimental solid state NMR of gas hydrates : problems and solutions

    Energy Technology Data Exchange (ETDEWEB)

    Moudrakovski, I.; Lu, H.; Ripmeester, J. [National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences; Kumar, R.; Susilo, R. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemical and Biological Engineering; Luzi, M. [GeoForschungsZentrum Potsdam, Potsdam (Germany)

    2008-07-01

    Solid State NMR is a suitable spectroscopic technique for hydrate research for several reasons, including its capability to distinguish between different structural types of hydrates, its quantitative nature and potential for both in-situ and time resolved experiments. This study illustrated the applications of solid state NMR for compositional and structural studies of clathrate hydrates, with particular emphasis on experimental techniques and potential ways to overcome technical difficulties. In order to use the method to its full capacity, some instrumental developments are needed to adapt it to the specific experimental requirements of hydrate studies, such as very low temperatures and high pressures. This presentation discussed the quantification of the Carbon-13 spectra with examples from natural and synthetic hydrates prepared from multi-component mixtures of hydrocarbons. The main approach used for the first two examples was Carbon-13 NMR with Magic Angle Spinning (MAS) at -100 degrees C. The detailed characterization of mixed hydrogen hydrates required low temperature hydrogen MAS. The quantification problems encountered during these experiments were also discussed. The purpose of these recent experimental developments was to prompt wider application of Solid State NMR in hydrate research. NMR proved to be a viable method for analyzing the composition and structure of multi-component mixed gas hydrates; characterizing natural gas hydrates; and, evaluating the formation conditions and properties of mixed hydrogen hydrates. The limitations of the method were highlighted and sensible choices of experimental conditions and techniques that ensure accurate results were discussed. 34 refs., 10 figs.

  2. A model on valence state evaluation of TRU nuclides in reprocessing solutions

    International Nuclear Information System (INIS)

    Uchiyama, Gunzo; Fujine, Sachio; Yoshida, Zenko; Maeda, Mitsuru; Motoyama, Satoshi.

    1998-02-01

    A mathematical model was developed to evaluate the valence state of TRU nuclides in reprocessing process solutions. The model consists of mass balance equations, Nernst equations, reaction rate equations and electrically neutrality equations. The model is applicable for the valence state evaluation of TRU nuclides in both steady state and transient state conditions in redox equilibrium. The valence state which is difficult to measure under high radiation and multi component conditions is calculated by the model using experimentally measured data for the TRU nuclide concentrations, nitric acid and redox reagent concentrations, electrode potential and solution temperature. (author)

  3. Some studies on the formation of excited states of aromatic solutes in hydrocarbons and other solvents

    Energy Technology Data Exchange (ETDEWEB)

    Salmon, G A [Leeds Univ. (UK). Cookridge High Energy Radiation Research Centre

    1976-01-01

    This paper reviews the work of the author and his co-workers on the radiation-induced formation of excited states of aromatic compounds in solution. The experimental methods used are surveyed and in particular the method of measuring the yields of triplet and singlet excited states of the solute are described. The problems discussed are: (1) the effect of solvent on the yields of excited states, (2) formation of excited states in cyclohexane and other alicyclic hydrocarbons, (3) the formation of excited states in benzene and (4) the identification of T-T absorption spectra.

  4. Mixed-Valent Metals Bridged by a Radical Ligand: Fact, or Fiction Based on Structure-Oxidation State Correlations

    Czech Academy of Sciences Publication Activity Database

    Sarkar, B.; Patra, S.; Fiedler, Jan; Sunoj, R. B.; Janardanan, D.; Lahiri, G. K.; Kaim, W.

    2008-01-01

    Roč. 130, č. 11 (2008), s. 3532-3542 ISSN 0002-7863 R&D Projects: GA MŠk 1P05OC068; GA MŠk OC 140 Institutional research plan: CEZ:AV0Z40400503 Keywords : electron transfer series * quinone-related ligand s * ruthenium complexes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.091, year: 2008

  5. Polymorphism of Ag29(BDT)12(TPP)43- cluster: interactions of secondary ligands and their effect on solid state luminescence.

    Science.gov (United States)

    Nag, Abhijit; Chakraborty, Papri; Bodiuzzaman, Mohammad; Ahuja, Tripti; Antharjanam, Sudhadevi; Pradeep, Thalappil

    2018-05-31

    We present the first example of polymorphism (cubic & trigonal) in single crystals of an atomically precise monolayer protected cluster, Ag29(BDT)12(TPP)43-. We demonstrate that C-Hπ interactions of the secondary ligands (TPP) are dominant in a cubic lattice compared to a trigonal lattice, resulting in a greater rigidity of the structure, which in turn, results in a higher luminescence efficiency in it.

  6. OUTSOURCING – IS IT A SOLUTION FOR THE STATE?

    Directory of Open Access Journals (Sweden)

    Victor-Adrian Troacă

    2012-03-01

    Full Text Available In terms of scientific research, we consider the need for an attempt to address both scientific and practical efficiency of the state apparatus. The issue of outsourcing seems to be most common in the field of microeconomics, because private firms are willing to maximize profits. On the other hand, the state seeks to minimize social risks in the first place, even though these often lead to improper functioning of the device. Fight for survival in an economic reality located in a changing requires constant adaptation to all those who live this reality. So far only those interested keeping pace with new demands remain in the market On the other hand, macroeconomic policy makers continue to show interest in minimizing "social" costs however would maximize these government spending. The paper will track how outsourcing would ensure a recovery in the national economy, use resources economically, efficiently could lead to a recovery of national economy, to a maximum income and expenses to minimize In other words the economic growth - the desire of any macroeconomic policy decider.

  7. Solution for state constrained optimal control problems applied to power split control for hybrid vehicles

    NARCIS (Netherlands)

    Keulen, van T.A.C.; Gillot, J.; Jager, de A.G.; Steinbuch, M.

    2014-01-01

    This paper presents a numerical solution for scalar state constrained optimal control problems. The algorithm rewrites the constrained optimal control problem as a sequence of unconstrained optimal control problems which can be solved recursively as a two point boundary value problem. The solution

  8. Evaluation of LexisNexis Batch Solutions in the New York State Cancer Registry

    OpenAIRE

    Pradhan, Eva; Boscoe, Francis P.

    2014-01-01

    Using Lexis Nexis Batch Solutions, the New York State Cancer Registry was able to identify substantial numbers of missing addresses, birth dates, and social security numbers, for persons diagnosed as far back as 1976.

  9. Excited state redox properties of phthalocyanines: influence of the axial ligand on the rates of relaxation and electron-transfer quenching of the lowest /sup 3/. pi pi. /sup */ excited state

    Energy Technology Data Exchange (ETDEWEB)

    Ferraudi, G J; Prasad, D R

    1874-01-01

    Laser flash excitations at 640 nm have been used to generate the transient spectra of the lowest-lying /sup 3/..pi pi../sup */ state of phthalocyaninatoruthenium(II) complexes. The properties of this excited state such as the properties of the maxima, lambda/sub max/ = 500 +/- 30 nm, and lifetimes, t/sub 1/2/ = 70-4500 ns, exhibit a large dependence on the electron-accepting and electron-withdrawing tendencies of the axial ligands. A similar influence was observed upon the rate of electron-transfer quenching of the /sup 3/..pi pi../sup */ state. Values between 10/sup 6/ and 10/sup 7/ dm/sup 3/ mol/sup -1/ s/sup -1/ for the self-exchange rate constant have been obtained, according to Marcus-Hush theoretical treatments, for (Ru(pc.)LL')/sup +//(/sup 3/..pi pi../sup */)(Ru(pc)LL') (L and L' = neutral axial ligands; pc = phthalocyaninate (2-)) and isoelectronic cobalt(III) and rhodium(III) couples. The redox properties of the ground and excited states are correlated with axial ligand-induced perturbations of the electronic structure.

  10. Structural stability of Riemann solutions for strictly hyperbolic systems with three piecewise constant states

    Directory of Open Access Journals (Sweden)

    Xuefeng Wei

    2016-12-01

    Full Text Available This article concerns the wave interaction problem for a strictly hyperbolic system of conservation laws whose Riemann solutions involve delta shock waves. To cover all situations, the global solutions are constructed when the initial data are taken as three piecewise constant states. It is shown that the Riemann solutions are stable with respect to a specific small perturbation of the Riemann initial data. In addition, some interesting nonlinear phenomena are captured during the process of constructing the solutions, such as the generation and decomposition of delta shock waves.

  11. Green function iterative solution of ground state wave function for Yukawa potential

    International Nuclear Information System (INIS)

    Zhang Zhao

    2003-01-01

    The newly developed single trajectory quadrature method is applied to solve central potentials. First, based on the series expansion method an exact analytic solution of the ground state for Hulthen potential and an approximate solution for Yukawa potential are obtained respectively. Second, the newly developed iterative method based on Green function defined by quadratures along the single trajectory is applied to solve Yukawa potential using the Coulomb solution and Hulthen solution as the trial functions respectively. The results show that a more proper choice of the trial function will give a better convergence. To further improve the convergence the iterative method is combined with the variational method to solve the ground state wave function for Yukawa potential, using variational solutions of the Coulomb and Hulthen potentials as the trial functions. The results give much better convergence. Finally, the obtained critical screen coefficient is applied to discuss the dissociate temperature of J/ψ in high temperature QGP

  12. Ultrafast excited-state relaxation of a binuclear Ag(i) phosphine complex in gas phase and solution.

    Science.gov (United States)

    Kruppa, S V; Bäppler, F; Klopper, W; Walg, S P; Thiel, W R; Diller, R; Riehn, C

    2017-08-30

    The binuclear complex [Ag 2 (dcpm) 2 ](PF 6 ) 2 (dcpm = bis(dicyclohexylphosphino)methane) exhibits a structure with a close silver-silver contact mediated by the bridging ligand and thus a weak argentophilic interaction. Upon electronic excitation this cooperative effect is strongly increased and determines the optical and luminescence properties of the compound. We have studied here the ultrafast electronic dynamics in parallel in gas phase by transient photodissociation and in solution by transient absorption. In particular, we report the diverse photofragmentation pathways of isolated [Ag 2 (dcpm) 2 ] 2+ in an ion trap and its gas phase UV photodissociation spectrum. By pump-probe fragmentation action spectroscopy (λ ex = 260 nm) in the gas phase, we have obtained fragment-specific transients which exhibit a common ultrafast multiexponential decay. This is fitted to four time constants (0.6/5.8/100/>1000 ps), highlighting complex intrinsic photophysical processes. Remarkably, multiexponential dynamics (0.9/8.5/73/604 ps) are as well found for the relaxation dynamics in acetonitrile solution. Ab initio calculations at the level of approximate coupled-cluster singles-doubles (CC2) theory of ground and electronically excited states of the reduced model system [Ag 2 (dmpm) 2 ] 2+ (dmpm = bis(dimethylphosphino)methane) indicate a shortening of the Ag-Ag distance upon excitation by 0.3-0.4 Å. In C 2 geometry two close-lying singlet states S 1 ( 1 MC(dσ*-pπ), 1 B, 4.13 eV) and S 2 ( 1 MC(dσ*-pσ), 1 A, 4.45 eV) are found. The nearly dark S 1 state has not been reported so far. The excitation of the S 2 state carries a large oscillator strength for the calculated vertical transition (266 nm). Two related triplets are calculated at T 1 (3.87 eV) and T 2 (3.90 eV). From these findings we suggest possible relaxation pathways with the two short time constants ascribed to ISC/IVR and propose from the obtained similar values in gas phase that the fast solution dynamics

  13. Kinetic Isotope Effect Determination Probes the Spin of the Transition State, Its Stereochemistry, and Its Ligand Sphere in Hydrogen Abstraction Reactions of Oxoiron(IV) Complexes.

    Science.gov (United States)

    Mandal, Debasish; Mallick, Dibyendu; Shaik, Sason

    2018-01-16

    identify the reactive-TS in terms of not only its spin state but also its geometry and ligand-sphere constitution. Since tunneling "cuts through" barriers, it serves as a chemical selectivity factor. Thus, we show that in a family of oxoirons reacting with one hydrocarbon, the tunneling efficiency increases as the ligands become better electron donors. This generates counterintuitive-reactivity patterns, like antielectrophilic reactivity, and induces spin-state reactivity reversals because of differing steric demands of the corresponding 2S+1 TS species, etc. Finally, for the same series, the Account reaches intuitive understanding of tunneling trends. It is shown that the increase of ligand's donicity results in electrostatic narrowing of the barrier, while the decrease of donicity and increase of bond-order asymmetry in the TS (inter alia due to Bell-Evans-Polanyi effects) broadens the barrier. Predictions are made that usage of powerful electron-donating ligands may train H-abstractors to activate the strongest C-H bond in a molecule. The concepts developed here are likely to be applicable to other oxometals in the d- and f-blocks.

  14. A study of the removal of heavy metals from aqueous solutions by Moringa oleifera seeds and amine-based ligand 1,4-bis[N,N-bis(2-picoyl)amino]butane

    International Nuclear Information System (INIS)

    Obuseng, Veronica; Nareetsile, Florence; Kwaambwa, Habauka M.

    2012-01-01

    Highlights: ► Materials are effective and selective in simultaneous removal of heavy metal ions. ► Use of composite adsorbent of both materials may result in more effective material. ► Seeds biomass has various functional groups involves in metal removal. ► Attainment of sorption equilibrium is rapid for the seeds biomass. ► Seeds biomass effectiveness is not affected over wide effective pH range. - Abstract: Uptake for lead, copper, cadmium, nickel and manganese from aqueous solution using the Moringa oleifera seeds biomass (MOSB) and amine-based ligand (ABL) was investigated. Experiments on two synthetic multi-solute systems revealed that MOSB performed well in the biosorption and followed the decreasing orders Pb(II) > Cu(II) > Cd(II) > Ni(II) > Mn(II) and Zn(II) > Cu(II) > Ni(II). The general trend of the heavy metal ions uptake by the amine-based ligand followed decreased in the order Mn > Cd > Cu > Ni > Pb, which is the reverse trend for what was observed for MOSB. Comparing the single- and multi-metal solutions, there was no clear effect in the biosorption capacity of MOSB suggesting the presence of sufficient active binding sites for all metal ions studied. The MOSB performance is also not affected by pH in the range 3.5–8.

  15. A study of the removal of heavy metals from aqueous solutions by Moringa oleifera seeds and amine-based ligand 1,4-bis[N,N-bis(2-picoyl)amino]butane

    Energy Technology Data Exchange (ETDEWEB)

    Obuseng, Veronica; Nareetsile, Florence [Department of Chemistry, University of Botswana, Private Bag UB 00704, Gaborone (Botswana); Kwaambwa, Habauka M., E-mail: hmkwaambwa@yahoo.com [Department of Chemistry, University of Botswana, Private Bag UB 00704, Gaborone (Botswana)

    2012-06-12

    Highlights: Black-Right-Pointing-Pointer Materials are effective and selective in simultaneous removal of heavy metal ions. Black-Right-Pointing-Pointer Use of composite adsorbent of both materials may result in more effective material. Black-Right-Pointing-Pointer Seeds biomass has various functional groups involves in metal removal. Black-Right-Pointing-Pointer Attainment of sorption equilibrium is rapid for the seeds biomass. Black-Right-Pointing-Pointer Seeds biomass effectiveness is not affected over wide effective pH range. - Abstract: Uptake for lead, copper, cadmium, nickel and manganese from aqueous solution using the Moringa oleifera seeds biomass (MOSB) and amine-based ligand (ABL) was investigated. Experiments on two synthetic multi-solute systems revealed that MOSB performed well in the biosorption and followed the decreasing orders Pb(II) > Cu(II) > Cd(II) > Ni(II) > Mn(II) and Zn(II) > Cu(II) > Ni(II). The general trend of the heavy metal ions uptake by the amine-based ligand followed decreased in the order Mn > Cd > Cu > Ni > Pb, which is the reverse trend for what was observed for MOSB. Comparing the single- and multi-metal solutions, there was no clear effect in the biosorption capacity of MOSB suggesting the presence of sufficient active binding sites for all metal ions studied. The MOSB performance is also not affected by pH in the range 3.5-8.

  16. Probes of the metal-to-ligand charge-transfer excited states in ruthenium-Am(m)ine-bipyridine complexes: the effects of NH/ND and CH/CD isotopic substitution on the 77 K luminescence.

    Science.gov (United States)

    Chen, Yuan-Jang; Xie, Puhui; Endicott, John F; Odongo, Onduru S

    2006-06-29

    The effects of ligand perdeuteration on the metal-to-ligand charge-transfer (MLCT) excited-state emission properties at 77 K are described for several [Ru(L)(4)bpy](2+) complexes in which the emission process is nominally [uIII,bpy-] --> [RuII,bpy]. The perdeuteration of the 2,2'-bipyridine (bpy) ligand is found to increase the zero-point energy differences between the ground states and MLCT excited states by amounts that vary from 0 +/- 10 to 70 +/- 10 cm(-1) depending on the ligands L. This indicates that there are some vibrational modes with smaller force constants in the excited states than in the ground states for most of these complexes. These blue shifts increase approximately as the energy difference between the excited and ground states decreases, but they are otherwise not strongly correlated with the number of bipyridine ligands in the complex. Careful comparisons of the [Ru(L)(4)(d(8)-bpy)](2+) and [Ru(L)(4)(h(8)-bpy](2+) emission spectra are used to resolve the very weak vibronic contributions of the C-H stretching modes as the composite contributions of the corresponding vibrational reorganizational energies. The largest of these, 25 +/- 10 cm(-1), is found for the complexes with L = py or bpy/2 and smaller when L = NH(3). Perdeuteration of the am(m)ine ligands (NH(3), en, or [14]aneN(4)) has no significant effect on the zero-point energy difference, and the contributions of the NH stretching vibrational modes to the emission band shape are too weak to resolve. Ligand perdeuteration does increase the excited-state lifetimes by a factor that is roughly proportional to the excited-state-ground-state energy difference, even though the CH and NH vibrational reorganizational energies are too small for nuclear tunneling involving these modes to dominate the relaxation process. It is proposed that metal-ligand skeletal vibrational modes and configurational mixing between metal-centered, bpy-ligand-centered, and MLCT excited states are important in

  17. Online size-exclusion high-performance liquid chromatography light scattering and differential refractometry methods to determine degree of polymer conjugation to proteins and protein-protein or protein-ligand association states.

    Science.gov (United States)

    Kendrick, B S; Kerwin, B A; Chang, B S; Philo, J S

    2001-12-15

    Characterizing the solution structure of protein-polymer conjugates and protein-ligand interactions is important in fields such as biotechnology and biochemistry. Size-exclusion high-performance liquid chromatography with online classical light scattering (LS), refractive index (RI), and UV detection offers a powerful tool in such characterization. Novel methods are presented utilizing LS, RI, and UV signals to rapidly determine the degree of conjugation and the molecular mass of the protein conjugate. Baseline resolution of the chromatographic peaks is not required; peaks need only be sufficiently separated to represent relatively pure fractions. An improved technique for determining the polypeptide-only mass of protein conjugates is also described. These techniques are applied to determining the degree of erythropoietin glycosylation, the degree of polyethylene glycol conjugation to RNase A and brain-derived neurotrophic factor, and the solution association states of these molecules. Calibration methods for the RI, UV, and LS detectors will also be addressed, as well as online methods to determine protein extinction coefficients and dn/dc values both unconjugated and conjugated protein molecules. (c)2001 Elsevier Science.

  18. Investigation of Sc(3) state in nonaqueous solutions by the 45Sc NMR method of high permission

    International Nuclear Information System (INIS)

    Buslaev, Yu.A.; Kirakosyan, G.A.; Tarasov, V.P.

    1980-01-01

    The ScCl 3 + CH 3 CN and ScCl 3 + KNCS + CH 3 CN solutions have been studied by a high-resolution NMR 45 Sc method. It has been estimated that in acetonitrile solutions, with competing ligands of Cl - and NCS - being available, hexacoordination Sc(3) complexes of various compositions are formed, and solvent molecules also take part in formation of the coordination sphere of scandium. Chemical shifts in NMR 45 Sc signals depend linearly on the number of chlor- or NCS - ions bound to scandium(3). This made it possible to determine the value of chemical shifts in signals of all 28 potential complexes formed in a system with three competing ligands

  19. Singular perturbation solutions of steady-state Poisson-Nernst-Planck systems.

    Science.gov (United States)

    Wang, Xiang-Sheng; He, Dongdong; Wylie, Jonathan J; Huang, Huaxiong

    2014-02-01

    We study the Poisson-Nernst-Planck (PNP) system with an arbitrary number of ion species with arbitrary valences in the absence of fixed charges. Assuming point charges and that the Debye length is small relative to the domain size, we derive an asymptotic formula for the steady-state solution by matching outer and boundary layer solutions. The case of two ionic species has been extensively studied, the uniqueness of the solution has been proved, and an explicit expression for the solution has been obtained. However, the case of three or more ions has received significantly less attention. Previous work has indicated that the solution may be nonunique and that even obtaining numerical solutions is a difficult task since one must solve complicated systems of nonlinear equations. By adopting a methodology that preserves the symmetries of the PNP system, we show that determining the outer solution effectively reduces to solving a single scalar transcendental equation. Due to the simple form of the transcendental equation, it can be solved numerically in a straightforward manner. Our methodology thus provides a standard procedure for solving the PNP system and we illustrate this by solving some practical examples. Despite the fact that for three ions, previous studies have indicated that multiple solutions may exist, we show that all except for one of these solutions are unphysical and thereby prove the existence and uniqueness for the three-ion case.

  20. Complexation study of a tert-butyl-calix[4]arene-based 2-hydroxynaphthalene ligand with uranium(VI) in non-aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Anne; Schmeide, Katja [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    The actinide uranium, well known from nuclear power cycle, plays also a role in rare earth production as it is an undesired constituent of the respective ores. To facilitate the production of rare earth elements, uranium has to be removed. Due to their modifiable selectivity and solubility calix[n]arenes are interesting compounds for the extraction of actinides and lanthanides. The mechanism of uranium(VI) interaction with a tert-butyl-calix[4]arene-based 2-hydroxynaphthalene ligand (L1) was studied by TRLFS, UV-vis spectroscopy and isothermal calorimetry.

  1. f-state luminescence of lanthanide and actinide ions in solution

    International Nuclear Information System (INIS)

    Beitz, J.V.

    1993-01-01

    Detailed studies of the luminescence of aquated Am 3+ are presented in the context of prior lanthanide and actinide ion work. The luminescing state of aquated Am 3+ is confirmed to be 5 D l based on observed emission and excitation spectra. The luminescence lifetime of Am 3+ in H 2 O solution is (22 ± 3) ns and (155 ± 4) ns in D 2 O solution at 295 K. Judd-Ofelt transition intensity theory qualitatively describes the observed Am 3+ relative integrated fluorescence intensities. Recent luminescence studies on complexed trivalent f-element ions in solution are reviewed as to the similarities and differences between lanthanide ion 4f state and actinide ion 5f state properties

  2. Analytical steady-state solutions for water-limited cropping systems using saline irrigation water

    Science.gov (United States)

    Skaggs, T. H.; Anderson, R. G.; Corwin, D. L.; Suarez, D. L.

    2014-12-01

    Due to the diminishing availability of good quality water for irrigation, it is increasingly important that irrigation and salinity management tools be able to target submaximal crop yields and support the use of marginal quality waters. In this work, we present a steady-state irrigated systems modeling framework that accounts for reduced plant water uptake due to root zone salinity. Two explicit, closed-form analytical solutions for the root zone solute concentration profile are obtained, corresponding to two alternative functional forms of the uptake reduction function. The solutions express a general relationship between irrigation water salinity, irrigation rate, crop salt tolerance, crop transpiration, and (using standard approximations) crop yield. Example applications are illustrated, including the calculation of irrigation requirements for obtaining targeted submaximal yields, and the generation of crop-water production functions for varying irrigation waters, irrigation rates, and crops. Model predictions are shown to be mostly consistent with existing models and available experimental data. Yet the new solutions possess advantages over available alternatives, including: (i) the solutions were derived from a complete physical-mathematical description of the system, rather than based on an ad hoc formulation; (ii) the analytical solutions are explicit and can be evaluated without iterative techniques; (iii) the solutions permit consideration of two common functional forms of salinity induced reductions in crop water uptake, rather than being tied to one particular representation; and (iv) the utilized modeling framework is compatible with leading transient-state numerical models.

  3. Analytical solution and simplified analysis of coupled parent-daughter steady-state transport with multirate mass transfer

    Science.gov (United States)

    R. Haggerty

    2013-01-01

    In this technical note, a steady-state analytical solution of concentrations of a parent solute reacting to a daughter solute, both of which are undergoing transport and multirate mass transfer, is presented. Although the governing equations are complicated, the resulting solution can be expressed in simple terms. A function of the ratio of concentrations, In (daughter...

  4. Local Properties of Solutions to Non-Autonomous Parabolic PDEs with State-Dependent Delays

    Czech Academy of Sciences Publication Activity Database

    Rezunenko, Oleksandr

    2012-01-01

    Roč. 2, č. 2 (2012), s. 56-71 ISSN 2158-611X R&D Projects: GA ČR(CZ) GAP103/12/2431 Institutional support: RVO:67985556 Keywords : partial differential equations * state-dependent delay * invariance principle Subject RIV: BC - Control Systems Theory http://library.utia.cas.cz/separaty/2012/AS/rezunenko- local properties of solutions to non-autonomous parabolic PDEs with state-dependent delay s.pdf

  5. Singlet versus Triplet Excited State Mediated Photoinduced Dehalogenation Reactions of Itraconazole in Acetonitrile and Aqueous Solutions.

    Science.gov (United States)

    Zhu, Ruixue; Li, Ming-de; Du, Lili; Phillips, David Lee

    2017-04-06

    Photoinduced dehalogenation of the antifungal drug itraconazole (ITR) in acetonitrile (ACN) and ACN/water mixed solutions was investigated using femtosecond and nanosecond time-resolved transient absorption (fs-TA and ns-TA, respectively) and nanosecond time-resolved resonance Raman spectroscopy (ns-TR 3 ) experiments. An excited resonance energy transfer is found to take place from the 4-phenyl-4,5-dihydro-3H-1,2,4-triazol-3-one part of the molecule to the 1,3-dichlorobenzene part of the molecule when ITR is excited by ultraviolet light. This photoexcitation is followed by a fast carbon-halogen bond cleavage that leads to the generation of radical intermediates via either triplet and/or singlet excited states. It is found that the singlet excited state-mediated carbon-halogen cleavage is the predominant dehalogenation process in ACN solvent, whereas a triplet state-mediated carbon-halogen cleavage prefers to occur in the ACN/water mixed solutions. The singlet-to-triplet energy gap is decreased in the ACN/water mixed solvents and this helps facilitate an intersystem crossing process, and thus, the carbon-halogen bond cleavage happens mostly through an excited triplet state in the aqueous solutions examined. The ns-TA and ns-TR 3 results also provide some evidence that radical intermediates are generated through a homolytic carbon-halogen bond cleavage via predominantly the singlet excited state pathway in ACN but via mainly the triplet state pathway in the aqueous solutions. In strong acidic solutions, protonation at the oxygen and/or nitrogen atoms of the 1,2,4-triazole-3-one group appears to hinder the dehalogenation reactions. This may offer the possibility that the phototoxicity of ITR due to the generation of aryl or halogen radicals can be reduced by protonation of certain moieties in suitably designed ITR halogen-containing derivatives.

  6. Parallel shooting methods for finding steady state solutions to engine simulation models

    DEFF Research Database (Denmark)

    Andersen, Stig Kildegård; Thomsen, Per Grove; Carlsen, Henrik

    2007-01-01

    Parallel single- and multiple shooting methods were tested for finding periodic steady state solutions to a Stirling engine model. The model was used to illustrate features of the methods and possibilities for optimisations. Performance was measured using simulation of an experimental data set...

  7. An Efficient Implementation of Non-Linear Limit State Analysis Based on Lower-Bound Solutions

    DEFF Research Database (Denmark)

    Damkilde, Lars; Schmidt, Lotte Juhl

    2005-01-01

    Limit State analysis has been used in design for decades e.g. the yield line theory for concrete slabs or slip line solutions in geotechnics. In engineering practice manual methods have been dominating but in recent years the interest in numerical methods has been increasing. In this respect it i...

  8. Investigation of the oxidation states of Pu isotopes in a hydrochloric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Lee, M.H. [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, P. O. Box 105, Yuseong, Daejeon 305-353 (Korea, Republic of)], E-mail: mhlee@kaeri.re.kr; Kim, J.Y.; Kim, W.H.; Jung, E.C.; Jee, K.Y. [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, P. O. Box 105, Yuseong, Daejeon 305-353 (Korea, Republic of)

    2008-12-15

    The characteristics of the oxidation states of Pu in a hydrochloric acid solution were investigated and the results were applied to a separating of Pu isotopes from IAEA reference soils. The oxidation states of Pu(III) and Pu(IV) were prepared by adding hydroxylamine hydrochloride and sodium nitrite to a Pu stock solution, respectively. Also, the oxidation state of Pu(VI) was adjusted with concentrated HNO{sub 3} and HClO{sub 4}. The stability of the various oxidation states of plutonium in a HCl solution with elapsed time after preparation were found to be in the following order: Pu(III){approx}Pu(VI)>Pu(IV)>Pu(V). The chemical recoveries of Pu(IV) in a 9 M HCl solution with an anion exchange resin were similar to those of Pu(VI). This method for the determination of Pu isotopes with an anion exchange resin in a 9 M HCl medium was applied to IAEA reference soils where the activity concentrations of {sup 239,240}Pu and {sup 238}Pu in IAEA-375 and IAEA-326 were consistent with the reference values reported by the IAEA.

  9. Existence of periodic solutions for Rayleigh equations with state-dependent delay

    Directory of Open Access Journals (Sweden)

    Jehad O. Alzabut

    2012-05-01

    Full Text Available We establish sufficient conditions for the existence of periodic solutions for a Rayleigh-type equation with state-dependent delay. Our approach is based on the continuation theorem in degree theory, and some analysis techniques. An example illustrates that our approach to this problem is new.

  10. Ultrafast excited and ground-state dynamics of the green fluorescent protein chromophore in solution

    NARCIS (Netherlands)

    Vengris, M.; van Stokkum, I.H.M.; He, X.; Bell, A.F.; Tonge, P.J.; van Grondelle, R.; Larsen, D.S.

    2004-01-01

    Ultrafast dispersed pump-dump-probe spectroscopy was applied to HBDI (4′-hydroxybenzylidene-2,3-dimethylimidazolinone), a model green fluorescent protein (GFP) chromophore in solution with different protonation states. The measured three-dimensional data was analyzed using a global analysis method

  11. High-resolution solution-state NMR of unfractionated plant cell walls

    Science.gov (United States)

    John Ralph; Fachuang Lu; Hoon Kim; Dino Ress; Daniel J. Yelle; Kenneth E. Hammel; Sally A. Ralph; Bernadette Nanayakkara; Armin Wagner; Takuya Akiyama; Paul F. Schatz; Shawn D. Mansfield; Noritsugu Terashima; Wout Boerjan; Bjorn Sundberg; Mattias Hedenstrom

    2009-01-01

    Detailed structural studies on the plant cell wall have traditionally been difficult. NMR is one of the preeminent structural tools, but obtaining high-resolution solution-state spectra has typically required fractionation and isolation of components of interest. With recent methods for dissolution of, admittedly, finely divided plant cell wall material, the wall can...

  12. Existence of Mild Solutions for Impulsive Fractional Integro-Differential Inclusions with State-Dependent Delay

    Directory of Open Access Journals (Sweden)

    Selvaraj Suganya

    2017-01-01

    Full Text Available In this manuscript, we implement Bohnenblust–Karlin’s fixed point theorem to demonstrate the existence of mild solutions for a class of impulsive fractional integro-differential inclusions (IFIDI with state-dependent delay (SDD in Banach spaces. An example is provided to illustrate the obtained abstract results.

  13. A fluorescent chemosensor for Zn(II). Exciplex formation in solution and the solid state.

    Science.gov (United States)

    Bencini, Andrea; Berni, Emanuela; Bianchi, Antonio; Fornasari, Patrizia; Giorgi, Claudia; Lima, Joao C; Lodeiro, Carlos; Melo, Maria J; de Melo, J Seixas; Parola, Antonio Jorge; Pina, Fernando; Pina, Joao; Valtancoli, Barbara

    2004-07-21

    The macrocyclic phenanthrolinophane 2,9-[2,5,8-triaza-5-(N-anthracene-9-methylamino)ethyl]-[9]-1,10-phenanthrolinophane (L) bearing a pendant arm containing a coordinating amine and an anthracene group forms stable complexes with Zn(II), Cd(II) and Hg(II) in solution. Stability constants of these complexes were determined in 0.10 mol dm(-3) NMe(4)Cl H(2)O-MeCN (1:1, v/v) solution at 298.1 +/- 0.1 K by means of potentiometric (pH metric) titration. The fluorescence emission properties of these complexes were studied in this solvent. For the Zn(II) complex, steady-state and time-resolved fluorescence studies were performed in ethanol solution and in the solid state. In solution, intramolecular pi-stacking interaction between phenanthroline and anthracene in the ground state and exciplex emission in the excited state were observed. From the temperature dependence of the photostationary ratio (I(Exc)/I(M)), the activation energy for the exciplex formation (E(a)) and the binding energy of the exciplex (-DeltaH) were determined. The crystal structure of the [ZnLBr](ClO(4)).H(2)O compound was resolved, showing that in the solid state both intra- and inter-molecular pi-stacking interactions are present. Such interactions were also evidenced by UV-vis absorption and emission spectra in the solid state. The absorption spectrum of a thin film of the solid complex is red-shifted compared with the solution spectra, whereas its emission spectrum reveals the unique featureless exciplex band, blue shifted compared with the solution. In conjunction with X-ray data the solid-state data was interpreted as being due to a new exciplex where no pi-stacking (full overlap of the pi-electron cloud of the two chromophores - anthracene and phenanthroline) is observed. L is a fluorescent chemosensor able to signal Zn(II) in presence of Cd(II) and Hg(II), since the last two metal ions do not give rise either to the formation of pi-stacking complexes or to exciplex emission in solution.

  14. A finite state projection algorithm for the stationary solution of the chemical master equation

    Science.gov (United States)

    Gupta, Ankit; Mikelson, Jan; Khammash, Mustafa

    2017-10-01

    The chemical master equation (CME) is frequently used in systems biology to quantify the effects of stochastic fluctuations that arise due to biomolecular species with low copy numbers. The CME is a system of ordinary differential equations that describes the evolution of probability density for each population vector in the state-space of the stochastic reaction dynamics. For many examples of interest, this state-space is infinite, making it difficult to obtain exact solutions of the CME. To deal with this problem, the Finite State Projection (FSP) algorithm was developed by Munsky and Khammash [J. Chem. Phys. 124(4), 044104 (2006)], to provide approximate solutions to the CME by truncating the state-space. The FSP works well for finite time-periods but it cannot be used for estimating the stationary solutions of CMEs, which are often of interest in systems biology. The aim of this paper is to develop a version of FSP which we refer to as the stationary FSP (sFSP) that allows one to obtain accurate approximations of the stationary solutions of a CME by solving a finite linear-algebraic system that yields the stationary distribution of a continuous-time Markov chain over the truncated state-space. We derive bounds for the approximation error incurred by sFSP and we establish that under certain stability conditions, these errors can be made arbitrarily small by appropriately expanding the truncated state-space. We provide several examples to illustrate our sFSP method and demonstrate its efficiency in estimating the stationary distributions. In particular, we show that using a quantized tensor-train implementation of our sFSP method, problems admitting more than 100 × 106 states can be efficiently solved.

  15. A finite state projection algorithm for the stationary solution of the chemical master equation.

    Science.gov (United States)

    Gupta, Ankit; Mikelson, Jan; Khammash, Mustafa

    2017-10-21

    The chemical master equation (CME) is frequently used in systems biology to quantify the effects of stochastic fluctuations that arise due to biomolecular species with low copy numbers. The CME is a system of ordinary differential equations that describes the evolution of probability density for each population vector in the state-space of the stochastic reaction dynamics. For many examples of interest, this state-space is infinite, making it difficult to obtain exact solutions of the CME. To deal with this problem, the Finite State Projection (FSP) algorithm was developed by Munsky and Khammash [J. Chem. Phys. 124(4), 044104 (2006)], to provide approximate solutions to the CME by truncating the state-space. The FSP works well for finite time-periods but it cannot be used for estimating the stationary solutions of CMEs, which are often of interest in systems biology. The aim of this paper is to develop a version of FSP which we refer to as the stationary FSP (sFSP) that allows one to obtain accurate approximations of the stationary solutions of a CME by solving a finite linear-algebraic system that yields the stationary distribution of a continuous-time Markov chain over the truncated state-space. We derive bounds for the approximation error incurred by sFSP and we establish that under certain stability conditions, these errors can be made arbitrarily small by appropriately expanding the truncated state-space. We provide several examples to illustrate our sFSP method and demonstrate its efficiency in estimating the stationary distributions. In particular, we show that using a quantized tensor-train implementation of our sFSP method, problems admitting more than 100 × 10 6 states can be efficiently solved.

  16. 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)

  17. Dinitrosyl iron complexes with natural thiol-containing ligands in aqueous solutions: Synthesis and some physico-chemical characteristics (A methodological review).

    Science.gov (United States)

    Vanin, Anatoly F; Borodulin, Rostislav R; Mikoyan, Vasak D

    2017-06-01

    Two approaches to the synthesis of dinitrosyl iron complexes (DNIC) with glutathione and l-cysteine in aqueous solutions based on the use of gaseous NO and appropriate S-nitrosothiols, viz., S-nitrosoglutathione (GS-NO) or S-nitrosocysteine (Cys-NO), respectively, are considered. A schematic representation of a vacuum unit for generation and accumulation of gaseous NO purified from the NO 2 admixture and its application for obtaining aqueous solutions of DNIC in a Thunberg apparatus is given. To achieve this, a solution of bivalent iron in distilled water is loaded into the upper chamber of the Thunberg apparatus, while the thiol solution in an appropriate buffer (рН 7.4) is loaded into its lower chamber. Further steps, which include degassing, addition of gaseous NO, shaking of both solutions and formation of the Fe 2+ -thiol mixture, culminate in the synthesis of DNIC. The second approach consists in a stepwise addition of Fe 2+ salts and nitrite to aqueous solutions of glutathione or cysteine. In the presence of Fe 2+ and after the increase in рН to the physiological level, GS-NO or Cys-NO generated at acid media (pH nitrosonium ions (NO + ) and the peculiar characteristics of the EPR signal of their mononuclear form (M-DNIC). Copyright © 2017. Published by Elsevier Inc.

  18. Molecular recognition of naphthalene diimide ligands by telomeric quadruplex-DNA: the importance of the protonation state and mediated hydrogen bonds.

    Science.gov (United States)

    Spinello, A; Barone, G; Grunenberg, J

    2016-01-28

    In depth Monte Carlo conformational scans in combination with molecular dynamics (MD) simulations and electronic structure calculations were applied in order to study the molecular recognition process between tetrasubstituted naphthalene diimide (ND) guests and G-quadruplex (G4) DNA receptors. ND guests are a promising class of telomere stabilizers due to which they are used in novel anticancer therapeutics. Though several ND guests have been studied experimentally in the past, the protonation state under physiological conditions is still unclear. Based on chemical intuition, in the case of N-methyl-piperazine substitution, different protonation states are possible and might play a crucial role in the molecular recognition process by G4-DNA. Depending on the proton concentration, different nitrogen atoms of the N-methyl-piperazine might (or might not) be protonated. This fact was considered in our simulation in terms of a case by case analysis, since the process of molecular recognition is determined by possible donor or acceptor positions. The results of our simulations show that the electrostatic interactions between the ND ligands and the G4 receptor are maximized in the case of the protonation of the terminal nitrogen atoms, forming compact ND G4 complexes inside the grooves. The influence of different protonation states in terms of the ability to form hydrogen bonds with the sugar-phosphate backbone, as well as the importance of mediated vs. direct hydrogen bonding, was analyzed in detail by MD and relaxed force constant (compliance constant) simulations.

  19. Rational Ligand Design for U(VI) and Pu(IV)

    International Nuclear Information System (INIS)

    Szigethy, Geza

    2009-01-01

    Nuclear power is an attractive alternative to hydrocarbon-based energy production at a time when moving away from carbon-producing processes is widely accepted as a significant developmental need. Hence, the radioactive actinide power sources for this industry are necessarily becoming more widespread, which is accompanied by the increased risk of exposure to both biological and environmental systems. This, in turn, requires the development of technology designed to remove such radioactive threats efficiently and selectively from contaminated material, whether that be contained nuclear waste streams or the human body. Raymond and coworkers (University of California, Berkeley) have for decades investigated the interaction of biologically-inspired, hard Lewis-base ligands with high-valent, early-actinide cations. It has been established that such ligands bind strongly to the hard Lewis-acidic early actinides, and many poly-bidentate ligands have been developed and shown to be effective chelators of actinide contaminants in vivo. Work reported herein explores the effect of ligand geometry on the linear U(IV) dioxo dication (uranyl, UO 2 2+ ). The goal is to utilize rational ligand design to develop ligands that exhibit shape selectivity towards linear dioxo cations and provides thermodynamically favorable binding interactions. The uranyl complexes with a series of tetradentate 3-hydroxy-pyridin-2-one (3,2-HOPO) ligands were studied in both the crystalline state as well as in solution. Despite significant geometric differences, the uranyl affinities of these ligands vary only slightly but are better than DTPA, the only FDA-approved chelation therapy for actinide contamination. The terepthalamide (TAM) moiety was combined into tris-beidentate ligands with 1,2- and 3,2-HOPO moieties were combined into hexadentate ligands whose structural preferences and solution thermodynamics were measured with the uranyl cation. In addition to achieving coordinative saturation, these

  20. Rational Ligand Design for U(VI) and Pu(IV)

    Energy Technology Data Exchange (ETDEWEB)

    Szigethy, Geza [Univ. of California, Berkeley, CA (United States)

    2009-08-12

    Nuclear power is an attractive alternative to hydrocarbon-based energy production at a time when moving away from carbon-producing processes is widely accepted as a significant developmental need. Hence, the radioactive actinide power sources for this industry are necessarily becoming more widespread, which is accompanied by the increased risk of exposure to both biological and environmental systems. This, in turn, requires the development of technology designed to remove such radioactive threats efficiently and selectively from contaminated material, whether that be contained nuclear waste streams or the human body. Raymond and coworkers (University of California, Berkeley) have for decades investigated the interaction of biologically-inspired, hard Lewis-base ligands with high-valent, early-actinide cations. It has been established that such ligands bind strongly to the hard Lewis-acidic early actinides, and many poly-bidentate ligands have been developed and shown to be effective chelators of actinide contaminants in vivo. Work reported herein explores the effect of ligand geometry on the linear U(IV) dioxo dication (uranyl, UO2 2+). The goal is to utilize rational ligand design to develop ligands that exhibit shape selectivity towards linear dioxo cations and provides thermodynamically favorable binding interactions. The uranyl complexes with a series of tetradentate 3-hydroxy-pyridin-2-one (3,2-HOPO) ligands were studied in both the crystalline state as well as in solution. Despite significant geometric differences, the uranyl affinities of these ligands vary only slightly but are better than DTPA, the only FDA-approved chelation therapy for actinide contamination. The terepthalamide (TAM) moiety was combined into tris-beidentate ligands with 1,2- and 3,2-HOPO moieties were combined into hexadentate ligands whose structural preferences and solution thermodynamics were measured with the uranyl cation. In addition to achieving coordinative

  1. Unraveling the Solution-State Supramolecular Structures of Donor-Acceptor Polymers and their Influence on Solid-State Morphology and Charge-Transport Properties.

    Science.gov (United States)

    Zheng, Yu-Qing; Yao, Ze-Fan; Lei, Ting; Dou, Jin-Hu; Yang, Chi-Yuan; Zou, Lin; Meng, Xiangyi; Ma, Wei; Wang, Jie-Yu; Pei, Jian

    2017-11-01

    Polymer self-assembly in solution prior to film fabrication makes solution-state structures critical for their solid-state packing and optoelectronic properties. However, unraveling the solution-state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution-state structure and the charge-transport properties in field-effect transistors. Here, for the first time, it is revealed that the thin-film morphology of a conjugated polymer inherits the features of its solution-state supramolecular structures. A "solution-state supramolecular structure control" strategy is proposed to increase the electron mobility of a benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV)-based polymer. It is shown that the solution-state structures of the BDOPV-based conjugated polymer can be tuned such that it forms a 1D rod-like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution-state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm 2 V -1 s -1 . This work demonstrates that "solution-state supramolecular structure" control is critical for understanding and optimization of the thin-film morphology and charge-transport properties of conjugated polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Estimation of free acid content in lanthanide salt solution used for pH-potentiometric determination of their stability constants with organic ligands

    International Nuclear Information System (INIS)

    Zheltvaj, I.I.; Tishchenko, M.A.

    1985-01-01

    To improve the pH-potentiometric method for determining complex stability constants the possibility of alkalimetric titration of a free acid in the lanthanide perchlorate solution after binding metal ions by disodium salt of ethylene-diamine-tetraacetic acid is studied. The stability constants were determined from the difference between the total acid content after complexon addition and doubled metal cation content in the solution which has been preliminarily determined by the complexonometric method. It is shown that the alkaline (NaOH) equivalent quantities spent for free acid titration either in the absence or presence of the complexon is different. With increase of free acid content in the solution the difference in determinations with complexon and without it is somewhat reduced. Thus, the use of complexon contributes to a higher accuracy in determining the free acid, and in the first place in case of minor contents

  3. Reciprocal Estimation of Pedestrian Location and Motion State toward a Smartphone Geo-Context Computing Solution

    Directory of Open Access Journals (Sweden)

    Jingbin Liu

    2015-06-01

    Full Text Available The rapid advance in mobile communications has made information and services ubiquitously accessible. Location and context information have become essential for the effectiveness of services in the era of mobility. This paper proposes the concept of geo-context that is defined as an integral synthesis of geographical location, human motion state and mobility context. A geo-context computing solution consists of a positioning engine, a motion state recognition engine, and a context inference component. In the geo-context concept, the human motion states and mobility context are associated with the geographical location where they occur. A hybrid geo-context computing solution is implemented that runs on a smartphone, and it utilizes measurements of multiple sensors and signals of opportunity that are available within a smartphone. Pedestrian location and motion states are estimated jointly under the framework of hidden Markov models, and they are used in a reciprocal manner to improve their estimation performance of one another. It is demonstrated that pedestrian location estimation has better accuracy when its motion state is known, and in turn, the performance of motion state recognition can be improved with increasing reliability when the location is given. The geo-context inference is implemented simply with the expert system principle, and more sophisticated approaches will be developed.

  4. Steady-state solution growth of microcrystalline silicon on nanocrystalline seed layers on glass

    Science.gov (United States)

    Bansen, R.; Ehlers, C.; Teubner, Th.; Boeck, T.

    2016-09-01

    The growth of polycrystalline silicon layers on glass from tin solutions at low temperatures is presented. This approach is based on the steady-state solution growth of Si crystallites on nanocrystalline seed layers, which are prepared in a preceding process step. Scanning electron microscopy and atomic force microscopy investigations reveal details about the seed layer surfaces, which consist of small hillocks, as well as about Sn inclusions and gaps along the glass substrate after solution growth. The successful growth of continuous microcrystalline Si layers with grain sizes up to several ten micrometers shows the feasibility of the process and makes it interesting for photovoltaics. Project supported by the German Research Foundation (DFG) (No. BO 1129/5-1).

  5. Unified semiclassical theory for the two-state system: an analytical solution for general nonadiabatic tunneling.

    Science.gov (United States)

    Zhu, Chaoyuan; Lin, Sheng Hsien

    2006-07-28

    Unified semiclasical solution for general nonadiabatic tunneling between two adiabatic potential energy surfaces is established by employing unified semiclassical solution for pure nonadiabatic transition [C. Zhu, J. Chem. Phys. 105, 4159 (1996)] with the certain symmetry transformation. This symmetry comes from a detailed analysis of the reduced scattering matrix for Landau-Zener type of crossing as a special case of nonadiabatic transition and nonadiabatic tunneling. Traditional classification of crossing and noncrossing types of nonadiabatic transition can be quantitatively defined by the rotation angle of adiabatic-to-diabatic transformation, and this rotational angle enters the analytical solution for general nonadiabatic tunneling. The certain two-state exponential potential models are employed for numerical tests, and the calculations from the present general nonadiabatic tunneling formula are demonstrated in very good agreement with the results from exact quantum mechanical calculations. The present general nonadiabatic tunneling formula can be incorporated with various mixed quantum-classical methods for modeling electronically nonadiabatic processes in photochemistry.

  6. The optimal solution of a non-convex state-dependent LQR problem and its applications.

    Directory of Open Access Journals (Sweden)

    Xudan Xu

    Full Text Available This paper studies a Non-convex State-dependent Linear Quadratic Regulator (NSLQR problem, in which the control penalty weighting matrix [Formula: see text] in the performance index is state-dependent. A necessary and sufficient condition for the optimal solution is established with a rigorous proof by Euler-Lagrange Equation. It is found that the optimal solution of the NSLQR problem can be obtained by solving a Pseudo-Differential-Riccati-Equation (PDRE simultaneously with the closed-loop system equation. A Comparison Theorem for the PDRE is given to facilitate solution methods for the PDRE. A linear time-variant system is employed as an example in simulation to verify the proposed optimal solution. As a non-trivial application, a goal pursuit process in psychology is modeled as a NSLQR problem and two typical goal pursuit behaviors found in human and animals are reproduced using different control weighting [Formula: see text]. It is found that these two behaviors save control energy and cause less stress over Conventional Control Behavior typified by the LQR control with a constant control weighting [Formula: see text], in situations where only the goal discrepancy at the terminal time is of concern, such as in Marathon races and target hitting missions.

  7. Radiolytic effect on the chemical state of iodine in aqueous solution

    International Nuclear Information System (INIS)

    Shiraishi, H.; Kimiya, T.; Ohmae, M.; Ishigure, K.

    1988-01-01

    The oxidation state of iodine dissolved in an aqueous solution is easily changed in the presence of radiation field. Hence, it is essential to take the radiolytic effect into account when one is to estimate chemical forms of iodine after being released into the containment under an LOCA condition. This paper summarizes results of γ-radiolysis experiments on aqueous solutions containing iodine species, which have been carried out to extend the previously reported study on the same system. Variation in iodine product distribution with time has been examined as before, utilizing a flow system under irradiation. Attention has been paid to the effect of oxygen, to that of an initial oxidation state of iodine, and to the influence of temperature. Some kinetic analysis on the system was also undertaken

  8. The theory and experiment of solute migration caused by excited state absorptions

    International Nuclear Information System (INIS)

    Xiao, Jin; Ying-Lin, Song; Yu-Xiao, Wang; Min, Shui; Chang-Wei, Li; Jun-Yi, Yang; Xue-Ru, Zhang; Kun, Yang

    2010-01-01

    Nonsymmetrical transition from reverse-saturable absorption (RSA) to saturable absorption (SA) caused by excited state absorption induced mass transport of the CuPcTs dissolved in dimethyl sulfoxide is observed in an open aperture Z-scan experiment with a 21-ps laser pulse. The nonsymmetrical transition from RSA to SA is ascribed neither to saturation of excited state absorption nor to thermal induced mass transport, the so-called Soret effect. In our consideration, strong nonlinear absorption causes the rapid accumulation of the non-uniform kinetic energy of the solute molecules. The non-uniform kinetic field in turn causes the migration of the solute molecules. Additionally, an energy-gradient-induced mass transport theory is presented to interpret the experimental results, and the theoretical calculations are also taken to fit our experimental results. (classical areas of phenomenology)

  9. Periodic solution for state-dependent impulsive shunting inhibitory CNNs with time-varying delays.

    Science.gov (United States)

    Şaylı, Mustafa; Yılmaz, Enes

    2015-08-01

    In this paper, we consider existence and global exponential stability of periodic solution for state-dependent impulsive shunting inhibitory cellular neural networks with time-varying delays. By means of B-equivalence method, we reduce these state-dependent impulsive neural networks system to an equivalent fix time impulsive neural networks system. Further, by using Mawhin's continuation theorem of coincide degree theory and employing a suitable Lyapunov function some new sufficient conditions for existence and global exponential stability of periodic solution are obtained. Previous results are improved and extended. Finally, we give an illustrative example with numerical simulations to demonstrate the effectiveness of our theoretical results. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. A radioimmunoassay to screen for antibodies to native conformational antigens and analyse ligand-induced structural states of antigenic proteins

    International Nuclear Information System (INIS)

    Bernotat-Danielowski, S.; Koepsell, H.

    1988-01-01

    A radioimmunoassay is described in which antigenic protein was immobilized by incubating nitrocellulose filters of defined diameter with antigen-containing solutions. Antigenic sites which are sensitive to protein denaturation by drying could be detected with the assay. The assay was also used to screen hybridoma supernatants for antibodies directed against Na + cotransport proteins from renal brush-border membranes. Monoclonal antibodies were selected which showed different binding charactertics depending on whether or not substrates of Na + cotransporters were present. One of the antibodies, which showed different antibody binding after addition of D-glucose or L-lactate, bound to a polypeptide component of the renal N + -D-glucose cotransporter and was able to inhibit Na + gradient-dependent. To investigate the effects of D-glucose and L-lactate on the binding of this antibody concentration dependence was measured. High and low affinity binding sites for D-glucose and L-lactate were characterized thereby demonstrating that the radioimmunoassay permits investigations of the properties of high and low affinity substrate binding sites. (author). refs.; 6 figs.; 2 tabs

  11. Characterization of nonderivatized plant cell walls using high-resolution solution-state NMR spectroscopy

    Science.gov (United States)

    Daniel J. Yelle; John Ralph; Charles R. Frihart

    2008-01-01

    A recently described plant cell wall dissolution system has been modified to use perdeuterated solvents to allow direct in-NMR-tube dissolution and high-resolution solution-state NMR of the whole cell wall without derivatization. Finely ground cell wall material dissolves in a solvent system containing dimethylsulfoxide-d6 and 1-methylimidazole-d6 in a ratio of 4:1 (v/...

  12. Relating dynamic brain states to dynamic machine states: Human and machine solutions to the speech recognition problem.

    Directory of Open Access Journals (Sweden)

    Cai Wingfield

    2017-09-01

    Full Text Available There is widespread interest in the relationship between the neurobiological systems supporting human cognition and emerging computational systems capable of emulating these capacities. Human speech comprehension, poorly understood as a neurobiological process, is an important case in point. Automatic Speech Recognition (ASR systems with near-human levels of performance are now available, which provide a computationally explicit solution for the recognition of words in continuous speech. This research aims to bridge the gap between speech recognition processes in humans and machines, using novel multivariate techniques to compare incremental 'machine states', generated as the ASR analysis progresses over time, to the incremental 'brain states', measured using combined electro- and magneto-encephalography (EMEG, generated as the same inputs are heard by human listeners. This direct comparison of dynamic human and machine internal states, as they respond to the same incrementally delivered sensory input, revealed a significant correspondence between neural response patterns in human superior temporal cortex and the structural properties of ASR-derived phonetic models. Spatially coherent patches in human temporal cortex responded selectively to individual phonetic features defined on the basis of machine-extracted regularities in the speech to lexicon mapping process. These results demonstrate the feasibility of relating human and ASR solutions to the problem of speech recognition, and suggest the potential for further studies relating complex neural computations in human speech comprehension to the rapidly evolving ASR systems that address the same problem domain.

  13. Planning and Implementing Immunization Billing Programs at State and Local Health Departments: Barriers and Possible Solutions.

    Science.gov (United States)

    Corriero, Rosemary; Redmon, Ginger

    Before participating in a project funded by the Centers for Disease Control and Prevention, most state and local health departments (LHDs) were not seeking reimbursement or being fully reimbursed by insurance plans for the cost of immunization services (including vaccine costs and administration fees) they provided to insured patients. Centers for Disease Control and Prevention's Billables Project was designed to enable state and LHDs to bill public and private insurance plans for immunization services provided to insured patients. Identify and describe key barriers state and LHDs may encounter while planning and implementing a billing program, as well as possible solutions for overcoming those barriers. This study used reports from Billables Project participants to explore barriers they encountered when planning and implementing a billing program and steps taken to address those barriers. Thirty-eight state immunization programs. Based on project participants' reports, barriers were noted in 7 categories: (1) funding and costs, (2) staff, (3) health department characteristics, (4) third-party payers and insurance plans, (5) software, (6) patient insurance status, and (7) other barriers. Possible solutions for overcoming those barriers included hiring or seeking external help, creating billing guides and training modules, streamlining workflows, and modifying existing software systems. Overcoming barriers during planning and implementation of a billing program can be challenging for state and LHDs, but the experiences and suggestions of past Billables Project participants can help guide future billing program efforts.

  14. Four Thermochromic o-Hydroxy Schiff Bases of α-Aminodiphenylmethane: Solution and Solid State Study

    Directory of Open Access Journals (Sweden)

    Marija Zbačnik

    2017-01-01

    Full Text Available More than a hundred years after the first studies of the photo- and thermochromism of o-hydroxy Schiff bases (imines, it is still an intriguing topic that fascinates several research groups around the world. The reasons for such behavior are still under investigation, and this work is a part of it. We report the solution-based and mechanochemical synthesis of four o-hydroxy imines derived from α-aminodiphenylmethane. The thermochromic properties were studied for the single crystal and polycrystalline samples of the imines. The supramolecular impact on the keto-enol tautomerism in the solid state was studied using SCXRD and NMR, while NMR spectroscopy was used for the solution state. All four imines are thermochromic, although the color changes of the single crystals are not as strong as of the polycrystalline samples. One of the imines shows negative thermochromism, and that one is in keto-amine tautomeric form, both in the solid state as in solution.

  15. Ligand induced change of β2 adrenergic receptor from active to inactive conformation and its implication for the closed/open state of the water channel: insight from molecular dynamics simulation, free energy calculation and Markov state model analysis.

    Science.gov (United States)

    Bai, Qifeng; Pérez-Sánchez, Horacio; Zhang, Yang; Shao, Yonghua; Shi, Danfeng; Liu, Huanxiang; Yao, Xiaojun

    2014-08-14

    The reported crystal structures of β2 adrenergic receptor (β2AR) reveal that the open and closed states of the water channel are correlated with the inactive and active conformations of β2AR. However, more details about the process by which the water channel states are affected by the active to inactive conformational change of β2AR remain illusive. In this work, molecular dynamics simulations are performed to study the dynamical inactive and active conformational change of β2AR induced by inverse agonist ICI 118,551. Markov state model analysis and free energy calculation are employed to explore the open and close states of the water channel. The simulation results show that inverse agonist ICI 118,551 can induce water channel opening during the conformational transition of β2AR. Markov state model (MSM) analysis proves that the energy contour can be divided into seven states. States S1, S2 and S5, which represent the active conformation of β2AR, show that the water channel is in the closed state, while states S4 and S6, which correspond to the intermediate state conformation of β2AR, indicate the water channel opens gradually. State S7, which represents the inactive structure of β2AR, corresponds to the full open state of the water channel. The opening mechanism of the water channel is involved in the ligand-induced conformational change of β2AR. These results can provide useful information for understanding the opening mechanism of the water channel and will be useful for the rational design of potent inverse agonists of β2AR.

  16. Application of the van der Waals equation of state to polymers .4. Correlation and prediction of lower critical solution temperatures for polymer solutions

    DEFF Research Database (Denmark)

    Goncalves, Ana Saraiva; Kontogeorgis, Georgios; Harismiadis, Vassilis I.

    1996-01-01

    The van der Waals equation of state is used for the correlation and the prediction of the lower critical solution behavior or mixtures including a solvent and a polymer. The equation of state parameters for the polymer are estimated from experimental volumetric data at low pressures. The equation...

  17. Multiple solutions of steady-state Poisson–Nernst–Planck equations with steric effects

    International Nuclear Information System (INIS)

    Lin, Tai-Chia; Eisenberg, Bob

    2015-01-01

    Experiments measuring currents through single protein channels show unstable currents. Channels switch between ‘open’ or ‘closed’ states in a spontaneous stochastic process called gating. Currents are either (nearly) zero or at a definite level, characteristic of each type of protein, independent of time, once the channel is open. The steady state Poisson–Nernst–Planck equations with steric effects (PNP-steric equations) describe steady current through the open channel quite well, in a wide variety of conditions. Here we study the existence of multiple solutions of steady state PNP-steric equations to see if they themselves, without modification or augmentation, can describe two levels of current. We prove that there are two steady state solutions of PNP-steric equations for (a) three types of ion species (two types of cations and one type of anion) with a positive constant permanent charge, and (b) four types of ion species (two types of cations and their counter-ions) with a constant permanent charge but no sign condition. The excess currents (due to steric effects) associated with these two steady state solutions are derived and expressed as two distinct formulas. Our results indicate that PNP-steric equations may become a useful model to study spontaneous gating of ion channels. Spontaneous gating is thought to involve small structural changes in the channel protein that perhaps produce large changes in the profiles of free energy that determine ion flow. Gating is known to be modulated by external structures. Both can be included in future extensions of our present analysis. (paper)

  18. Sensitive Constrained Optimal PMU Allocation with Complete Observability for State Estimation Solution

    Directory of Open Access Journals (Sweden)

    R. Manam

    2017-12-01

    Full Text Available In this paper, a sensitive constrained integer linear programming approach is formulated for the optimal allocation of Phasor Measurement Units (PMUs in a power system network to obtain state estimation. In this approach, sensitive buses along with zero injection buses (ZIB are considered for optimal allocation of PMUs in the network to generate state estimation solutions. Sensitive buses are evolved from the mean of bus voltages subjected to increase of load consistently up to 50%. Sensitive buses are ranked in order to place PMUs. Sensitive constrained optimal PMU allocation in case of single line and no line contingency are considered in observability analysis to ensure protection and control of power system from abnormal conditions. Modeling of ZIB constraints is included to minimize the number of PMU network allocations. This paper presents optimal allocation of PMU at sensitive buses with zero injection modeling, considering cost criteria and redundancy to increase the accuracy of state estimation solution without losing observability of the whole system. Simulations are carried out on IEEE 14, 30 and 57 bus systems and results obtained are compared with traditional and other state estimation methods available in the literature, to demonstrate the effectiveness of the proposed method.

  19. Heterometallic molecular precursors for a lithium-iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition.

    Science.gov (United States)

    Han, Haixiang; Wei, Zheng; Barry, Matthew C; Filatov, Alexander S; Dikarev, Evgeny V

    2017-05-02

    Three heterometallic single-source precursors with a Li : Fe = 1 : 1 ratio for a LiFeO 2 oxide material are reported. Heterometallic compounds LiFeL 3 (L = tbaoac (1), ptac (2), and acac(3)) have been obtained on a large scale, in nearly quantitative yields by one-step reactions that employ readily available reagents. The heterometallic precursor LiFe(acac) 3 (3) with small, symmetric substituents on the ligand (acac = pentane-2,4-dionate), maintains a 1D polymeric structure in the solid state that limits its volatility and prevents solubility in non-coordinating solvents. The application of the unsymmetrical ligands, tbaoac (tert-butyl acetoacetate) and ptac (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate), that exhibit different bridging properties at the two ends of the ligand, allowed us to change the connectivity pattern within the heterometallic assembly. The latter was demonstrated by structural characterization of heterometallic complexes LiFe(tbaoac) 3 (1) and LiFe(ptac) 3 (2) that consist of discrete heterocyclic tetranuclear molecules Li 2 Fe 2 L 6 . The compounds are highly volatile and exhibit a congruent sublimation character. DART mass spectrometric investigation revealed the presence of heterometallic molecules in the gas phase. The positive mode spectra are dominated by the presence of [M - L] + peaks (M = Li 2 Fe 2 L 6 ). In accord with their discrete molecular structure, complexes 1 and 2 are highly soluble in nearly all common solvents. In order to test the retention of the heterometallic structure in solution, the diamagnetic analog of 1, LiMg(tbaoac) 3 (4), has been isolated. Its tetranuclear molecular structure was found to be isomorphous to that of the iron counterpart. 1 H and 7 Li NMR spectroscopy unambiguously confirmed the presence of heterometallic molecules in solutions of non-coordinating solvents. The heterometallic precursor 1 was shown to exhibit clean thermal decomposition in air that results in phase-pure

  20. A series of Zn/Cd coordination polymers constructed from 1,4-naphthalenedicarboxylate and N-donor ligands: Syntheses, structures and luminescence sensing of Cr{sup 3+} in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Dong-Cheng [College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China); Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou 515063 (China); Fan, Yan; Si, Chang-Dai; Wu, Ya-Jun; Dong, Xiu-Yan; Yang, Yun-Xia; Yao, Xiao-Qiang [College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China); Liu, Jia-Cheng, E-mail: jcliu8@nwnu.edu.cn [College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China)

    2016-09-15

    A novel series of Zn/Cd coordination polymers based on H{sub 3}L, namely, [Zn{sub 2}(HL){sub 2}(bipy){sub 2}(H{sub 2}O){sub 6}]{sub n} (1), [Zn(HL)(phen)]{sub n} (2), [Cd{sub 3}L{sub 2}(bbi){sub 3}]{sub n} (3), [Zn{sub 3}L{sub 2}(bbi){sub 3}]{sub n} (4) [(H{sub 3}L =4-[(1-carboxynaphthalen-2-yl)oxy]phthalic acid, bipy =4,4′-bipyridine, phen =1,10-phenanthroline, bbi =1,1′-(1,4-butanediyl)bis(imidazole] have been successfully synthesized by solvothermal reaction. Compound 1 possesses two diverse 1D chains constructed by different bipy coligands, which were further connected to form a 3D supramolecular architecture by hydrogen bonding interactions. Compound 2 possesses a complicated 1D chain based on secondary building unit (SBU) with binuclear Zn cluster. Compounds 3 and 4 exhibit similar 2D→3D framework, which can be rationalized as (3,4,4)-connected 3D net with a Schläfli symbol of (6{sup 3}.8.10{sup 2}){sub 2}(6{sup 3}){sub 2}(6{sup 4}.8.10). In particular, compound 3 exhibited a high sensitivity for Cr{sup 3+} in aqueous solutions, which suggest that compound 3 is a promising luminescent probe for selectively sensing Cr{sup 3+}. - Graphical abstract: A series of novel Zn/Cd coordination polymers have been successfully synthesized by solvothermal reaction. The unique 3D Cd{sup 2+} polymer containing bbi as second ligand demonstrates high sensitivity for detection of toxic Cr{sup 3+} in aqueous solutions. Display Omitted - Highlights: • π-conjugated semirigid tricarboxylate ligands with naphthalene rings(H{sub 3}L) were rationally designed. • Four Zn/Cd coordination polymers based on H{sub 3}L have been successfully synthesized by solvothermal reaction. • Compound 3 is a promising luminescent probe for selectively sensing Cr{sup 3+} with high sensitivity in aqueous solutions.

  1. Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa

    2016-08-11

    Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(CtBu)(CH(2)tBu)(3) with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(SiOH)(SiNH2)], leads to [(SiNH2-)(SiO-)W(CHtBu)(CH(2)tBu)(2)] and [(SiNH2-)(SiO-)W(=CHtBu)(2)(CH(2)tBu). Variable temperature, H-1-H-1 2D double-quantum, H-1-C-13 HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(Si-OH)(Si-NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 degrees C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.

  2. Interaction of chemokine receptor CXCR4 in monomeric and dimeric state with its endogenous ligand CXCL12: coarse-grained simulations identify differences.

    Science.gov (United States)

    Cutolo, Pasquale; Basdevant, Nathalie; Bernadat, Guillaume; Bachelerie, Françoise; Ha-Duong, Tâp

    2017-02-01

    Despite the recent resolutions of the crystal structure of the chemokine receptor CXCR4 in complex with small antagonists or viral chemokine, a description at the molecular level of the interactions between the full-length CXCR4 and its endogenous ligand, the chemokine CXCL12, in relationship with the receptor recognition and activation, is not yet completely elucidated. Moreover, since CXCR4 is able to form dimers, the question of whether the CXCR4-CXCL12 complex has a 1:1 or 2:1 preferential stoichiometry is still an open question. We present here results of coarse-grained protein-protein docking and molecular dynamics simulations of CXCL12 in association with CXCR4 in monomeric and dimeric states. Our proposed models for the 1:1 and 2:1 CXCR4-CXCL12 quaternary structures are consistent with recognition and activation motifs of both partners provided by the available site-directed mutagenesis data. Notably, we observed that in the 2:1 complex, the chemokine N-terminus makes more steady contacts with the receptor residues critical for binding and activation than in the 1:1 structure, suggesting that the 2:1 stoichiometry would favor the receptor signaling activity with respect to the 1:1 association.

  3. Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa; Sofack-Kreutzer, Julien; Minenkov, Yury; Abou-Hamad, Edy; Hamzaoui, Bilel; Werghi, Baraa; Anjum, Dalaver H.; Cavallo, Luigi; Huang, Kuo-Wei; Basset, Jean-Marie

    2016-01-01

    Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(CtBu)(CH(2)tBu)(3) with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(SiOH)(SiNH2)], leads to [(SiNH2-)(SiO-)W(CHtBu)(CH(2)tBu)(2)] and [(SiNH2-)(SiO-)W(=CHtBu)(2)(CH(2)tBu). Variable temperature, H-1-H-1 2D double-quantum, H-1-C-13 HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(Si-OH)(Si-NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 degrees C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.

  4. Two high-affinity ligand binding states of uterine estrogen receptor distinguished by modulation of hydrophobic environment

    International Nuclear Information System (INIS)

    Hutchens, T.W.; Li, C.M.; Zamah, N.M.; Besch, P.K.

    1987-01-01

    The steroid binding function of soluble (cytosolic) estrogen receptors from calf uteri was evaluated under conditions known to modify the extent of hydrophobic interaction with receptor-associated proteins. Receptor preparations were equilibrated into 6 M urea buffers and control buffers by chromatography through small columns of Sephadex G-25 or by dialysis at 0.6 0 C. Equilibrium dissociation constants (K/sub d/) and binding capacities (n) of experimental and control receptor preparations were determined by 13-point Scatchard analyses using concentrations of 17β-[ 3 H]estradiol from 0.05 to 10 nM. Nonspecific binding was determined at each concentration by parallel incubations with a 200-fold molar excess of the receptor-specific competitor diethylstilbestrol. The control receptor population was consistently found to be a single class of binding sites with a high affinity for estradiol which was unaffected by G-25 chromatography, by dialysis, by dilution, or by the presence of 0.4 M KCl. However, equilibration into 6 M urea induced a discrete (10-fold) reduction in receptor affinity to reveal a second, thermodynamically stable, high-affinity binding state. The presence of 0.4 M KCl did not significantly influence the discrete change in receptor affinity induced by urea. The effects of urea on both receptor affinity and binding capacity were reversible, suggesting a lack of covalent modification. These results demonstrate nonenzymatic means by which not only the binding capacity but also the affinity of receptor for estradiol can be reversibly controlled, suggesting that high concentrations of urea might be more effectively utilized during the physicochemical characterization and purification of steroid receptor proteins

  5. [Correction of acute psychotic states in schizophrenia by rispolept solution per os].

    Science.gov (United States)

    Panteleeva, G P; Korenev, A N; Barkhatova, A N

    2004-01-01

    To stop acute psychotic states during the first episode or relapses of schizophrenia, 37 patients were treated with rispolept solution per os during 2 weeks. A procedure of a fast transition to optimal daily doses of the drug after 1 day of treatment (searching period) with a following stabilization of mean daily doses (5.02-5.7 mg) at the stage of 14 day treatment course was used. Positive therapeutic effect by PANSS total score reduction, along with minor side-effects, were found in 91.9% patients. Stopping effect of rispolept on acute psychotic states, emerging from day 1 of the treatment, and general antipsychotic and therapeutic action, beginning from day 2-3 and increasing to day 14, were stated out. Efficacy of the drug in syndromes differing by psychopathological structure is emphasized.

  6. Ruthenium (4) and ruthenium (3) state in hydrochloric acid solutions under microwave irradiation

    International Nuclear Information System (INIS)

    Bashilov, A.V.; Kuz'min, N.M.; Nesterov, A.A.; Runov, V.K.

    2000-01-01

    Reactions of hydration, poly- and depolymerization, oxidation-reduction processes with ruthenium (4) and ruthenium (3) participation are investigated in hydrochloric acid solutions under microwave irradiation by the methods of molecular absorption spectroscopy in UV visible region taking K 4 [Ru 2 OCl 10 ] as an example. Content of state forms of ruthenium (4) and ruthenium (3), absorption characteristics of forming complexes are calculated. Variation of microwave irradiation parameters and HCl concentration permits to prepare solutions containing [RuCl 6 ] 2+ (95 %) and [(RuOH) 2 (H 2 O) 6 (OH) 2 ] 4+ (98 %) preeminently predominant forms. The role of microwave effect directly is established taking as an example the process of ruthenium (4) hydration [ru

  7. THERMODYNAMIC PROPERTIES OF NONAQUEOUS SINGLE SALT SOLUTIONS USING THE Q-ELECTROLATTICE EQUATION OF STATE

    Directory of Open Access Journals (Sweden)

    A. Zuber

    2015-09-01

    Full Text Available AbstractThe correlation of thermodynamic properties of nonaqueous electrolyte solutions is relevant to design and operation of many chemical processes, as in fertilizer production and the pharmaceutical industry. In this work, the Q-electrolattice equation of state (EOS is used to model vapor pressure, mean ionic activity coefficient, osmotic coefficient, and liquid density of sixteen methanol and ten ethanol solutions containing single strong 1:1 and 2:1 salts. The Q-electrolattice comprises the lattice-based Mattedi-Tavares-Castier (MTC EOS, the Born term and the explicit MSA term. The model requires two adjustable parameters per ion, namely the ionic diameter and the solvent-ion interaction energy. Predictions of osmotic coefficient at 298.15 K and liquid density at different temperatures are also presented.

  8. Recent Advances in Characterization of Lignin Polymer by Solution-State Nuclear Magnetic Resonance (NMR Methodology

    Directory of Open Access Journals (Sweden)

    Run-Cang Sun

    2013-01-01

    Full Text Available The demand for efficient utilization of biomass induces a detailed analysis of the fundamental chemical structures of biomass, especially the complex structures of lignin polymers, which have long been recognized for their negative impact on biorefinery. Traditionally, it has been attempted to reveal the complicated and heterogeneous structure of lignin by a series of chemical analyses, such as thioacidolysis (TA, nitrobenzene oxidation (NBO, and derivatization followed by reductive cleavage (DFRC. Recent advances in nuclear magnetic resonance (NMR technology undoubtedly have made solution-state NMR become the most widely used technique in structural characterization of lignin due to its versatility in illustrating structural features and structural transformations of lignin polymers. As one of the most promising diagnostic tools, NMR provides unambiguous evidence for specific structures as well as quantitative structural information. The recent advances in two-dimensional solution-state NMR techniques for structural analysis of lignin in isolated and whole cell wall states (in situ, as well as their applications are reviewed.

  9. Training Course of Experimental Chemistry in the Nuclear Fuel Cycle: Solid State and Solution Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ju hyeong; Park, Kwangheon; Kim, Tae hoon; Park, Hyoung gyu; Kim, Jisu [Kyunghee University, Yongin (Korea, Republic of); Song, Hyuk jin [Dongguk University, Gyeongju (Korea, Republic of); Lee, Chan ki; Kang, Do kyu; Jeong, Hyeon jun [UNIST, Ulsan (Korea, Republic of)

    2016-10-15

    In this experimental study program in Tohoku University, basic experiments were done by the participants. First one is the hydrogen reduction experiment of the mixture of UO{sub 2} and ZrO{sub 2}. Second one is to observe microscopic structure of solid solution of UO{sub 2} and ZrO{sub 2} using SEM/EDX and XRD system, simulated fuel debris. Third one is milking process of {sup 239}Np from {sup 243}Am by solvent extraction using Tri-n-Octylamine (TOA). Last one is solvent extraction in PUREX by the simulated mixed aqueous solution of U, {sup 85}Sr and {sup 239}Np which is represented minor actinide elements included in the spent nuclear fuel. Uranium is separated from aqueous phase to organic phase during solvent extraction procedure using TBP and dodecane. Also, neptunium can be extracted to organic phase as nitric acid concentration change. The extraction behavior of neptunium is different by oxidation state in aqueous phase. The behavior of neptunium is represented as a combined form of these oxidation states in experiment. Therefore, because the oxidation states of neptunium can be controlled by controlling the concentration of nitric acid, the extractability of neptunium can be controlled.

  10. Ground State Solutions for a Class of Fractional Differential Equations with Dirichlet Boundary Value Condition

    Directory of Open Access Journals (Sweden)

    Zhigang Hu

    2014-01-01

    Full Text Available In this paper, we apply the method of the Nehari manifold to study the fractional differential equation (d/dt((1/2 0Dt-β(u′(t+(1/2 tDT-β(u′(t=  f(t,u(t, a.e. t∈[0,T], and u0=uT=0, where  0Dt-β, tDT-β are the left and right Riemann-Liouville fractional integrals of order 0≤β<1, respectively. We prove the existence of a ground state solution of the boundary value problem.

  11. Positive ground state solutions to Schrodinger-Poisson systems with a negative non-local term

    Directory of Open Access Journals (Sweden)

    Yan-Ping Gao

    2015-04-01

    Full Text Available In this article, we study the Schrodinger-Poisson system $$\\displaylines{ -\\Delta u+u-\\lambda K(x\\phi(xu=a(x|u|^{p-1}u, \\quad x\\in\\mathbb{R}^3, \\cr -\\Delta\\phi=K(xu^{2},\\quad x\\in\\mathbb{R}^3, }$$ with $p\\in(1,5$. Assume that $a:\\mathbb{R}^3\\to \\mathbb{R^{+}}$ and $K:\\mathbb{R}^3\\to \\mathbb{R^{+}}$ are nonnegative functions and satisfy suitable assumptions, but not requiring any symmetry property on them, we prove the existence of a positive ground state solution resolved by the variational methods.

  12. Numerical solution of the Schrodinger equation for stationary bound states using nodel theorem

    International Nuclear Information System (INIS)

    Chen Zhijiang; Kong Fanmei; Din Yibin

    1987-01-01

    An iterative procedure for getting the numerical solution of Schrodinger equation on stationary bound states is introduced. The theoretical foundtion, the practical steps and the method are presented. An example is added at the end. Comparing with other methods, the present one requires less storage, less running time but posesses higher accuracy. It can be run on the personal computer or microcomputer with 256 K memory and 16 bit word length such as IBM/PC, MC68000/83/20, PDP11/23 etc

  13. Ground state solutions for Choquard type equations with a singular potential

    Directory of Open Access Journals (Sweden)

    Tao Wang

    2017-02-01

    Full Text Available This article concerns the Choquard type equation $$ -\\Delta u+V(xu=\\Big(\\int_{\\mathbb{R}^N}\\frac{|u(y|^p}{|x-y|^{N-\\alpha}}dy\\Big |u|^{p-2}u,\\quad x\\in \\mathbb{R}^N, $$ where $N\\geq3$, $\\alpha\\in ((N-4_+,N$, $2\\leq p <(N+\\alpha/(N-2$ and V(x is a possibly singular potential and may be unbounded below. Applying a variant of the Lions' concentration-compactness principle, we prove the existence of ground state solution of the above equations.

  14. A Solution Space for a System of Null-State Partial Differential Equations: Part 3

    Science.gov (United States)

    Flores, Steven M.; Kleban, Peter

    2015-01-01

    This article is the third of four that completely and rigorously characterize a solution space for a homogeneous system of 2 N + 3 linear partial differential equations (PDEs) in 2 N variables that arises in conformal field theory (CFT) and multiple Schramm-Löwner evolution (SLE κ ). The system comprises 2 N null-state equations and three conformal Ward identities that govern CFT correlation functions of 2 N one-leg boundary operators. In the first two articles (Flores and Kleban, in Commun Math Phys, arXiv:1212.2301, 2012; Commun Math Phys, arXiv:1404.0035, 2014), we use methods of analysis and linear algebra to prove that dim , with C N the Nth Catalan number. Extending these results, we prove in this article that dim and entirely consists of (real-valued) solutions constructed with the CFT Coulomb gas (contour integral) formalism. In order to prove this claim, we show that a certain set of C N such solutions is linearly independent. Because the formulas for these solutions are complicated, we prove linear independence indirectly. We use the linear injective map of Lemma 15 in Flores and Kleban (Commun Math Phys, arXiv:1212.2301, 2012) to send each solution of the mentioned set to a vector in , whose components we find as inner products of elements in a Temperley-Lieb algebra. We gather these vectors together as columns of a symmetric matrix, with the form of a meander matrix. If the determinant of this matrix does not vanish, then the set of C N Coulomb gas solutions is linearly independent. And if this determinant does vanish, then we construct an alternative set of C N Coulomb gas solutions and follow a similar procedure to show that this set is linearly independent. The latter situation is closely related to CFT minimal models. We emphasize that, although the system of PDEs arises in CFT in away that is typically non-rigorous, our treatment of this system here and in Flores and Kleban (Commun Math Phys, arXiv:1212.2301, 2012; Commun Math Phys, arXiv:1404

  15. Colloidal-quantum-dot photovoltaics using atomic-ligand passivation

    KAUST Repository

    Tang, Jiang

    2011-09-18

    Colloidal-quantum-dot (CQD) optoelectronics offer a compelling combination of solution processing and spectral tunability through quantum size effects. So far, CQD solar cells have relied on the use of organic ligands to passivate the surface of the semiconductor nanoparticles. Although inorganic metal chalcogenide ligands have led to record electronic transport parameters in CQD films, no photovoltaic device has been reported based on such compounds. Here we establish an atomic ligand strategy that makes use of monovalent halide anions to enhance electronic transport and successfully passivate surface defects in PbS CQD films. Both time-resolved infrared spectroscopy and transient device characterization indicate that the scheme leads to a shallower trap state distribution than the best organic ligands. Solar cells fabricated following this strategy show up to 6% solar AM1.5G power-conversion efficiency. The CQD films are deposited at room temperature and under ambient atmosphere, rendering the process amenable to low-cost, roll-by-roll fabrication. © 2011 Macmillan Publishers Limited. All rights reserved.

  16. Reduction of dinitrogen ligands

    International Nuclear Information System (INIS)

    Richards, R.L.

    1983-01-01

    Processes of dinitrogen ligand reduction in complexes of transition metals are considered. The basic character of the dinitrogen ligand is underlined. Data on X-ray photoelectronic spectroscopy and intensities of bands ν (N 2 ) in IR-spectra of nitrogen complexes are given. The mechanism of protonation of an edge dinitrogen ligand is discussed. Model systems and mechanism of nitrogenogenase are compared

  17. A Complete Parametric Solutions of Eigenstructure Assignment by State-Derivative Feedback for Linear Control Systems

    Directory of Open Access Journals (Sweden)

    T. H. S. Abdelaziz

    2005-01-01

    Full Text Available In this paper we introduce a complete parametric approach for solving the problem of eigenstructure assignment via state-derivative feedback for linear systems. This problem is always solvable for any controllable systems iff the open-loop system matrix is nonsingular. In this work, two parametric solutions to the feedback gain matrix are introduced that describe the available degrees of freedom offered by the state-derivative feedback in selecting the associated eigenvectors from an admissible class. These freedoms can be utilized to improve robustness of the closed-loop system. Accordingly, the sensitivity of the assigned eigenvalues to perturbations in the system and gain matrix is minimized. Numerical examples are included to show the effectiveness of the proposed approach. 

  18. Stability of periodic steady-state solutions to a non-isentropic Euler-Poisson system

    Science.gov (United States)

    Liu, Cunming; Peng, Yue-Jun

    2017-06-01

    We study the stability of periodic smooth solutions near non-constant steady-states for a non-isentropic Euler-Poisson system without temperature damping term. The system arises in the theory of semiconductors for which the doping profile is a given smooth function. In this stability problem, there are no special restrictions on the size of the doping profile, but only on the size of the perturbation. We prove that small perturbations of periodic steady-states are exponentially stable for large time. For this purpose, we introduce new variables and choose a non-diagonal symmetrizer of the full Euler equations to recover dissipation estimates. This also allows to make the proof of the stability result very simple and concise.

  19. Implicit unified gas-kinetic scheme for steady state solutions in all flow regimes

    Science.gov (United States)

    Zhu, Yajun; Zhong, Chengwen; Xu, Kun

    2016-06-01

    This paper presents an implicit unified gas-kinetic scheme (UGKS) for non-equilibrium steady state flow computation. The UGKS is a direct modeling method for flow simulation in all regimes with the updates of both macroscopic flow variables and microscopic gas distribution function. By solving the macroscopic equations implicitly, a predicted equilibrium state can be obtained first through iterations. With the newly predicted equilibrium state, the evolution equation of the gas distribution function and the corresponding collision term can be discretized in a fully implicit way for fast convergence through iterations as well. The lower-upper symmetric Gauss-Seidel (LU-SGS) factorization method is implemented to solve both macroscopic and microscopic equations, which improves the efficiency of the scheme. Since the UGKS is a direct modeling method and its physical solution depends on the mesh resolution and the local time step, a physical time step needs to be fixed before using an implicit iterative technique with a pseudo-time marching step. Therefore, the physical time step in the current implicit scheme is determined by the same way as that in the explicit UGKS for capturing the physical solution in all flow regimes, but the convergence to a steady state speeds up through the adoption of a numerical time step with large CFL number. Many numerical test cases in different flow regimes from low speed to hypersonic ones, such as the Couette flow, cavity flow, and the flow passing over a cylinder, are computed to validate the current implicit method. The overall efficiency of the implicit UGKS can be improved by one or two orders of magnitude in comparison with the explicit one.

  20. One-electron reduction of 1,2-dihydroxy-9,10-anthraquinone and some of its transition metal complexes in aqueous solution and in aqueous isopropanol-acetone-mixed solvent: a steady-state and pulse radiolysis study

    International Nuclear Information System (INIS)

    Das, S.; Bhattacharya, A.; Mandal, P.C.; Rath, M.C.; Mukherjee, T.

    2002-01-01

    One-electron reduction of 1,2-dihydroxy-9,10-anthraquinone (DHA) and its complexes with Cu(II), Ni(II) and Fe(III), by acetone ketyl radical, (CH 3 ) 2 C·OH, was carried out in aqueous solution and in aqueous isopropanol acetone mixed solvent using both steady-state gamma radiolysis and pulse radiolysis techniques. The rate constants for the reduction of DHA at different pH values by the ketyl radical are in the order of ∼10 9 dm 3 mol -1 s -1 , whereas those for the metal complexes are comparatively less. These rate constants are, however, in conformity with the one-electron reduction potentials of the ligand in free DHA and in its metal complexes. Decay kinetics of the one-electron reduced semiquinones of the free ligand and its metal complexes suggest disproportionation of the semiquinone in the case of the free ligand and intermolecular electron transfer from the co-ordinated semiquinone radical to the metal centre in the case of the metal complexes

  1. Chapter 6. Scaling Up Solutions to State, National and Global Levels

    Directory of Open Access Journals (Sweden)

    Daniel Kammen

    2016-12-01

    Full Text Available Scaling-up solutions require learning and adapting lessons between locations and at different scales. To accomplish this, common metrics are vital to building a shared language. For California, this has meant careful financial, cradle-to-grave life-cycle assessment methods leading to carbon accounting in many avenues of government (via the Low Carbon Fuel Standard or the Cap and Trade program. These methods themselves interact, such as the use of carbon accounting for the resources needed to manage water and other key resources; the use of criteria air pollution monitoring to identify environmental injustices; and the use of carbon market revenues to address these inequalities, through investment in best available abatement technologies (BACT and in job creation in disadvantaged communities anticipated in the emerging clean energy sector.  Creating interdisciplinary partnerships across the UC Campuses and the National Laboratories to innovate science and technology is critical to scalable carbon neutrality solutions. As an example, we can build coordinated research and development programs across UC and California, with strong partnerships with the Federal government to coordinate and “multiply” resources that accelerate development and deployment. These partnerships should be strongly goal-focused, i.e., they are created to solve specific, large problems, to enable quantitatively measurable outcomes within energy generation, efficiency and CO2 abatement categories. Intersectoral partnerships should be fostered across campuses, laboratories, with state, federal and multi-lateral organizations funding to develop technologies and deploy solutions at scale. Integrated partnerships with industry are required to influence markets, deploy solutions, and create new industries and jobs.  Beyond California, we need to establish consortia with industry and foundations to deploy solutions at the regional, state, national, and international scale to

  2. Ligands and modifiers in vitreous materials the spectroscopy of condensed systems

    CERN Document Server

    Margaryan, Alfred

    1999-01-01

    The study of the effect of ligand and modifier ions on the spectroscopic properties of dn or fn elements in vitreous materials is important for the development of controllable lasers and amplifiers. The spectroscopic characteristics of inorganic compounds of transition elements and their solutions are well understood theoretically in the spectrochemistry of complexes, but developments for vitreous materials in these conditions have not been well documented. This book fills the gap by applying the ligand field theory of solid materials to the vitreous state, and presenting the data obtained fro

  3. A Versatile Dinucleating Ligand Containing Sulfonamide Groups

    DEFF Research Database (Denmark)

    Sundberg, Jonas; Witt, Hannes; Cameron, Lisa

    2014-01-01

    ligand can be prepared in aqueous solutions using only divalent metal ions. Two of the copper(II) complexes, [Cu2(psmp)(OH)] and [Cu2(psmp)(OAc)2]-, demonstrate the anticipated 1:2 ligand/metal stoichiometry and show that the dimetallic binding site created for exogenous ligands possesses high inherent...... of antiferromagnetic coupling. This is corroborated computationally by broken-symmetry density functional theory, which for isotropic modeling of the coupling predicts an antiferromagnetic coupling strength of J = 70.5 cm-1....

  4. Combined solid state and solution NMR studies of α,ε-15N labeled bovine rhodopsin

    International Nuclear Information System (INIS)

    Werner, Karla; Lehner, Ines; Dhiman, Harpreet Kaur; Richter, Christian; Glaubitz, Clemens; Schwalbe, Harald; Klein-Seetharaman, Judith; Khorana, H. Gobind

    2007-01-01

    Rhodopsin is the visual pigment of the vertebrate rod photoreceptor cell and is the only member of the G protein coupled receptor family for which a crystal structure is available. Towards the study of dynamics in rhodopsin, we report NMR-spectroscopic investigations of α,ε- 15 N-tryptophan labeled rhodopsin in detergent micelles and reconstituted in phospholipids. Using a combination of solid state 13 C, 15 N-REDOR and HETCOR experiments of all possible 13 C' i-1 carbonyl/ 15 N i -tryptophan isotope labeled amide pairs, and H/D exchange 1 H, 15 N-HSQC experiments conducted in solution, we assigned chemical shifts to all five rhodopsin tryptophan backbone 15 N nuclei and partially to their bound protons. 1 H, 15 N chemical shift assignment was achieved for indole side chains of Trp35 1.30 and Trp175 4.65 . 15 N chemical shifts were found to be similar when comparing those obtained in the native like reconstituted lipid environment and those obtained in detergent micelles for all tryptophans except Trp175 4.65 at the membrane interface. The results suggest that the integrated solution and solid state NMR approach presented provides highly complementary information in the study of structure and dynamics of large membrane proteins like rhodopsin

  5. Multiple Multidentate Halogen Bonding in Solution, in the Solid State, and in the (Calculated) Gas Phase.

    Science.gov (United States)

    Jungbauer, Stefan H; Schindler, Severin; Herdtweck, Eberhardt; Keller, Sandro; Huber, Stefan M

    2015-09-21

    The binding properties of neutral halogen-bond donors (XB donors) bearing two multidentate Lewis acidic motifs toward halides were investigated. Employing polyfluorinated and polyiodinated terphenyl and quaterphenyl derivatives as anion receptors, we obtained X-ray crystallographic data of the adducts of three structurally related XB donors with tetraalkylammonium chloride, bromide, and iodide. The stability of these XB complexes in solution was determined by isothermal titration calorimetry (ITC), and the results were compared to X-ray analyses as well as to calculated binding patterns in the gas phase. Density functional theory (DFT) calculations on the gas-phase complexes indicated that the experimentally observed distortion of the XB donors during multiple multidentate binding can be reproduced in 1:1 complexes with halides, whereas adducts with two halides show a symmetric binding pattern in the gas phase that is markedly different from the solid state structures. Overall, this study demonstrates the limitations in the transferability of binding data between solid state, solution, and gas phase in the study of complex multidentate XB donors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Two-state model of excess electron relaxation and geminate recombination in water and aqueous solutions

    International Nuclear Information System (INIS)

    Fedorenko, S.G.

    2010-01-01

    Graphical abstract: After photo-induced ionization a free electron suffers a quick conversion to a solvated state, and then recombines with the parent atom or ion. However, high mobility and reactivity of a free electron can allow the electron to delocalize and recombine in the free state. The theory of two channel processes of geminate electron recombination is developed and applied to the experiment of three-pulse generation of excess electrons in water. - Abstract: After photo-induced ionization a free electron suffers a quick conversion to a solvated state, and then can recombine with the parent atom or ion. However, high mobility and reactivity of a free electron can allow the electron to delocalize and recombine in the free state. The theory of two channel processes of geminate electron recombination is developed here for the general type of the Markovian motion of reactants. A contact model is used for analytical solution of the problem of geminate recombination of neutral and charged reactants. The theory is applied to the experiment of three-pulse generation of excess electrons in water.

  7. Organoactinide chemistry: synthesis, structure, and solution dynamics

    International Nuclear Information System (INIS)

    Brennan, J.G.

    1985-12-01

    This thesis considers three aspects of organoactinide chemistry. In chapter one, a bidentate phosphine ligand was used to kinetically stabilize complexes of the type Cp 2 MX 2 . Ligand redistribution processes are present throughout the synthetic work, as has often been observed in uranium cyclopentadienyl chemistry. The effects of covalent M-L bonding on the solution and solid state properties of U(III) coordination complexes are considered. In particular, the nature of the more subtle interaction between the metal and the neutral ligand are examined. Using relative basicity data obtained in solution, and solid state structural data (and supplemented by gas phase photoelectron measurements), it is demonstrated that the more electron rich U(III) centers engage in significant U → L π-donation. Trivalent uranium is shown to be capable of acting either as a one- or two-electron reducing agent toward a wide variety of unsaturated organic and inorganic molecules, generating molecular classes unobtainable via traditional synthetic approaches, as well as offering an alternative synthetic approach to molecules accessible via metathesis reactions. Ligand redistribution processes are again observed, but given the information concerning ligand lability, this reactivity pattern is applied to the synthesis of pure materials inaccessible from redox chemistry. 214 refs., 33 figs., 10 tabs

  8. Bound state solution of Dirac equation for Hulthen plus trigonometric Rosen Morse non-central potential using Romanovski polynomial

    Energy Technology Data Exchange (ETDEWEB)

    Suparmi, A., E-mail: suparmiuns@gmail.com; Cari, C., E-mail: suparmiuns@gmail.com [Physics Department, Post Graduate Study, Sebelas Maret University (Indonesia); Angraini, L. M. [Physics Department, Mataram University (Indonesia)

    2014-09-30

    The bound state solutions of Dirac equation for Hulthen and trigonometric Rosen Morse non-central potential are obtained using finite Romanovski polynomials. The approximate relativistic energy spectrum and the radial wave functions which are given in terms of Romanovski polynomials are obtained from solution of radial Dirac equation. The angular wave functions and the orbital quantum number are found from angular Dirac equation solution. In non-relativistic limit, the relativistic energy spectrum reduces into non-relativistic energy.

  9. Ligands in PSI structures

    International Nuclear Information System (INIS)

    Kumar, Abhinav; Chiu, Hsiu-Ju; Axelrod, Herbert L.; Morse, Andrew; Elsliger, Marc-André; Wilson, Ian A.; Deacon, Ashley

    2010-01-01

    A survey of the types and frequency of ligands that are bound to PSI structures is analyzed as well as their utility in functional annotation of previously uncharacterized proteins. Approximately 65% of PSI structures report some type of ligand(s) that is bound in the crystal structure. Here, a description is given of how such ligands are handled and analyzed at the JCSG and a survey of the types, variety and frequency of ligands that are observed in the PSI structures is also compiled and analyzed, including illustrations of how these bound ligands have provided functional clues for annotation of proteins with little or no previous experimental characterization. Furthermore, a web server was developed as a tool to mine and analyze the PSI structures for bound ligands and other identifying features

  10. A Heteroleptic Ferrous Complex with Mesoionic Bis(1,2,3-triazol-5-ylidene) Ligands: Taming the MLCT Excited State of Iron(II)

    DEFF Research Database (Denmark)

    Liu, Yizhu; Kjær, Kasper Skov; Fredin, Lisa A.

    2015-01-01

    based on sequentially furnishing the Fe-II center with the benchmark 2,2-bipyridine (bpy) ligand and the more strongly sigma-donating mesoionic ligand, 4,4-bis(1,2,3-triazol-5-ylidene) (btz). Complex1 was comprehensively characterized by electrochemistry, static and ultrafast spectroscopy, and quantum...... chemical calculations and compared to [Fe(bpy)(3)](PF6)(2) and (TBA)(2)[Fe(bpy)(CN)(4)]. Heteroleptic complex1 extends the absorption spectrum towards longer wavelengths compared to a previously synthesized homoleptic Fe-II NHC complex. The combination of the mesoionic nature of btz and the heteroleptic...

  11. A Solution Space for a System of Null-State Partial Differential Equations: Part 1

    Science.gov (United States)

    Flores, Steven M.; Kleban, Peter

    2015-01-01

    This article is the first of four that completely and rigorously characterize a solution space for a homogeneous system of 2 N + 3 linear partial differential equations (PDEs) in 2 N variables that arises in conformal field theory (CFT) and multiple Schramm-Löwner evolution (SLE). In CFT, these are null-state equations and conformal Ward identities. They govern partition functions for the continuum limit of a statistical cluster or loop-gas model, such as percolation, or more generally the Potts models and O( n) models, at the statistical mechanical critical point. (SLE partition functions also satisfy these equations.) For such a lattice model in a polygon with its 2 N sides exhibiting a free/fixed side-alternating boundary condition , this partition function is proportional to the CFT correlation function where the w i are the vertices of and where is a one-leg corner operator. (Partition functions for "crossing events" in which clusters join the fixed sides of in some specified connectivity are linear combinations of such correlation functions.) When conformally mapped onto the upper half-plane, methods of CFT show that this correlation function satisfies the system of PDEs that we consider. In this first article, we use methods of analysis to prove that the dimension of this solution space is no more than C N , the Nth Catalan number. While our motivations are based in CFT, our proofs are completely rigorous. This proof is contained entirely within this article, except for the proof of Lemma 14, which constitutes the second article (Flores and Kleban, in Commun Math Phys, arXiv:1404.0035, 2014). In the third article (Flores and Kleban, in Commun Math Phys, arXiv:1303.7182, 2013), we use the results of this article to prove that the solution space of this system of PDEs has dimension C N and is spanned by solutions constructed with the CFT Coulomb gas (contour integral) formalism. In the fourth article (Flores and Kleban, in Commun Math Phys, arXiv:1405

  12. State of the Art in LP-WAN Solutions for Industrial IoT Services

    Directory of Open Access Journals (Sweden)

    Ramon Sanchez-Iborra

    2016-05-01

    Full Text Available The emergence of low-cost connected devices is enabling a new wave of sensorization services. These services can be highly leveraged in industrial applications. However, the technologies employed so far for managing this kind of system do not fully cover the strict requirements of industrial networks, especially those regarding energy efficiency. In this article a novel paradigm, called Low-Power Wide Area Networking (LP-WAN, is explored. By means of a cellular-type architecture, LP-WAN–based solutions aim at fulfilling the reliability and efficiency challenges posed by long-term industrial networks. Thus, the most prominent LP-WAN solutions are reviewed, identifying and discussing the pros and cons of each of them. The focus is also on examining the current deployment state of these platforms in Spain. Although LP-WAN systems are at early stages of development, they represent a promising alternative for boosting future industrial IIoT (Industrial Internet of Things networks and services.

  13. State of the Art in LP-WAN Solutions for Industrial IoT Services.

    Science.gov (United States)

    Sanchez-Iborra, Ramon; Cano, Maria-Dolores

    2016-05-17

    The emergence of low-cost connected devices is enabling a new wave of sensorization services. These services can be highly leveraged in industrial applications. However, the technologies employed so far for managing this kind of system do not fully cover the strict requirements of industrial networks, especially those regarding energy efficiency. In this article a novel paradigm, called Low-Power Wide Area Networking (LP-WAN), is explored. By means of a cellular-type architecture, LP-WAN-based solutions aim at fulfilling the reliability and efficiency challenges posed by long-term industrial networks. Thus, the most prominent LP-WAN solutions are reviewed, identifying and discussing the pros and cons of each of them. The focus is also on examining the current deployment state of these platforms in Spain. Although LP-WAN systems are at early stages of development, they represent a promising alternative for boosting future industrial IIoT (Industrial Internet of Things) networks and services.

  14. Fabrication and Performance of All-Solid-State Chloride Sensors in Synthetic Concrete Pore Solutions

    Directory of Open Access Journals (Sweden)

    Hongwei Deng

    2010-11-01

    Full Text Available One type of all-solid-state chloride sensor was fabricated using a MnO2 electrode and a Ag/AgCl electrode. The potentiometric response of the sensor to chloride in synthetic concrete pore solutions was systematically studied, and the polarization performance was also evaluated. The results show a good linear relationship between the potential reading of the sensor and the logarithm of chloride activity (concentration ranges from 0.05 to 5.0 M, and the potential value remains stable with increasing immersion time. The existence of K+, Ca2+, Na+ and SO42− ions have little influence on the potentiometric response of the sensor to chloride, but the pH has a significant influence on the potential value of the sensor at low chloride concentration. The potential reading of the sensor increases linearly with the solution temperature over the range from 5 to 45 °C. Meanwhile, an excellent polarization behavior is proven by galvanostatic and potentiodynamic tests. All of the results reveal that the developed sensor has a great potential for monitoring chloride ions in concrete environments.

  15. Fabrication and performance of all-solid-state chloride sensors in synthetic concrete pore solutions.

    Science.gov (United States)

    Gao, Xiaojian; Zhang, Jian; Yang, Yingzi; Deng, Hongwei

    2010-01-01

    One type of all-solid-state chloride sensor was fabricated using a MnO(2) electrode and a Ag/AgCl electrode. The potentiometric response of the sensor to chloride in synthetic concrete pore solutions was systematically studied, and the polarization performance was also evaluated. The results show a good linear relationship between the potential reading of the sensor and the logarithm of chloride activity (concentration ranges from 0.05 to 5.0 M), and the potential value remains stable with increasing immersion time. The existence of K(+), Ca(2+), Na(+) and SO(4) (2-) ions have little influence on the potentiometric response of the sensor to chloride, but the pH has a significant influence on the potential value of the sensor at low chloride concentration. The potential reading of the sensor increases linearly with the solution temperature over the range from 5 to 45 °C. Meanwhile, an excellent polarization behavior is proven by galvanostatic and potentiodynamic tests. All of the results reveal that the developed sensor has a great potential for monitoring chloride ions in concrete environments.

  16. Structural parameters of polyethylenes obtained using a palladium catalyst: dilute solution and solid state studies

    International Nuclear Information System (INIS)

    Meneghetti, Simoni Plentz; Lutz, Pierre J.; Duval, M.; Kress, Jacky; Lapp, A.

    2001-01-01

    Polyethylenes were obtained using palladium catalyst [(Ar N=C(Me)-C(Me)=N Ar) Pd(CH 2 ) 3 (COOMe)] + BAr' 4 - (VERSIPOL TM ); Ar2,6-i-Pr 2 -C 6 H 3 and Ar'3,5-(CF 3 ) 2 -C 6 H 3 . The combination of dilute solution and solid state characterization of these polyethylenes revealed strong differences between structural parameters of samples prepared under almost identical conditions except ethylene pressure (6, 3 and 1 bar). These differences can be explained by the fact that samples prepared at 6 bar are almost linear, with only a few short branches, whereas those synthesized at 1 bar are highly branched or even hyper branched. (author)

  17. On the application of finite element method in the solution of steady state diffusion equation

    International Nuclear Information System (INIS)

    Ono, S.

    1982-01-01

    The solution of the steady state neutron diffusion equation is obtained by using the finite element method. Specifically the variational approach is used for one dimensional problems and the weighted residual method (Galerkin) for one and two dimensional problems. The spatial domain is divided into retangular elements and the neutron flux is approximated by linear (one dimensional case), and bilinear (two-dimensional case) functions. Numerical results are obtained with a FORTRAN IV computer program and compared with those obtained by the finite difference CITATION code. The results show that linear or bilinear functions, do not satisfactorily describe the differential parameters in highly heterogeneous reactor cases, but provide good results for integral parameters such as multiplication factor. (Author) [pt

  18. Investigating the Mechanisms of Amylolysis of Starch Granules by Solution-State NMR

    Science.gov (United States)

    2015-01-01

    Starch is a prominent component of the human diet and is hydrolyzed by α-amylase post-ingestion. Probing the mechanism of this process has proven challenging, due to the intrinsic heterogeneity of individual starch granules. By means of solution-state NMR, we demonstrate that flexible polysaccharide chains protruding from the solvent-exposed surfaces of waxy rice starch granules are highly mobile and that during hydrothermal treatment, when the granules swell, the number of flexible residues on the exposed surfaces increases by a factor of 15. Moreover, we show that these flexible chains are the primary substrates for α-amylase, being cleaved in the initial stages of hydrolysis. These findings allow us to conclude that the quantity of flexible α-glucan chains protruding from the granule surface will greatly influence the rate of energy acquisition from digestion of starch. PMID:25815624

  19. Existence of non-unique steady state solutions to the RMF current drive equations

    Energy Technology Data Exchange (ETDEWEB)

    Hugrass, W N [Flinders Univ. of South Australia, Bedford Park. School of Physical Sciences

    1985-05-04

    It is shown that the value of the d.c. current driven in a plasma cylinder by means of a rotating magnetic field (RMF) is not unique for R/delta >= 6 and eBsub(..omega..)/..nu..sub(ei)m approx.R/delta, where R is the radius of the plasma cylinder, delta is the classical skin depth, ..nu..sub(ei) is the electron-ion momentum transfer collision frequency, Bsub(..omega..) is the magnitude of the rotating magnetic field, e is the electron charge and m is the electron mass. This effect is predicted using three distinct approaches: (i) a steady state anaysis which ignores the second and higher harmonics of the fields and currents; (ii) a qualitative model which utilizes the analogy between the RMF current drive technique and the operation of the induction motor; (iii) a solution of the initial boundary value equations describing the RMF current drive in cylindrical plasmas.

  20. Adaptive solution of some steady-state fluid-structure interaction problems

    International Nuclear Information System (INIS)

    Etienne, S.; Pelletier, D.

    2003-01-01

    This paper presents a general integrated and coupled formulation for modeling the steady-state interaction of a viscous incompressible flow with an elastic structure undergoing large displacements (geometric non-linearities). This constitutes an initial step towards developing a sensitivity analysis formulation for this class of problems. The formulation uses velocity and pressures as unknowns in a flow domain and displacements in the structural components. An interface formulation is presented that leads to clear and simple finite element implementation of the equilibrium conditions at the fluid-solid interface. Issues of error estimation and mesh adaptation are discussed. The adaptive formulation is verified on a problem with a closed form solution. It is then applied to a sample case for which the structure undergoes large displacements induced by the flow. (author)

  1. The steady state solutions of radiatively driven stellar winds for a non-Sobolev, pure absorption model

    International Nuclear Information System (INIS)

    Poe, C.H.; Owocki, S.P.; Castor, J.I.

    1990-01-01

    The steady state solution topology for absorption line-driven flows is investigated for the condition that the Sobolev approximation is not used to compute the line force. The solution topology near the sonic point is of the nodal type with two positive slope solutions. The shallower of these slopes applies to reasonable lower boundary conditions and realistic ion thermal speed v(th) and to the Sobolev limit of zero of the usual Castor, Abbott, and Klein model. At finite v(th), this solution consists of a family of very similar solutions converging on the sonic point. It is concluded that a non-Sobolev, absorption line-driven flow with a realistic values of v(th) has no uniquely defined steady state. To the extent that a pure absorption model of the outflow of stellar winds is applicable, radiatively driven winds should be intrinsically variable. 34 refs

  2. Conflicts between sandhill cranes and farmers in the western United States: evolving issues and solutions

    Science.gov (United States)

    Austin, Jane E.

    2012-01-01

    The main conflicts between Sandhill Cranes (Grus canadensis) and farmers in western United States occur in the Rocky Mountain region during migration and wintering periods. Most crop damage by cranes occurs in mature wheat (Triticum aestivum) and barley (Hordeum vulgare), young shoots of alfalfa (Medicago sativa) and cereal grains, chilies (Capsicum annuum), and silage corn (Zea mays). Damage is related to proximity of crop fields to roost sites and timing of crane concentrations relative to crop maturity or vulnerability. The evolution of conflicts between farmers and cranes and current solutions are described for two areas of the Rocky Mountains used by staging, migrating, or wintering cranes: Grays Lake, Idaho, and the Middle Rio Grande Valley, New Mexico. In both areas, conflicts with growing crane populations were aggravated by losses of wetlands and cropland, proximity of crops to roosts and other wetland areas, changing crop types and practices, and increasing urbanization. At Grays Lake, fall-staging cranes damaged barley fields near an important breeding refuge as well as fields 15-50 km away. In the Middle Rio Grande Valley, migrating and wintering cranes damaged young alfalfa fields, chilies, and silage corn. Solutions in both areas have been addressed through cooperative efforts among federal and state agencies, that manage wetlands and croplands to increase food availability and carrying capacity on public lands, provide hazing programs for private landowners, and strategically target crane hunting to problem areas. Sustaining the success of these programs will be challenging. Areas important to Sandhill Cranes in the western United Sates experience continued loss of habitat and food resources due to urbanization, changes in agricultural crops and practices, and water-use conflicts, which threaten the abilities of both public and private landowners to manage wetlands and croplands for cranes. Conservation of habitats and water resources are important

  3. LigandRFs: random forest ensemble to identify ligand-binding residues from sequence information alone

    KAUST Repository

    Chen, Peng

    2014-12-03

    Background Protein-ligand binding is important for some proteins to perform their functions. Protein-ligand binding sites are the residues of proteins that physically bind to ligands. Despite of the recent advances in computational prediction for protein-ligand binding sites, the state-of-the-art methods search for similar, known structures of the query and predict the binding sites based on the solved structures. However, such structural information is not commonly available. Results In this paper, we propose a sequence-based approach to identify protein-ligand binding residues. We propose a combination technique to reduce the effects of different sliding residue windows in the process of encoding input feature vectors. Moreover, due to the highly imbalanced samples between the ligand-binding sites and non ligand-binding sites, we construct several balanced data sets, for each of which a random forest (RF)-based classifier is trained. The ensemble of these RF classifiers forms a sequence-based protein-ligand binding site predictor. Conclusions Experimental results on CASP9 and CASP8 data sets demonstrate that our method compares favorably with the state-of-the-art protein-ligand binding site prediction methods.

  4. A Fluid Membrane-Based Soluble Ligand Display System for Live CellAssays

    Energy Technology Data Exchange (ETDEWEB)

    Nam, Jwa-Min; Nair, Pradeep N.; Neve, Richard M.; Gray, Joe W.; Groves, Jay T.

    2005-10-14

    Cell communication modulates numerous biological processes including proliferation, apoptosis, motility, invasion and differentiation. Correspondingly, there has been significant interest in the development of surface display strategies for the presentation of signaling molecules to living cells. This effort has primarily focused on naturally surface-bound ligands, such as extracellular matrix components and cell membranes. Soluble ligands (e.g. growth factors and cytokines) play an important role in intercellular communications, and their display in a surface-bound format would be of great utility in the design of array-based live cell assays. Recently, several cell microarray systems that display cDNA, RNAi, or small molecules in a surface array format were proven to be useful in accelerating high-throughput functional genetic studies and screening therapeutic agents. These surface display methods provide a flexible platform for the systematic, combinatorial investigation of genes and small molecules affecting cellular processes and phenotypes of interest. In an analogous sense, it would be an important advance if one could display soluble signaling ligands in a surface assay format that allows for systematic, patterned presentation of soluble ligands to live cells. Such a technique would make it possible to examine cellular phenotypes of interest in a parallel format with soluble signaling ligands as one of the display parameters. Herein we report a ligand-modified fluid supported lipid bilayer (SLB) assay system that can be used to functionally display soluble ligands to cells in situ (Figure 1A). By displaying soluble ligands on a SLB surface, both solution behavior (the ability to become locally enriched by reaction-diffusion processes) and solid behavior (the ability to control the spatial location of the ligands in an open system) could be combined. The method reported herein benefits from the naturally fluid state of the supported membrane, which allows

  5. A Solution Space for a System of Null-State Partial Differential Equations: Part 4

    Science.gov (United States)

    Flores, Steven M.; Kleban, Peter

    2015-01-01

    This article is the last of four that completely and rigorously characterize a solution space for a homogeneous system of 2 N + 3 linear partial differential equations in 2 N variables that arises in conformal field theory (CFT) and multiple Schramm-Löwner evolution (SLE). The system comprises 2 N null-state equations and three conformal Ward identities that govern CFT correlation functions of 2 N one-leg boundary operators. In the first two articles (Flores and Kleban in Commun Math Phys, 2012; Flores and Kleban, in Commun Math Phys, 2014), we use methods of analysis and linear algebra to prove that dim , with C N the Nth Catalan number. Using these results in the third article (Flores and Kleban, in Commun Math Phys, 2013), we prove that dim and is spanned by (real-valued) solutions constructed with the Coulomb gas (contour integral) formalism of CFT. In this article, we use these results to prove some facts concerning the solution space . First, we show that each of its elements equals a sum of at most two distinct Frobenius series in powers of the difference between two adjacent points (unless is odd, in which case a logarithmic term may appear). This establishes an important element in the operator product expansion for one-leg boundary operators, assumed in CFT. We also identify particular elements of , which we call connectivity weights, and exploit their special properties to conjecture a formula for the probability that the curves of a multiple-SLE process join in a particular connectivity. This leads to new formulas for crossing probabilities of critical lattice models inside polygons with a free/fixed side-alternating boundary condition, which we derive in Flores et al. (Partition functions and crossing probabilities for critical systems inside polygons, in preparation). Finally, we propose a reason for why the exceptional speeds [certain values that appeared in the analysis of the Coulomb gas solutions in Flores and Kleban (Commun Math Phys, 2013)] and

  6. Electrochemistry of oxo-technetium(V) complexes containing Schiff base and 8-quinolinol ligands

    International Nuclear Information System (INIS)

    Refosco, F.; Mazzi, U.; Deutsch, E.; Kirchhoff, J.R.; Heineman, W.R.; Seeber, R.

    1988-01-01

    The electrochemistry of six-coordinate, monooxo technetium(V) complexes containing Schiff base ligands has been studied in acetonitrile and N,N'-dimethylformamide solutions. The complexes have the general formula TcOCl(L B ) 2 or TcO(L T )(L B ), where L B represents a bidentate-N,O Schiff base ligand or a bidentate-N,O 8-quinolinol ligand and L T represents a tridentate-O,N,O Schiff base ligand. Cyclic voltammetry at a platinum-disk electrode, controlled-potential coulometry, and thin-layer spectroelectrochemistry were used to probe both the oxidation and the reduction of these complexes. The results of these studies, and previously reported results on the analogous Re(V) complexes, can be understood within a single general reaction scheme. The salient features of this scheme are (i) one-electron reduction of Tc(V) to Tc(IV), (ii) subsequent loss of a ligand situated cis to the Tc≡O linkage, and (iii) subsequent isomerization of this unstable Tc(IV) product to more stable complex in which the site trans to the Tc≡O linkage is vacant. The Tc(IV) complexes can also be reduced to analogous Tc(III) species, which appear to undergo the same ligand loss and isomerization reactions. The technetium complexes are 400-500 mV easier to reduce than are their rhenium analogues. The 8-quinolinol ligands, and especially the 5-nitro derivative, both thermodynamically and kinetically stabilize the Tc(IV) and Tc(III) oxidation states. These electrogenerated species are unusual in that they constitute the bulk of the known examples of monomeric Tc(IV) and Tc(III) complexes containing only N- and O-donating ligands. 34 refs., 9 figs., 1 tab

  7. Luminescence properties of copper(I), zinc(II) and cadmium(II) coordination compounds with picoline ligands

    Energy Technology Data Exchange (ETDEWEB)

    Małecki, Jan Grzegorz, E-mail: gmalecki@us.edu.pl; Maroń, Anna

    2017-06-15

    Mononuclear coordination compounds of copper(I) – [Cu(PPh{sub 3}){sub 2}(picoline)(NO{sub 3})], zinc(II) – [ZnCl{sub 2}(picoline){sub 2}] (picoline=3– and 4–methylpyridine) and polymeric cadmium(II) – [CdCl{sub 2}(β-picoline){sub 2}]{sub n} were prepared and their luminescence properties in solid state and acetonitrile solutions were determined. Single crystal X-ray crystallography revealed distorted tetrahedral geometry around the central ions of the compounds. The compounds exhibit green photoluminescence in solid state and in acetonitrile solutions. The emission of copper(I) compounds originated from metal-to-ligand charge transfer state combined with nitrato-to-picoline charge transfer state i.e. ({sup 1}(M+X)LCT). The presence of nitrato ligand in the coordination sphere of copper(I) compounds quenches the emission. Luminescence of zinc(II) and cadmium(II) compounds results from chloride-to-picoline charge transfer state and the quantum efficiency in the case of the polymeric Cd(II) compound reaches 39%. The photoluminescence quantum yields of the mononuclear zinc(II) compounds vary from 10 to 16% depending on the conditions (solid state, solution). - Graphical abstract: Coordination compounds of copper(I), zinc(II) and polymeric cadmium(II) with picoline ligands were prepared and their luminescence properties in solid state and acetonitrile solutions were determined. The compounds exhibit green photoluminescence in solid state and in acetonitrile solutions. Emission of copper(I) compounds originated from {sup 1}(M+X)LCT state. Luminescence of zinc(II) and cadmium(II) compounds results from chloride-to-picoline charge transfer state and the quantum efficiency in the case of the polymeric Cd(II) compound reaches 39%. The photoluminescence quantum yields of the mononuclear zinc(II) compounds vary from 10 to 16% depending on the conditions (solid state, solution).

  8. Determination of formal redox potentials in aqueous solution of copper(II) complexes with ligands having nitrogen and oxygen donor atoms and comparison with their EPR and UV-Vis spectral features.

    Science.gov (United States)

    Tabbì, Giovanni; Giuffrida, Alessandro; Bonomo, Raffaele P

    2013-11-01

    Formal redox potentials in aqueous solution were determined for copper(II) complexes with ligands having oxygen and nitrogen as donor atoms. All the chosen copper(II) complexes have well-known stereochemistries (pseudo-octahedral, square planar, square-based pyramidal, trigonal bipyramidal or tetrahedral) as witnessed by their reported spectroscopic, EPR and UV-visible (UV-Vis) features, so that a rough correlation between the measured redox potential and the typical geometrical arrangement of the copper(II) complex could be established. Negative values have been obtained for copper(II) complexes in tetragonally elongated pseudo-octahedral geometries, when measured against Ag/AgCl reference electrode. Copper(II) complexes in tetrahedral environments (or flattened tetrahedral geometries) show positive redox potential values. There is a region, always in the field of negative redox potentials which groups the copper(II) complexes exhibiting square-based pyramidal arrangements. Therefore, it is suggested that a measurement of the formal redox potential could be of great help, when some ambiguities might appear in the interpretation of spectroscopic (EPR and UV-Vis) data. Unfortunately, when the comparison is made between copper(II) complexes in square-based pyramidal geometries and those in square planar environments (or a pseudo-octahedral) a little perturbed by an equatorial tetrahedral distortion, their redox potentials could fall in the same intermediate region. In this case spectroscopic data have to be handled with great care in order to have an answer about a copper complex geometrical characteristics. © 2013.

  9. Networked solutions of radiation control of state borders and urban areas

    International Nuclear Information System (INIS)

    Kulik, Victor; Gordeev, Alexander; Mamedov, Arif

    2008-01-01

    Full text: Prevention of illicit trafficking in radioactive and nuclear materials through state borders as well as the disperse of radioactive materials in urban area is a challenging task of national security departments in many countries. To solve this task, appropriate actions of personnel on-site equipped by radiation detectors such as fixed radiation portal monitors or mobile personal radiation detectors are required. However, users of radiation equipment such as Customs, Border Guard and Police Services often perform radiation control as additional responsibility to their main duties. Furthermore, these users have no sufficient expertise in radiation control and need real-time remote expert help to interpret readings of radiation equipment and expert support in decision making process. Polimaster has developed complete solution called Nuclear Protection Network system (NPNET) for high-effective radiation control on State Borders as well as inside a country. NPNET system intended for efficient interaction and on-line data exchange between a user, radiation control instrument, for example a personal radiation detector or radioisotope identifier, and remote Command Center. Availability of such system allows to solve more efficiently tasks of detection, localization and identification of ionizing radiation sources, to properly interpret false alarms (e.g. at detention of a passenger having passed radio-therapy etc.) and effectively prevent illicit trafficking radioactive and nuclear materials. The NPNET system can cover territory as large as city or even a state and provides assistant of infinite number of independent user groups. NPNET has a module structure and could be easily adapted to any specific user's requirements. Thus, the radiation mobile system NPNET is an effective tool for prevention of illicit trafficking of nuclear and radioactive materials and is recommended for use by Border guards, Customs, Securities and emergency situations services. (author)

  10. Impact of protein and ligand impurities on ITC-derived protein-ligand thermodynamics.

    Science.gov (United States)

    Grüner, Stefan; Neeb, Manuel; Barandun, Luzi Jakob; Sielaff, Frank; Hohn, Christoph; Kojima, Shun; Steinmetzer, Torsten; Diederich, François; Klebe, Gerhard

    2014-09-01

    The thermodynamic characterization of protein-ligand interactions by isothermal titration calorimetry (ITC) is a powerful tool in drug design, giving valuable insight into the interaction driving forces. ITC is thought to require protein and ligand solutions of high quality, meaning both the absence of contaminants as well as accurately determined concentrations. Ligands synthesized to deviating purity and protein of different pureness were titrated by ITC. Data curation was attempted also considering information from analytical techniques to correct stoichiometry. We used trypsin and tRNA-guanine transglycosylase (TGT), together with high affinity ligands to investigate the effect of errors in protein concentration as well as the impact of ligand impurities on the apparent thermodynamics. We found that errors in protein concentration did not change the thermodynamic properties obtained significantly. However, most ligand impurities led to pronounced changes in binding enthalpy. If protein binding of the respective impurity is not expected, the actual ligand concentration was corrected for and the thus revised data compared to thermodynamic properties obtained with the respective pure ligand. Even in these cases, we observed differences in binding enthalpy of about 4kJ⋅mol(-1), which is considered significant. Our results indicate that ligand purity is the critical parameter to monitor if accurate thermodynamic data of a protein-ligand complex are to be recorded. Furthermore, artificially changing fitting parameters to obtain a sound interaction stoichiometry in the presence of uncharacterized ligand impurities may lead to thermodynamic parameters significantly deviating from the accurate thermodynamic signature. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Schiff base ligand

    Indian Academy of Sciences (India)

    Unknown

    Low-temperature stoichiometric Schiff base reaction in air in 3 : 1 mole ratio between benz- aldehyde and triethylenetetramine (trien) in methanol yields a novel tetraaza µ-bis(bidentate) acyclic ligand L. It was .... electrochemical work was performed as reported in ..... change in ligand shape through change in oxidation.

  12. A Solution Space for a System of Null-State Partial Differential Equations: Part 2

    Science.gov (United States)

    Flores, Steven M.; Kleban, Peter

    2015-01-01

    This article is the second of four that completely and rigorously characterize a solution space for a homogeneous system of 2 N + 3 linear partial differential equations in 2 N variables that arises in conformal field theory (CFT) and multiple Schramm-Löwner evolution (SLE). The system comprises 2 N null-state equations and three conformal Ward identities which govern CFT correlation functions of 2 N one-leg boundary operators. In the first article (Flores and Kleban, Commun Math Phys, arXiv:1212.2301, 2012), we use methods of analysis and linear algebra to prove that dim , with C N the Nth Catalan number. The analysis of that article is complete except for the proof of a lemma that it invokes. The purpose of this article is to provide that proof. The lemma states that if every interval among ( x 2, x 3), ( x 3, x 4),…,( x 2 N-1, x 2 N ) is a two-leg interval of (defined in Flores and Kleban, Commun Math Phys, arXiv:1212.2301, 2012), then F vanishes. Proving this lemma by contradiction, we show that the existence of such a nonzero function implies the existence of a non-vanishing CFT two-point function involving primary operators with different conformal weights, an impossibility. This proof (which is rigorous in spite of our occasional reference to CFT) involves two different types of estimates, those that give the asymptotic behavior of F as the length of one interval vanishes, and those that give this behavior as the lengths of two intervals vanish simultaneously. We derive these estimates by using Green functions to rewrite certain null-state PDEs as integral equations, combining other null-state PDEs to obtain Schauder interior estimates, and then repeatedly integrating the integral equations with these estimates until we obtain optimal bounds. Estimates in which two interval lengths vanish simultaneously divide into two cases: two adjacent intervals and two non-adjacent intervals. The analysis of the latter case is similar to that for one vanishing

  13. Marshak Lectureship Talk: Women in Physics in the Baltic States Region: Problems and Solutions

    Science.gov (United States)

    Satkovskiene, Dalia

    2008-03-01

    In this contribution the gender equality problem in physics will be discussed on the basis of the results obtained implementing the project ``Baltic States Network: Women in Sciences and High Technology'' (BASNET) initiated by Lithuanian women physicists and financed by European Commission. The main goal of BASNET project was creation of the regional Strategy how to deal with women in sciences problem in the Baltic States. It has some stages and the contribution follows them. The first one was in depth sociological study aiming to find out disincentives and barriers women scientists face in their career and work at science and higher education institutions. Analysis of results revealed wide range of problems concerned with science organization, management and financing common for both counterparts. However it also proved the existence of women discrimination in sciences. As main factors influencing women under-representation in Physics was found: the stereotypes existing in the society where physics is assigned to the masculine area of activity; failings of the science management system, where highest positions are distributed not using the institutionalized objective criteria but by voting, where the correctness of majority solutions is anticipated implicitly. In physics where male scientists are the majority (they also usually compose executive boards, committees etc.) results of such a procedures often are unfavorable for women. The same reasons also influence women ``visibility'' in physicist's community and as the consequence possibility to receive needed recourses for their research as well as appropriate presentation of results obtained. The study revealed also the conservatism of scientific community- reluctance to face existing in the scientific society problems and to start solving them. On the basis of the results obtained as well practice of other countries the common strategy of solving women in physics (sciences) in the Baltic States region was

  14. Final Report - Montana State University - Microbial Activity and Precipitation at Solution-Solution Mixing Zones in Porous Media

    Energy Technology Data Exchange (ETDEWEB)

    Gerlach, Robin [Montana State University

    2014-10-31

    Background. The use of biological and chemical processes that degrade or immobilize contaminants in subsurface environments is a cornerstone of remediation technology. The enhancement of biological and chemical processes in situ, involves the transport, displacement, distribution and mixing of one or more reactive agents. Biological and chemical reactions all require diffusive transport of solutes to reaction sites at the molecular scale and accordingly, the success of processes at the meter-scale and larger is dictated by the success of phenomena that occur at the micron-scale. However, current understanding of scaling effects on the mixing and delivery of nutrients in biogeochemically dynamic porous media systems is limited, despite the limitations this imposes on the efficiency and effectiveness of the remediation challenges at hand. Objectives. We therefore proposed to experimentally characterize and computationally describe the growth, evolution, and distribution of microbial activity and mineral formation as well as changes in transport processes in porous media that receive two or more reactive amendments. The model system chosen for this project was based on a method for immobilizing 90Sr, which involves stimulating microbial urea hydrolysis with ensuing mineral precipitation (CaCO3), and co-precipitation of Sr. Studies at different laboratory scales were used to visualize and quantitatively describe the spatial relationships between amendment transport and consumption that stimulate the production of biomass and mineral phases that subsequently modify the permeability and heterogeneity of porous media. Biomass growth, activity, and mass deposition in mixing zones was investigated using two-dimensional micro-model flow cells as well as flow cells that could be analyzed using synchrotron-based x-ray tomography. Larger-scale flow-cell experiments were conducted where the spatial distribution of media properties, flow, segregation of biological activity and

  15. Syntheses, X-ray structures, solid state high-field electron paramagnetic resonance, and density-functional theory investigations on chloro and aqua Mn(II) mononuclear complexes with amino-pyridine pentadentate ligands.

    Science.gov (United States)

    Hureau, Christelle; Groni, Sihem; Guillot, Régis; Blondin, Geneviève; Duboc, Carole; Anxolabéhère-Mallart, Elodie

    2008-10-20

    The two pentadentate amino-pyridine ligands L5(2) and L5(3) (L5(2) and L5(3) stand for the N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine and the N-methyl-N,N',N'-tris(2-pyridylmethyl)propane-1,3-diamine, respectively) were used to synthesize four mononuclear Mn(II) complexes, namely [(L5(2))MnCl](PF6) (1(PF6)), [(L5(3))MnCl](PF6) (2(PF6)), [(L5(2))Mn(OH2)](BPh4)2 (3(BPh4)2), and [(L5(3))Mn(OH2)](BPh4)2 (4(BPh4)2). The X-ray diffraction studies revealed different configurations for the ligand L5(n) (n = 2, 3) depending on the sixth exogenous ligand and/or the counterion. Solid state high-field electron paramagnetic resonance spectra were recorded on complexes 1-4 as on previously described mononuclear Mn(II) systems with tetra- or hexadentate amino-pyridine ligands. Positive and negative axial zero-field splitting (ZFS) parameters D were determined whose absolute values ranged from 0.090 to 0.180 cm(-1). Density-functional theory calculations were performed unraveling that, in contrast with chloro systems, the spin-spin and spin-orbit coupling contributions to the D-parameter are comparable for mixed N,O-coordination sphere complexes.

  16. Determination of boron in aqueous solutions by solid state nuclear track detectors technique, using a filtered neutron beam

    International Nuclear Information System (INIS)

    Moraes, M.A.P.V. de; Pugliesi, R.; Khouri, M.T.F.C.

    1985-11-01

    The solid state nuclear track detectors technique has been used for determination of boron in aqueous solutions, using a filtered neutron beam. The particles tracks from the 10 B(n,α)Li 7 reaction were registered in the CR-39 film, chemically etched in a (30%) KOH solution 70 0 C during 90 minutes. The obtained results showed the usefulness of this technique for boron determination in the ppm range. The inferior detectable limit was 9 ppm. The combined track registration efficiency factor K has been evaluated in the solutions, for the CR-39 detector and its values is K= (4,60 - + 0,06). 10 -4 cm. (Author) [pt

  17. Two-particle correlations in the one-dimensional Hubbard model: a ground-state analytical solution

    CERN Document Server

    Vallejo, E; Espinosa, J E

    2003-01-01

    A solution to the extended Hubbard Hamiltonian for the case of two-particles in an infinite one-dimensional lattice is presented, using a real-space mapping method and the Green function technique. This Hamiltonian considers the on-site (U) and the nearest-neighbor (V) interactions. The method is based on mapping the correlated many-body problem onto an equivalent site-impurity tight-binding one in a higher dimensional space. In this new space we obtained the analytical solution for the ground state binding energy. Results are in agreement with the numerical solution obtained previously [1], and with those obtained in the reciprocal space [2]. (Author)

  18. State of the art concerning optimum location of capacitors and studying the exhaustive search approach for optimising a given solution

    Directory of Open Access Journals (Sweden)

    Sergio Raúl Rivera Rodríguez

    2004-09-01

    Full Text Available The present article reviews the state of the art of optimum capacitor location in distribution systems, provideing guidelines for planners engaged in optimising tension profiles and controlling reagents in distribution networks.Optimising a given solution by exhastive search is studied here; the dimensions of a given problem are determined by evaluating the different possibilities for resolving it and the solution algorithm's computational times and requierements are visualised. An example system (9 node, IEEE is used for illustrating the exhaustive search approach, where it was found that methods used in the literature regarding this topic do not always lead to the optimum solution.

  19. State of technology, system and solution supporting on-line maintenance - company's activities and products

    International Nuclear Information System (INIS)

    Nishitani, Junichi; Shimizu, Shunichi; Higasa, Hisakazu

    2010-01-01

    The new inspection system based on operator's maintenance and monitoring program of nuclear power plants was introduced in Japan more than one year ago and recommended on-line maintenance (maintenance during operation) will be carried out to increase capacity factor with safe and reliable operation of the plant. In this feature article, nine experts described the state of technology, system and solution supporting on-line maintenance - company's activities and products. These were titled as 'MHI's technology supporting on-line maintenance'. 'Technology supporting on-line maintenance - Toshiba's activities to upgrade monitoring and diagnostic service and maintenance management', 'AsahiKASEI's activities of on-line maintenance', 'Importance of information sharing of on-line maintenance and its ideal method-function of impact plan of IBM Maximo Asset Management for Nuclear', 'US's on-line maintenance and information systems', 'SmartProcedures realizing safe operation of nuclear power plant - proposal of computerized procedures', 'Ultrasonic leak detection system SDT170', 'Application of infrared thermography for equipment maintenance in nuclear power plant' and 'On-line condition monitoring system - condition eye'. (T. Tanaka)

  20. Carrier Transport Enhancement in Conjugated Polymers through Interfacial Self-Assembly of Solution-State Aggregates

    KAUST Repository

    Zhao, Kui

    2016-07-13

    We demonstrate that local and long range orders of poly(3-hexylthiophene) (P3HT) semicrystalline films can be synergistically improved by combining chemical functionalization of the dielectric surface with solution-state disentanglement and pre-aggregation of P3HT in a theta solvent, leading to a very significant enhancement of the field effect carrier mobility. The pre-aggregation and surface functionalization effects combine to enhance the carrier mobility nearly 100-fold as compared with standard film preparation by spin-coating, and nearly 10-fold increase over the benefits of pre-aggregation alone. In situ quartz crystal microbalance with dissipation (QCM-D) experiments reveal enhanced deposition of pre-aggregates on surfaces modified with an alkyl-terminated self-assembled monolayer (SAM) in comparison to un-aggregated polymer chains. Additional investigations reveal the combined pre-aggregation and surface functionalization significantly enhances local order of the conjugated polymer through planarization and extension of the conjugated backbone of the polymer which clearly translate to significant improvements of carrier transport at the semiconductor-dielectric interface in organic thin film transistors. This study points to opportunities in combining complementary routes, such as well-known pre-aggregation with substrate chemical functionalization, to enhance the polymer self-assembly and improve its interfacial order with benefits for transport properties.

  1. Analytical solutions of steady-state conjugate heat transfer in ducts with turbulent flow

    International Nuclear Information System (INIS)

    Cerqueira, Djane R.; Jian Su

    2007-01-01

    In this work, we present an approximate analytical solution of the steady-state conjugate heat transfer of turbulent forced convection in a circular pipe with wall axial heat conduction and external convective boundary conditions. Improved lumped differential approach based on two points Hermite approximation for integrals was applied to reduce the heat conduction equation in the solid into a second-order ordinary differential equation for the radially averaged solid temperature. The energy equation in the fluid was solved by applying the generalized integral transform technique (GITT). The Sturm-Lioville eigenproblem for fluid energy equation in the cylindrical coordinate system was solved by the sign-count method. The truncated system of N ordinary differential equations for transformed potentials of the fluid temperature and the second-order ordinary differential equation for radially averaged solid temperature formed a homogeneous system of N+2 ordinary differential equations, which was solved analytically. The effects of the fluid-solid thermal conductivity ratio on the Nusselt number, the average fluid and solid temperatures, and the fluid-solid interface temperature were investigated. (author)

  2. Four crystal structures of human LLT1, a ligand of human NKR-P1, in varied glycosylation and oligomerization states

    Czech Academy of Sciences Publication Activity Database

    Skálová, Tereza; Bláha, J.; Harlos, K.; Dušková, Jarmila; Koval, Tomáš; Stránský, Jan; Hašek, Jindřich; Vaněk, O.; Dohnálek, Jan

    2015-01-01

    Roč. 71, č. 3 (2015), s. 578-591 ISSN 1399-0047 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0109; GA ČR GAP302/11/0855; GA ČR(CZ) GA15-15181S; GA MŠk LG14009; GA MŠk(CZ) EE2.3.30.0029 Institutional support: RVO:86652036 ; RVO:61389013 Keywords : LLT1 * C-type lectin-like ligand * NATURAL-KILLER-CELLS Subject RIV: EB - Genetics ; Molecular Biology; EB - Genetics ; Molecular Biology (UMCH-V) Impact factor: 2.674, year: 2014

  3. Selective oxoanion separation using a tripodal ligand

    Energy Technology Data Exchange (ETDEWEB)

    Custelcean, Radu; Moyer, Bruce A.; Rajbanshi, Arbin

    2016-02-16

    The present invention relates to urea-functionalized crystalline capsules self-assembled by sodium or potassium cation coordination and by hydrogen-bonding water bridges to selectively encapsulate tetrahedral divalent oxoanions from highly competitive aqueous alkaline solutions and methods using this system for selective anion separations from industrial solutions. The method involves competitive crystallizations using a tripodal tris(urea) functionalized ligand and, in particular, provides a viable approach to sulfate separation from nuclear wastes.

  4. Semiconductor Quantum Dots with Photoresponsive Ligands.

    Science.gov (United States)

    Sansalone, Lorenzo; Tang, Sicheng; Zhang, Yang; Thapaliya, Ek Raj; Raymo, Françisco M; Garcia-Amorós, Jaume

    2016-10-01

    Photochromic or photocaged ligands can be anchored to the outer shell of semiconductor quantum dots in order to control the photophysical properties of these inorganic nanocrystals with optical stimulations. One of the two interconvertible states of the photoresponsive ligands can be designed to accept either an electron or energy from the excited quantum dots and quench their luminescence. Under these conditions, the reversible transformations of photochromic ligands or the irreversible cleavage of photocaged counterparts translates into the possibility to switch luminescence with external control. As an alternative to regulating the photophysics of a quantum dot via the photochemistry of its ligands, the photochemistry of the latter can be controlled by relying on the photophysics of the former. The transfer of excitation energy from a quantum dot to a photocaged ligand populates the excited state of the species adsorbed on the nanocrystal to induce a photochemical reaction. This mechanism, in conjunction with the large two-photon absorption cross section of quantum dots, can be exploited to release nitric oxide or to generate singlet oxygen under near-infrared irradiation. Thus, the combination of semiconductor quantum dots and photoresponsive ligands offers the opportunity to assemble nanostructured constructs with specific functions on the basis of electron or energy transfer processes. The photoswitchable luminescence and ability to photoinduce the release of reactive chemicals, associated with the resulting systems, can be particularly valuable in biomedical research and can, ultimately, lead to the realization of imaging probes for diagnostic applications as well as to therapeutic agents for the treatment of cancer.

  5. Solution and solid-state electrochemiluminescence of a fac-tris(2-phenylpyridyl)iridium(III)-cored dendrimer

    International Nuclear Information System (INIS)

    Reid, Ellen F.; Burn, Paul L.; Lo, Shih-Chun; Hogan, Conor F.

    2013-01-01

    The solution phase and solid-state electrochemistry and electrochemiluminescence (ECL) of an iridium(III) complex-cored dendrimeric analogue of Ir(ppy) 3 , (G1pIr), are reported. The solid-state electrochemistry and solid-state ECL of Ir(ppy) 3 itself is also described for the first time. In solution phase, the dendrimer displays greater immunity to oxygen quenching in photoluminescence (PL) experiments and exhibits greater ECL efficiency compared to the parent Ir(ppy) 3 core under the same conditions, despite a lower photoluminescence quantum yield. It is proposed that the dendrons which effectively shield the core from PL quenching interactions in the solid-state counteract the effects of parasitic side-reactions during the solution ECL experiments. Electroactive and ECL-active solid-state films of both Ir(ppy) 3 and G1pIr were produced by drop-coating on boron doped diamond electrodes. Films of Ir(ppy) 3 produced stable co-reactant ECL. However, films of G1pIr produced lower than expected ECL intensity. This was attributed to poorer charge transport and the lipophilicity of the film limiting the rate of interaction with the co-reactant required for formation of the excited state

  6. Use of evidence-based interventions in state health departments: a qualitative assessment of barriers and solutions.

    Science.gov (United States)

    Dodson, Elizabeth A; Baker, Elizabeth A; Brownson, Ross C

    2010-01-01

    Existing knowledge on chronic disease prevention is not systematically disseminated and applied. State-level public health practitioners are in positions to implement programs and services related to chronic disease control. To advance dissemination science, this study sought to evaluate how and why evidence-based decision making (EBDM) is occurring. Specifically, it identified barriers to using EBDM commonly faced by state-level chronic disease practitioners and solutions for increasing the use of EBDM. Descriptive research using online survey methods. State health departments. Members of the National Association of Chronic Disease Directors. Barriers to using EBDM and solutions to increase the use of EBDM. In total, 469 people completed the survey (64% response rate). More than 60% of respondents described their position as project managers or coordinators. Nearly 80% of respondents were women, and 39% reported at least a master's degree as their highest degree. The survey elicited responses from every US state and the District of Columbia. Commonly-cited barriers to using EBDM included lack of time, resources, funding, and data. Participants noted that promising solutions to increase the use of EBDM include improved leadership, training, and collaboration. These results identify several modifiable barriers to EBDM among state-level public health practitioners. This information may improve state health departments' abilities to facilitate and encourage EBDM. In turn, this may assist chronic disease practitioners in implementing chronic disease interventions that have been proven effective. The use of such interventions will improve public health through the prevention of chronic diseases.

  7. Links between soil properties and steady-state solute transport through cultivated topsoil at the field scale

    DEFF Research Database (Denmark)

    Koestel, J. K.; Nørgaard, Trine; Loung, N. M.

    2013-01-01

    It is known that solute transport through soil is heterogeneous at all spatial scales. However, little data are available to allow quantification of these heterogeneities at the field scale or larger. In this study, we investigated the spatial patterns of soil properties, hydrologic state variables......, and tracer breakthrough curves (BTCs) at the field scale for the inert solute transport under a steady-state irrigation rate which produced near-saturated conditions. Sixty-five undisturbed soil columns approximately 20 cm in height and diameter were sampled from the loamy topsoil of an agricultural field...... to larger water saturation and the activation of larger macropores. Our study provides further evidence that it should be possible to estimate solute transport properties from soil properties such as soil texture or bulk density. We also demonstrated that estimation approaches established for the column...

  8. Laminating solution-processed silver nanowire mesh electrodes onto solid-state dye-sensitized solar cells

    KAUST Repository

    Hardin, Brian E.; Gaynor, Whitney; Ding, I-Kang; Rim, Seung-Bum; Peumans, Peter; McGehee, Michael D.

    2011-01-01

    Solution processed silver nanowire meshes (Ag NWs) were laminated on top of solid-state dye-sensitized solar cells (ss-DSCs) as a reflective counter electrode. Ag NWs were deposited in <1 min and were less reflective compared to evaporated Ag

  9. A solution-state NMR approach to elucidating pMDI-wood bonding mechanisms in loblolly pine

    Science.gov (United States)

    Daniel Joseph Yelle

    2009-01-01

    Solution-state NMR spectroscopy is a powerful tool for unambiguously determining the existence or absence of covalent chemical bonds between wood components and adhesives. Finely ground wood cell wall material dissolves in a solvent system containing DMSO-d6 and NMI-d6, keeping wood component polymers intact and in a near-...

  10. Investigating the reactivity of pMDI with wood cell walls using high-resolution solution-state NMR spectroscopy

    Science.gov (United States)

    Daniel J. Yelle; John Ralph; Charles R. Frihart

    2009-01-01

    The objectives of this study are the following: (1) Use solution-state NMR to assign contours in HSQC spectra of the reaction products between pMDI model compounds and: (a) lignin model compounds, (b) milled-wood lignin, (c) ball-milled wood, (d) microtomed loblolly pine; (2) Determine where and to what degree urethane formation occurs with loblolly pine cell wall...

  11. Solid state synthesis, crystal growth and optical properties of urea and p-chloronitrobenzene solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Rai, R.N., E-mail: rn_rai@yahoo.co.in [Department of Chemistry, Centre of Advanced Study, Banaras Hindu University, Varanasi 221005 (India); Kant, Shiva; Reddi, R.S.B. [Department of Chemistry, Centre of Advanced Study, Banaras Hindu University, Varanasi 221005 (India); Ganesamoorthy, S. [Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamilnadu (India); Gupta, P.K. [Laser Materials Development & Devices Division, Raja Ramanna Centre for Advanced Technology, Indore 452013 (India)

    2016-01-15

    Urea is an attractive material for frequency conversion of high power lasers to UV (for wavelength down to 190 nm), but its usage is hindered due to its hygroscopic nature, though there is no alternative organic NLO crystal which could be transparent up to 190 nm. The hygroscopic character of urea has been modified by making the solid solution (UCNB) of urea (U) and p-chloronitrobenzene (CNB). The formation of the solid solution of CNB in U is explained on the basis of phase diagram, powder XRD, FTIR, elemental analysis and single crystal XRD studies. The solubility of U, CNB and UCNB in ethanol solution is evaluated at different temperatures. Transparent single crystals of UCNB are grown from its saturated solution in ethanol. Optical properties e.g., second harmonic generation (SHG), refractive index and the band gap for UCNB crystal were measured and their values were compared with the parent compounds. Besides modification in hygroscopic nature, UCNB has also shown the higher SHG signal and mechanical hardness in comparison to urea crystal. - Highlights: • The hygroscopic character of urea was modified by making the solid solution • Solid solution formation is support by elemental, powder- and single crystal XRD • Crystal of solid solution has higher SHG signal and mechanical stability. • Refractive index and band gap of solid solution crystal have determined.

  12. Effects of Catalytic Action and Ligand Binding on Conformational Ensembles of Adenylate Kinase.

    Science.gov (United States)

    Onuk, Emre; Badger, John; Wang, Yu Jing; Bardhan, Jaydeep; Chishti, Yasmin; Akcakaya, Murat; Brooks, Dana H; Erdogmus, Deniz; Minh, David D L; Makowski, Lee

    2017-08-29

    Crystal structures of adenylate kinase (AdK) from Escherichia coli capture two states: an "open" conformation (apo) obtained in the absence of ligands and a "closed" conformation in which ligands are bound. Other AdK crystal structures suggest intermediate conformations that may lie on the transition pathway between these two states. To characterize the transition from open to closed states in solution, X-ray solution scattering data were collected from AdK in the apo form and with progressively increasing concentrations of five different ligands. Scattering data from apo AdK are consistent with scattering predicted from the crystal structure of AdK in the open conformation. In contrast, data from AdK samples saturated with Ap5A do not agree with that calculated from AdK in the closed conformation. Using cluster analysis of available structures, we selected representative structures in five conformational states: open, partially open, intermediate, partially closed, and closed. We used these structures to estimate the relative abundances of these states for each experimental condition. X-ray solution scattering data obtained from AdK with AMP are dominated by scattering from AdK in the open conformation. For AdK in the presence of high concentrations of ATP and ADP, the conformational ensemble shifts to a mixture of partially open and closed states. Even when AdK is saturated with Ap5A, a significant proportion of AdK remains in a partially open conformation. These results are consistent with an induced-fit model in which the transition of AdK from an open state to a closed state is initiated by ATP binding.

  13. Quantitative analysis of multiple kappa-opioid receptors by selective and nonselective ligand binding in guinea pig spinal cord: Resolution of high and low affinity states of the kappa 2 receptors by a computerized model-fitting technique

    International Nuclear Information System (INIS)

    Tiberi, M.; Magnan, J.

    1990-01-01

    The binding characteristics of selective and nonselective opioids have been studied in whole guinea pig spinal cord, using a computer fitting method to analyze the data obtained from saturation and competition studies. The delineation of specific binding sites labeled by the mu-selective opioid [3H]D-Ala2,MePhe4,Gly-ol5-enkephalin (Kd = 2.58 nM, R = 4.52 pmol/g of tissue) and by the delta-selective opioid [3H]D-Pen2, D-Pen5-enkephalin (Kd = 2.02 nM, R = 1.47 pmol/g of tissue) suggests the presence of mu and delta-receptors in the spinal cord tissue. The presence of kappa receptors was probed by the kappa-selective opioid [3H]U69593 (Kd = 3.31 nM, R = 2.00 pmol/g of tissue). The pharmacological characterization of the sites labeled by [3H]U69593 confirms the assumption that this ligand discriminates kappa receptors in guinea pig spinal cord. The benzomorphan [3H]ethylketazocine labels a population of receptors with one homogeneous affinity state (Kd = 0.65 nM, R = 7.39 pmol/g of tissue). The total binding capacity of this ligand was not different from the sum of the binding capacities of mu, delta-, and kappa-selective ligands. Under mu- and delta-suppressed conditions, [3H]ethylketazocine still binds to receptors with one homogeneous affinity state (Kd = 0.45 nM, R = 1.69 pmol/g of tissue). Competition studies performed against the binding of [3H]ethylketazocine under these experimental conditions reveal that the pharmacological profile of the radiolabeled receptors is similar to the profile of the kappa receptors labeled with [3H]U69593. Saturation studies using the nonselective opioid [3H]bremazocine demonstrate that this ligand binds to spinal cord membranes with heterogeneous affinities (Kd1 = 0.28 nM, R1 = 7.91 pmol/g of tissue; Kd2 = 3.24 nM, R2 = 11.2 pmol/g of tissue)

  14. Quantitative analysis of multiple kappa-opioid receptors by selective and nonselective ligand binding in guinea pig spinal cord: Resolution of high and low affinity states of the kappa 2 receptors by a computerized model-fitting technique

    Energy Technology Data Exchange (ETDEWEB)

    Tiberi, M.; Magnan, J. (Universite de Montreal, Quebec (Canada))

    1990-05-01

    The binding characteristics of selective and nonselective opioids have been studied in whole guinea pig spinal cord, using a computer fitting method to analyze the data obtained from saturation and competition studies. The delineation of specific binding sites labeled by the mu-selective opioid (3H)D-Ala2,MePhe4,Gly-ol5-enkephalin (Kd = 2.58 nM, R = 4.52 pmol/g of tissue) and by the delta-selective opioid (3H)D-Pen2, D-Pen5-enkephalin (Kd = 2.02 nM, R = 1.47 pmol/g of tissue) suggests the presence of mu and delta-receptors in the spinal cord tissue. The presence of kappa receptors was probed by the kappa-selective opioid (3H)U69593 (Kd = 3.31 nM, R = 2.00 pmol/g of tissue). The pharmacological characterization of the sites labeled by (3H)U69593 confirms the assumption that this ligand discriminates kappa receptors in guinea pig spinal cord. The benzomorphan (3H)ethylketazocine labels a population of receptors with one homogeneous affinity state (Kd = 0.65 nM, R = 7.39 pmol/g of tissue). The total binding capacity of this ligand was not different from the sum of the binding capacities of mu, delta-, and kappa-selective ligands. Under mu- and delta-suppressed conditions, (3H)ethylketazocine still binds to receptors with one homogeneous affinity state (Kd = 0.45 nM, R = 1.69 pmol/g of tissue). Competition studies performed against the binding of (3H)ethylketazocine under these experimental conditions reveal that the pharmacological profile of the radiolabeled receptors is similar to the profile of the kappa receptors labeled with (3H)U69593. Saturation studies using the nonselective opioid (3H)bremazocine demonstrate that this ligand binds to spinal cord membranes with heterogeneous affinities (Kd1 = 0.28 nM, R1 = 7.91 pmol/g of tissue; Kd2 = 3.24 nM, R2 = 11.2 pmol/g of tissue).

  15. The affinity of the uranyl ion for nitrogen donor ligands

    International Nuclear Information System (INIS)

    Jarvis, N.V.; De Sousa, A.S.; Hancock, R.D.

    1992-01-01

    Established ligand design principles are used to predict the solution chemistry of UO 2 2+ with nitrogen donor ligands which do not contain carboxylate donors. pK a 's of the nitrogen donors are lowered by addition of hydroxylalkyl groups causing UO 2 2+ to have a greater affinity for these ligands than for hydroxide. Potentiometric studies using the ligands N,N,N',N',N''-pentakis(2-hydroxypropyl)-1,4,7-triazaheptane; N,N,N',N',N''-pentakis(2-hydroxyethyl)-1,4,7-triazaheptane; N,N,N',N'-tetrakis(2-hydroxypropyl)1,2-diaminoethane, N,N,N',N'-tetrakis(2-hydroxyethyl)-trans-1,2-diaminocyclohexane; 1,4,8,11-tetrakis(2-hydroxyethyl)-1,4,8,11-tetraazacyclotetradecane and N,N-bis(2-hydroxyethyl)glycine with UO 2 2+ showed that UO 2 2+ has a considerable aqueous solution chemistry with these ligands. (orig.)

  16. Computing the stability of steady-state solutions of mathematical models of the electrical activity in the heart.

    Science.gov (United States)

    Tveito, Aslak; Skavhaug, Ola; Lines, Glenn T; Artebrant, Robert

    2011-08-01

    Instabilities in the electro-chemical resting state of the heart can generate ectopic waves that in turn can initiate arrhythmias. We derive methods for computing the resting state for mathematical models of the electro-chemical process underpinning a heartbeat, and we estimate the stability of the resting state by invoking the largest real part of the eigenvalues of a linearized model. The implementation of the methods is described and a number of numerical experiments illustrate the feasibility of the methods. In particular, we test the methods for problems where we can compare the solutions with analytical results, and problems where we have solutions computed by independent software. The software is also tested for a fairly realistic 3D model. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. Ammonia formation by metal-ligand cooperative hydrogenolysis of a nitrido ligand

    Science.gov (United States)

    Askevold, Bjorn; Nieto, Jorge Torres; Tussupbayev, Samat; Diefenbach, Martin; Herdtweck, Eberhardt; Holthausen, Max C.; Schneider, Sven

    2011-07-01

    Bioinspired hydrogenation of N2 to ammonia at ambient conditions by stepwise nitrogen protonation/reduction with metal complexes in solution has experienced remarkable progress. In contrast, the highly desirable direct hydrogenation with H2 remains difficult. In analogy to the heterogeneously catalysed Haber-Bosch process, such a reaction is conceivable via metal-centred N2 splitting and unprecedented hydrogenolysis of the nitrido ligands to ammonia. We report the synthesis of a ruthenium(IV) nitrido complex. The high nucleophilicity of the nitrido ligand is demonstrated by unusual N-C coupling with π-acidic CO. Furthermore, the terminal nitrido ligand undergoes facile hydrogenolysis with H2 at ambient conditions to produce ammonia in high yield. Kinetic and quantum chemical examinations of this reaction suggest cooperative behaviour of a phosphorus-nitrogen-phosphorus pincer ligand in rate-determining heterolytic hydrogen splitting.

  18. Extent of Intramolecular pi Stacks in Aqueous Solution in Mixed-Ligand Copper(II) Complexes Formed by Heteroaromatic Amines and 1-[2-(Phosphonomethoxy)ethyl]cytosine (PMEC), a Relative of Antivirally Active Acyclic Nucleotide Analogues (Part 72)

    Czech Academy of Sciences Publication Activity Database

    Blindauer, C. A.; Sigel, A.; Operschall, B. P.; Holý, Antonín; Sigel, H.

    2013-01-01

    Roč. 639, 8-9 (2013), s. 1661-1673 ISSN 0044-2313 Institutional support: RVO:61388963 Keywords : nucleotide analogues * antivirals * complex stabilities * isomers * equilibria * mixed ligand complexes Subject RIV: CC - Organic Chemistry Impact factor: 1.251, year: 2013

  19. The core spline method for solution of quantum-mechanical systems of differential equations for bound states

    International Nuclear Information System (INIS)

    Aleksandrov, L.; Drenska, M.; Karadzhov, D.

    1986-01-01

    A generalization of the core spline method is given in the case of solution of the general bound state problem for a system of M linear differential equations with coefficients depending on the spectral parameter. The recursion scheme for construction of basic splines is described. The wave functions are expressed as linear combinations of basic splines, which are approximate partial solutions of the system. The spectral parameter (the eigenvalue) is determined from the condition for existence of a nontrivial solution of a (MxM) linear algebraic system at the last collocation point. The nontrivial solutions of this system determine (M - 1) coefficients of the linear spans, expressing the wave functions. The last unknown coefficient is determined from a boundary (or normalization) condition for the system. The computational aspects of the method are discussed, in particular, its concrete algorithmic realization used in the RODSOL program. The numerical solution of the Dirac system for the bound states of a hydrogen atom is given is an example

  20. Monte Carlo simulation and equation of state for flexible charged hard-sphere chain fluids: Polyampholyte and polyelectrolyte solutions

    International Nuclear Information System (INIS)

    Jiang, Hao; Adidharma, Hertanto

    2014-01-01

    The thermodynamic modeling of flexible charged hard-sphere chains representing polyampholyte or polyelectrolyte molecules in solution is considered. The excess Helmholtz energy and osmotic coefficients of solutions containing short polyampholyte and the osmotic coefficients of solutions containing short polyelectrolytes are determined by performing canonical and isobaric-isothermal Monte Carlo simulations. A new equation of state based on the thermodynamic perturbation theory is also proposed for flexible charged hard-sphere chains. For the modeling of such chains, the use of solely the structure information of monomer fluid for calculating the chain contribution is found to be insufficient and more detailed structure information must therefore be considered. Two approaches, i.e., the dimer and dimer-monomer approaches, are explored to obtain the contribution of the chain formation to the Helmholtz energy. By comparing with the simulation results, the equation of state with either the dimer or dimer-monomer approach accurately predicts the excess Helmholtz energy and osmotic coefficients of polyampholyte and polyelectrolyte solutions except at very low density. It also well captures the effect of temperature on the thermodynamic properties of these solutions

  1. Electrocatalytic oxidation of methanol by the [Ru3O(OAc6(py2(CH3OH]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

    Directory of Open Access Journals (Sweden)

    Henrique E. Toma

    2010-01-01

    Full Text Available The [Ru3O(Ac6(py2(CH3OH]+ cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3III,II,II/Ru3III,III,II/Ru 3III,III,III /Ru3IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two RuIV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.

  2. Phosphorus ligand imaging with two-photon fluorescence spectroscopy: towards rational catalyst immobilization

    NARCIS (Netherlands)

    Marras, F.; Kluwer, A.M.; Siekierzycka, J.R.; Vozza, A.; Brouwer, A.M.; Reek, J.N.H.

    2010-01-01

    Spotless catalysts: Ligand immobilization was studied by two-photon fluorescence microscopy with a fluorescent nixantphos ligand as probe (see picture). In the immobilization process ligand aggregates form in solution and are deposited on the support, where they appear as bright spots in

  3. Determinable solutions for one-dimensional quantum potentials: scattering, quasi-bound and bound-state problems

    International Nuclear Information System (INIS)

    Lee, Hwasung; Lee, Y J

    2007-01-01

    We derive analytic expressions of the recursive solutions to Schroedinger's equation by means of a cutoff-potential technique for one-dimensional piecewise-constant potentials. These solutions provide a method for accurately determining the transmission probabilities as well as the wavefunction in both classically accessible regions and inaccessible regions for any barrier potentials. It is also shown that the energy eigenvalues and the wavefunctions of bound states can be obtained for potential-well structures by exploiting this method. Calculational results of illustrative examples are shown in order to verify this method for treating barrier and potential-well problems

  4. The discrimination of the oxidation states of neptunium in sodium hydroxide solutions by means of chromatography on alumina

    International Nuclear Information System (INIS)

    Shiokawa, Yoshinobu; Yamana, Hajimu; Sato, Akiko; Suzuki, Shin

    1982-01-01

    A method of discriminating the oxidation states of Np in a NaOH solution by means of chromatography on alumina is proposed. In a NaOH solution of 0.5 - 1.7 M (1 M = 1 mol dm - 3 ), the separation of Np (VI) from Np (VII) can be made effectively by means of chromatography on alumina. Only a little Np (VI) is adsorbed on alumina the Np (VII) adsorbed to some extent, and the Np (V), strongly, under the same conditions. By applying this chromatographic method, the method of preparing Np (VI) and Np (VII) of a tracer quantity in 1 M NaOH is established. (author)

  5. A closed-form solution for steady-state coupled phloem/xylem flow using the Lambert-W function.

    Science.gov (United States)

    Hall, A J; Minchin, P E H

    2013-12-01

    A closed-form solution for steady-state coupled phloem/xylem flow is presented. This incorporates the basic Münch flow model of phloem transport, the cohesion model of xylem flow, and local variation in the xylem water potential and lateral water flow along the transport pathway. Use of the Lambert-W function allows this solution to be obtained under much more general and realistic conditions than has previously been possible. Variation in phloem resistance (i.e. viscosity) with solute concentration, and deviations from the Van't Hoff expression for osmotic potential are included. It is shown that the model predictions match those of the equilibrium solution of a numerical time-dependent model based upon the same mechanistic assumptions. The effect of xylem flow upon phloem flow can readily be calculated, which has not been possible in any previous analytical model. It is also shown how this new analytical solution can handle multiple sources and sinks within a complex architecture, and can describe competition between sinks. The model provides new insights into Münch flow by explicitly including interactions with xylem flow and water potential in the closed-form solution, and is expected to be useful as a component part of larger numerical models of entire plants. © 2013 John Wiley & Sons Ltd.

  6. Limitations of steady state solutions to a two-state model of population oscillations and hole burning

    International Nuclear Information System (INIS)

    Payne, M. G.; Deng, L.; Jiang, K. J.

    2006-01-01

    We consider a two-state system driven by an on-resonance, continuous wave pump laser and a much weaker pulsed probe laser that is slightly detuned from the pump laser frequency (usually this detuning is about ω p -ω P =Δ≅1 kHz). The upper state population is assumed to be slowly decaying, but the off-diagonal element of the density matrix decays rapidly due to homogeneous broadening. This model has been solved by others in rare-earth-element-doped fibers and crystals in a usual steady state approximation for slow optical wave propagation. We show that in general the usual steady state approximation does not apply unless either Δτ>>1 or (2S+1)γ 2 τ>>1 where γ 2 is the decay rate of the excited state population, τ is the pulse length of the probe field, and 2S is the saturation parameter. Both conditions, however, are not satisfied in many population-oscillation- and corresponding group-velocity-reduction-related studies. Our theory and corresponding numerical simulations have indicated that for probe pulses that are much shorter than the lifetime of the upper state, there is no analytical theory for the amplitude, pulse shape, and group velocity of the probe field. In addition, there is no reason to assume that the group velocity remains small when γ 2 τ<<1 and there is no reason to believe that many pulse length decays can be obtained for such short pulses

  7. Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study.

    Science.gov (United States)

    Guo, Xugeng; Yuan, Huijuan; An, Beibei; Zhu, Qiuling; Zhang, Jinglai

    2016-04-21

    Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S1 state, which may undergo an ultrafast non-radiative deactivation to the S0 state. The lifetime of the S1 state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solventwater has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in watersolution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.

  8. Investigation into state of phosphomolybdovanadic heteropolyacids in aqueous solutions by the NMR method

    International Nuclear Information System (INIS)

    Maksimovskaya, R.I.; Fedotov, M.A.; Mastikhin, V.M.; Kuznetsova, L.I.; Matveev, K.I.

    1978-01-01

    The methods of 31 P, 51 V, and 17 O NMR have been used for studying the solutions of phospho-molybdenum-vanadium heteropolyacids (HPA) with x=0,1,2,3 (HPA-x) and their mixture with changing concentration, acidity, temperature, and upon partial reduction for separating the lines corresponding to HPA with a certain x. It has been found that in aqueous solutions HPA is present as a mixture of HPA of different compositions; the relationship has been observed between chemical shifts of the lines and the solution acidity which is of a different character for HPA with different x. This allows to make a conclusion about the mechanism of HPA protonation

  9. Current state in adsorption from multicomponent solutions of nonelectrolytes on solids

    International Nuclear Information System (INIS)

    Borowko, M.; Jaroniec, M.

    1983-01-01

    This paper surveys the research carried out on the adsorption from multicomponent liquid mixtures of nonelectrolytes on solids with emphasis on the work performed by the authors. The consistent theoretical treatment of adsorption from concentrated and dilute multicomponent solutions and its application to the liquid adsorption chromatography with the mixed mobile phase are presented. This treatment involved nonideality of the bulk and surface phases, energetic heterogeneity of the adsorbent surface and it may be extended to multilayer adsorption from solutions. The multicomponent liquid/solid adsorption systems, studied experimentally, are reviewed. Many of them have been examined by means of the equations derived for liquid adsorption on heterogeneous surfaces. These studies are summarized in this paper. Moreover, the model studies illustrating the influence of solution nonideality and adsorbent heterogeneity on the excess adsorption isotherms and the distribution coefficient are discussed. (orig.)

  10. State-of-the-Art System Solutions for Unmanned Underwater Vehicles

    Directory of Open Access Journals (Sweden)

    A. E. Yilmaz

    2009-12-01

    Full Text Available Unmanned Underwater Vehicles (UUVs have gained popularity for the last decades, especially for the purpose of not risking human life in dangerous operations. On the other hand, underwater environment introduces numerous challenges in navigation, control and communication of such vehicles. Certainly, this fact makes the development of these vehicles more interesting and engineering-wise more attractive. In this paper, we first revisit the existing technology and methodology for the solution of aforementioned problems, then we try to come up with a system solution of a generic unmanned underwater vehicles.

  11. Ab initio molecular dynamics simulation of aqueous solution of nitric oxide in different formal oxidation states

    Science.gov (United States)

    Venâncio, Mateus F.; Rocha, Willian R.

    2015-10-01

    Ab initio molecular dynamics simulations were used to investigate the early chemical events involved in the dynamics of nitric oxide (NOrad), nitrosonium cation (NO+) and nitroxide anion (NO-) in aqueous solution. The NO+ ion is very reactive in aqueous solution having a lifetime of ∼4 × 10-13 s, which is shorter than the value of 3 × 10-10 s predicted experimentally. The NO+ reacts generating the nitrous acid as an intermediate and the NO2- ion as the final product. The dynamics of NOrad revealed the reversibly formation of a transient anion radical species HONOrad -.

  12. Classical states of an electric dipole in an external magnetic field: Complete solution for the center of mass and trapped states

    Energy Technology Data Exchange (ETDEWEB)

    Atenas, Boris; Pino, Luis A. del; Curilef, Sergio, E-mail: scurilef@ucn.cl

    2014-11-15

    We study the classical behavior of an electric dipole in the presence of a uniform magnetic field. Using the Lagrangian formulation, we obtain the equations of motion, whose solutions are represented in terms of Jacobi functions. We also identify two constants of motion, namely, the energy E and a pseudomomentumC{sup →}. We obtain a relation between the constants that allows us to suggest the existence of a type of bound states without turning points, which are called trapped states. These results are consistent with and complementary to previous results. - Highlights: • Bound states without turning points. • Lagrangian Formulation for an electric dipole in a magnetic field. • Motion of the center of mass and trapped states. • Constants of motion: pseudomomentum and energy.

  13. Details of the general numerical solutions of the Friedberg-Lee soliton model for ground and exited states

    International Nuclear Information System (INIS)

    Koeppel, T.; Harvey, M.

    1984-06-01

    A new numerical method is applied to solving the equations of motion of the Friedberg-Lee Soliton model for both ground and spherically symmetric excited states. General results have been obtained over a wide range of parameters. Critical coupling constants and critical particle numbers have been determined below which soliton solutions cease to exist. The static properties of the proton are considered to show that as presently formulated the model fails to fit all experimental data for any set of parameters

  14. The state-of-the-art of the LTAN method in the solution of the transport equation in a slab

    International Nuclear Information System (INIS)

    Vieira Cardona, A.; Panta Pazos, R.; Tullio de Vilhena, M.

    2004-01-01

    In this work we report the state-of-the-art of the LTA N method, reporting the derivation of the LTA N homogeneous and particular solution in a slab for large N (N N method. We show that the LTA N method, consequently the Laplace transform technique, is a quite general approach to solve a wide class of transport problems in a slab mainly the ones requiring an arbitrary source and large N

  15. Hydrodynamic fluctuations, nonequilibrium equations of state, and the shift of the spinodal line in polymer solutions under flow

    International Nuclear Information System (INIS)

    Criado-Sancho, M.; Casas-Vazquez, J.; Jou, D.

    1997-01-01

    In the literature, the shift of the spinodal line of polymer solutions under flow is attributed either to an actual shift of the spinodal due to a nonequilibrium modification of the equation of state for the chemical potential, or to an apparent shift due to an increase of hydrodynamic fluctuations owing to the flow. Here we see that both approaches are compatible and that both effects add up. copyright 1997 The American Physical Society

  16. 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)

  17. Analytical Solutions for the Surface States of Bi1-xSbx (0 ≤ x ≲ 0.1)

    Science.gov (United States)

    Fuseya, Yuki; Fukuyama, Hidetoshi

    2018-04-01

    Analytical solutions for the surface state (SS) of an extended Wolff Hamiltonian, which is a common Hamiltonian for strongly spin-orbit coupled systems, are obtained both for semi-infinite and finite-thickness boundary conditions. For the semi-infinite system, there are two types of SS solutions: (I-a) linearly crossing SSs in the direct bulk band gap, and (I-b) SSs with linear dispersions entering the bulk conduction or valence bands away from the band edge. For the finite-thickness system, a gap opens in the SS of solution I-a. Numerical solutions for the SS are also obtained based on the tight-binding model of Liu and Allen [https://doi.org/10.1103/PhysRevB.52.1566" xlink:type="simple">Phys. Rev. B 52, 1566 (1995)] for Bi1-xSbx (0 ≤ x ≤ 0.1). A perfect correspondence between the analytic and numerical solutions is obtained around the \\bar{M} point including their thickness dependence. This is the first time that the character of the SS numerically obtained is identified with the help of analytical solutions. The size of the gap for I-a SS can be larger than that of bulk band gap even for a "thick" films ( ≲ 200 bilayers ≃ 80 nm) of pure bismuth. Consequently, in such a film of Bi1-xSbx, there is no apparent change in the SSs through the band inversion at x ≃ 0.04, even though the nature of the SS is changed from solution I-a to I-b. Based on our theoretical results, the experimental results on the SS of Bi1-xSbx (0 ≤ x ≲ 0.1) are discussed.

  18. Bound State Solutions of the Klein-Gordon Equation for the Mathews-Lakshmanan Oscillator

    International Nuclear Information System (INIS)

    Schulze-Halberg, Axel; Wang, Jie

    2014-01-01

    We study a boundary-value problem for the Klein-Gordon equation that is inspired by the well-known Mathews-Lakshmanan oscillator model. By establishing a link to the spheroidal equation, we show that our problem admits an infinite number of discrete energies, together with associated solutions that form an orthogonal set in a weighted L 2 -Hilbert space. (author)

  19. Oligomerization of hydrophobin SC3 in solution : From soluble state to self-assembly

    NARCIS (Netherlands)

    Wang, Xiaoqin; Graveland-Bikker, Johanna F.; Kruif, Cornelis G. de; Robillard, George T.

    2004-01-01

    Hydrophobin SC3 is a protein with special self-association properties that differ depending on whether it is in solution, on an air/water interface or on a solid surface. Its self-association on an air/water interface and solid surface have been extensively characterized. The current study focuses

  20. Decarbonization of the U.S. electricity sector: Are state energy policy portfolios the solution?

    International Nuclear Information System (INIS)

    Carley, Sanya

    2011-01-01

    State governments have taken the lead on U.S. energy and climate policy. It is not yet clear, however, whether state energy policy portfolios can generate results in a similar magnitude or manner to their presumed carbon mitigation potential. This article seeks to address this lack of policy evidence and contribute empirical insights on the carbon mitigation effects of state energy portfolios within the U.S. electricity sector. Using a dynamic, long-term electricity dispatch model with U.S. power plant, utility, and transmission and distribution data between 2010 and 2030, this analysis builds a series of state-level policy portfolio scenarios and performs a comparative scenario analysis. Results reveal that state policy portfolios have modest to minimal carbon mitigation effects in the long run if surrounding states do not adopt similar portfolios as well. The difference in decarbonization potential between isolated state policies and larger, more coordinated policy efforts is due in large part to carbon leakage, which is the export of carbon intensive fossil fuel-based electricity across state lines. Results also confirm that a carbon price of $50/metric ton CO 2 e can generate substantial carbon savings. Although both policy options - an energy policy portfolio or a carbon price - are effective at reducing carbon emissions in the present analysis, neither is as effective alone as when the two strategies are combined. - Research highlights: → Scenario modeling exercise to assess effectiveness of state energy policy portfolios. → Regional coordination has greater decarbonization potential than state policies. → Some states benefit more from regional policy coordination than others. → Emissions leakage attenuates the effect of isolated state policy portfolios. → Carbon price with coordinated energy portfolio has greatest decarbonization potential.

  1. Effects of electrostatic interactions on ligand dissociation kinetics

    Science.gov (United States)

    Erbaş, Aykut; de la Cruz, Monica Olvera; Marko, John F.

    2018-02-01

    We study unbinding of multivalent cationic ligands from oppositely charged polymeric binding sites sparsely grafted on a flat neutral substrate. Our molecular dynamics simulations are suggested by single-molecule studies of protein-DNA interactions. We consider univalent salt concentrations spanning roughly a 1000-fold range, together with various concentrations of excess ligands in solution. To reveal the ionic effects on unbinding kinetics of spontaneous and facilitated dissociation mechanisms, we treat electrostatic interactions both at a Debye-Hückel (DH) (or implicit ions, i.e., use of an electrostatic potential with a prescribed decay length) level and by the more precise approach of considering all ionic species explicitly in the simulations. We find that the DH approach systematically overestimates unbinding rates, relative to the calculations where all ion pairs are present explicitly in solution, although many aspects of the two types of calculation are qualitatively similar. For facilitated dissociation (FD) (acceleration of unbinding by free ligands in solution) explicit-ion simulations lead to unbinding at lower free-ligand concentrations. Our simulations predict a variety of FD regimes as a function of free-ligand and ion concentrations; a particularly interesting regime is at intermediate concentrations of ligands where nonelectrostatic binding strength controls FD. We conclude that explicit-ion electrostatic modeling is an essential component to quantitatively tackle problems in molecular ligand dissociation, including nucleic-acid-binding proteins.

  2. High resolution NMR study of cellulose in solid state and in solution

    International Nuclear Information System (INIS)

    Saint-Germain, Jean

    1983-01-01

    This research thesis reports the study of native cellulose (cotton) and wood by nuclear magnetic resonance (NMR). As far as the cotton spectrum is concerned, the author assigned resonances which more specifically corresponded to amorphous or crystalline areas. Wood was studied in its bulk condition, and resonances have been determined for the different wood components. The behaviour of cellulose in solution in a solvent has been studied by liquid high resolution NMR. The solvation mechanism has been determined and a study of model components of the macromolecule allowed a conformational study of cellulose in this solvent to be performed. Bi-dimensional NMR and longitudinal relaxation time measurements highlighted the existence of an intramolecular hydrogen bond in the cellulose in solution [fr

  3. Organic components and plutonium and americium state in soils and soil solutions

    International Nuclear Information System (INIS)

    Sokolik, G.A.; Ovsyannikova, S.V.; Kimlenko, I.M.

    2002-01-01

    The fraction composition of humus substances of different type soils and soil solutions have been studied. A distribution of Pu 239, 240 and Am 241 between humus substances fractions of different dispersity and mobility in soil-vegetation cover has been established. It was shown that humus of organic soils fixes plutonium and americium in soil medium in greater extent than humus of mineral soils. That leads to lower migration ability of radionuclides in organic soils. The lower ability of americium to form difficultly soluble organic and organic-mineral complexes and predomination of its anion complexes in soil solutions may be a reason of higher mobility and biological availability of americium in comparison to plutonium during soil-plant transfer (authors)

  4. Modeling of water and solute transport under variably saturated conditions: state of the art

    International Nuclear Information System (INIS)

    Lappala, E.G.

    1980-01-01

    This paper reviews the equations used in deterministic models of mass and energy transport in variably saturated porous media. Analytic, quasi-analytic, and numerical solution methods to the nonlinear forms of transport equations are discussed with respect to their advantages and limitations. The factors that influence the selection of a modeling method are discussed in this paper; they include the following: (1) the degree of coupling required among the equations describing the transport of liquids, gases, solutes, and energy; (2) the inclusion of an advection term in the equations; (3) the existence of sharp fronts; (4) the degree of nonlinearity and hysteresis in the transport coefficients and boundary conditions; (5) the existence of complex boundaries; and (6) the availability and reliability of data required by the models

  5. Glutamate receptor ligands

    DEFF Research Database (Denmark)

    Guldbrandt, Mette; Johansen, Tommy N; Frydenvang, Karla Andrea

    2002-01-01

    Homologation and substitution on the carbon backbone of (S)-glutamic acid [(S)-Glu, 1], as well as absolute stereochemistry, are structural parameters of key importance for the pharmacological profile of (S)-Glu receptor ligands. We describe a series of methyl-substituted 2-aminoadipic acid (AA...

  6. An algorithm for full parametric solution of problems on the statics of orthotropic plates by the method of boundary states with perturbations

    Science.gov (United States)

    Penkov, V. B.; Ivanychev, D. A.; Novikova, O. S.; Levina, L. V.

    2018-03-01

    The article substantiates the possibility of building full parametric analytical solutions of mathematical physics problems in arbitrary regions by means of computer systems. The suggested effective means for such solutions is the method of boundary states with perturbations, which aptly incorporates all parameters of an orthotropic medium in a general solution. We performed check calculations of elastic fields of an anisotropic rectangular region (test and calculation problems) for a generalized plane stress state.

  7. Chapter 6. Scaling Up Solutions to State, National and Global Levels

    OpenAIRE

    Kammen, Daniel; Rotman, Doug; Delmas, Magali; Feldman, David; Mielke, Mike; Ramesh, Ramamoorthy; Sperling, Daniel

    2016-01-01

    Scaling-up solutions require learning and adapting lessons between locations and at different scales. To accomplish this, common metrics are vital to building a shared language. For California, this has meant careful financial, cradle-to-grave life-cycle assessment methods leading to carbon accounting in many avenues of government (via the Low Carbon Fuel Standard or the Cap and Trade program). These methods themselves interact, such as the use of carbon accounting for the resources needed to...

  8. Radiation polymerization and crosslinking of N-isopropylacrylamide in aqueous solution and in solid state

    International Nuclear Information System (INIS)

    Safranj, A.; Yoshida, Masaru; Omichi, Hideki; Nagaoka, Noriyasu; Kubota, Hitoshi; Katakai, Ryoichi.

    1995-01-01

    Poly(N-isopropylacrylamide) hydrogels were synthesized by radiation induced simultaneous polymerization and cross-linking. Aqueous monomer solutions and pure monomer, without crosslinker, were irradiated in nitrogen atmosphere at a 60 Co gamma source. The conversion from monomer to polymer and cross-linked gel was investigated as a function of temperature and monomer concentration. The swelling behavior of the gels showed clear dependence on the synthesis conditions. (author)

  9. Inhibition of the solid state transformation of carbamazepine in aqueous solution: impact of polymeric properties.

    Science.gov (United States)

    Gift, Alan D; Hettenbaugh, Jacob A; Quandahl, Rachel A; Mapes, Madison

    2017-11-06

    The effects of polymers on the anhydrate-to-hydrate transformation of carbamazepine (CBZ) was investigated. The three types of polymers studied were polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and substituted celluloses which included hydroxypropyl methylcellulose (HPMC) and methylcellulose (MC). Anhydrous CBZ was added to dilute aqueous polymer solutions and Raman spectroscopy measurements were collected to monitor the kinetics of the solution-mediated transformation to CBZ dihydrate. Polymers exhibiting the greatest inhibition were able to reduce the growth phase of the solution-mediated transformation and change the habit of the hydrate crystal indicating polymer adsorption to the hydrate crystal surface as the mechanism of inhibition. The results of the various polymers showed that short chain substituted celluloses (HPMC and MC) inhibited the CBZ transformation to a much greater extent than longer chains. The same trend was observed for PVP and PVA, but to a lesser extent. These chain length effects were attributed to changes in polymer confirmation when adsorbed on the crystal surface. Additionally, decreasing the percentage of hydroxyl groups on the PVA polymer backbone reduced the ability of the polymer to inhibit the transformation and changing the degree of substitutions of methyl and hydroxypropyl groups on the cellulosic polymer backbone had no effect on the transformation.

  10. Henry constants in polymer solutions with the van der Waals equation of state

    DEFF Research Database (Denmark)

    Bithas, Sotiris; Kalospiros, Nikolaos; Kontogeorgis, Georgios

    1996-01-01

    parameter is satisfactory, with typical errors within the experimental uncertainty and comparable to those with the more complex Perturbed Hard Chain Theory-based equations of state with the same number of adjustable parameters. A predictive scheme for calculating Henry constants is also presented, which...... is a corresponding-states correlation for a dimensionless Henry constant defined based on the van der Waals equation of state. Satisfactory results-often close to the ones from the one-parameter correlation-are obtained for all systems investigated in this work. Compared with literature models that have been applied...

  11. Scattering state solutions of the Duffin-Kemmer-Petiau equation with the Varshni potential model

    Energy Technology Data Exchange (ETDEWEB)

    Oluwadare, O.J. [Federal University Oye-Ekiti, Department of Physics, Oye-Ekiti, Ekiti State (Nigeria); Oyewumi, K.J. [Federal University of Technology, Department of Physics, Minna, Niger State (Nigeria)

    2017-02-15

    The scattering state of the Duffin-Kemmer-Petiau equation with the Varshni potential was studied. The asymptotic wave function, the scattering phase shift and normalization constant were obtained for any J states by dealing with the centrifugal term using a suitable approximation. The analytical properties of the scattering amplitude and the bound state energy were obtained and discussed. Our numerical and graphical results indicate that the scattering phase shift depends largely on total angular momentum J, screening parameter β and potential strengths a and b. (orig.)

  12. Lanthanide(III) complexes of bis-semicarbazone and bis-imine-substituted phenanthroline ligands: solid-state structures, photophysical properties, and anion sensing.

    Science.gov (United States)

    Nadella, Sandeep; Selvakumar, Paulraj M; Suresh, Eringathodi; Subramanian, Palani S; Albrecht, Markus; Giese, Michael; Fröhlich, Roland

    2012-12-21

    Phenanthroline-based hexadentate ligands L(1) and L(2) bearing two achiral semicarbazone or two chiral imine moieties as well as the respective mononuclear complexes incorporating various lanthanide ions, such as La(III), Eu(III), Tb(III), Lu(III), and Y(III) metal ions, were synthesized, and the crystal structures of [ML(1)Cl(3)] (M=La(III), Eu(III), Tb(III), Lu(III), or Y(III)) complexes were determined. Solvent or water molecules act as coligands for the rare-earth metals in addition to halide anions. The big Ln(III) ion exhibits a coordination number (CN) of 10, whereas the corresponding Eu(III), Tb(III), Lu(III), and Y(III) centers with smaller ionic radii show CN=9. Complexes of L(2), namely [ML(2)Cl(3)] (M=Eu(III), Tb(III), Lu(III), or Y(III)) ions could also be prepared. Only the complex of Eu(III) showed red luminescence, whereas all the others were nonluminescent. The emission properties of the Eu derivative can be applied as a photophysical signal for sensing various anions. The addition of phosphate anions leads to a unique change in the luminescence behavior. As a case study, the quenching behavior of adenosine-5'-triphosphate (ATP) was investigated at physiological pH value in an aqueous solvent. A specificity of the sensor for ATP relative to adenosine-5'-diphosphate (ADP) and adenosine-5'-monophosphate (AMP) was found. (31)P NMR spectroscopic studies revealed the formation of a [EuL(2)(ATP)] coordination species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Adjustment of valence state of Pu and Np in nitric solution containing N,N-dimethylhydroxylamine and monomethylhydrazine by electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, H.; Ye, G.A.; Cong, H.F. [China Institute of Atomic Energy, Beijing (China)] [and others

    2012-07-01

    A study of the electrochemical behaviors of N,N-dimethylhydroxylamine (DMHAN) and monomethyl hydrazine (MMH) in nitric acid solution on Pt electrodes were carried out by cyclic voltammetry (CV) and linear sweep voltammetry (LSV) methods. The diffusion coefficients of DMHAN and MMH were obtained by CV. The values are found to be 0.53 x 10{sup -6}6 cm{sup 2}/s D{sub (DMHAN)} and 0.88 x 10{sup -5} cm{sup 2}/s D{sub (MMH)}. The equilibrium potentials (+0.47 V vs. SCE for DMHAN and +0.31 V vs. SCE for MMH) were also measured using Tafel curves. Various valence states of Pu and Np in HNO{sub 3} solution containing DMHAN and MMH in the electrolytic process were investigated by an electrolytic cell using a platinum as the anode and a titanium plate as the cathode. In this procedure, MMH was first electro-oxidized on the Pt anode and Np(V) was reduced to Np(IV) on the Ti cathode. After MMH was entirely consumed, the accumulation of HNO{sub 2} (due to the electrochemical reduction of nitric acid on the Ti cathode) caused a significantly fast catalytic reaction of DMHAN with HNO{sub 3} to form HNO{sub 2}. HNO{sub 2} can oxidize Pu(III) to Pu(IV) quickly. As a result, both oxidation states of Pu and Np were found to be tetravalent in the post-electrolysis solution. A convenient method to keep the post-electrolysis solution at 70 C was used to adjust the oxidation state of Np in it's pentavalent state while retaining the tetravalent state of Pu. This study developed an electrolytic process for the preparation of 2AF feed (the feed of Pu purification cycle) in APOR (Advanced Purex Process Based on Organic Reductants) process by electrochemically oxidizing Pu(III) and selectively adjusting the valence state of neptunium to either Np(IV) or Np(V). (orig.)

  14. Systematic Introduction of Aromatic Rings to Diphosphine Ligands for Emission Color Tuning of Dinuclear Copper(I) Iodide Complexes.

    Science.gov (United States)

    Okano, Yuka; Ohara, Hiroki; Kobayashi, Atsushi; Yoshida, Masaki; Kato, Masako

    2016-06-06

    We have newly synthesized two solution-stable luminescent dinuclear copper(I) complexes, [Cu2(μ-I)2(dpppy)2] (Cu-py) and [Cu2(μ-I)2(dpppyz)2] (Cu-pyz), where dpppy = 2,3-bis(diphenylphosphino)pyridine and dpppyz = 2,3-bis(diphenylphosphino)pyrazine, using chelating diphosphine ligands composed of N-heteroaromatic rings. X-ray analysis clearly indicates that the molecular structures of Cu-py and Cu-pyz are almost identical with that of the parent complex, [Cu2(μ-I)2(dppb)2] [Cu-bz; dppb = 2,3-bis(diphenylphosphino)benzene]. Complexes Cu-py and Cu-pyz exhibit luminescence [emission quantum yield (Φem) = 0.48 and 0.02, respectively] in the solid state at 298 K. A wide emission color tuning, from 497 to 638 nm (energy = 0.55 eV, with an emission color ranging from green to reddish-orange), was achieved in the solid state by the introduction of pyridinic N atoms into the bridging phenyl group between the two diphenylphosphine groups. Density functional theory calculations suggest that the emission could originate from the effective combination of the metal-to-ligand charge-transfer excited state with the halide-to-ligand charge-transfer excited state. Thus, the emission color change is due to stabilization of the π* levels of the central aryl group in the diphosphine ligand. Furthermore, these copper(I) complexes exhibit thermally activated delayed fluorescence at 298 K because of the small singlet-triplet energy difference (ΔE = 523 and 564 cm(-1) for Cu-py and Cu-pyz, respectively). The stability of these complexes in chloroform, due to the rigid bonds between the diphosphine ligands and the Cu(I) ions, enables the preparation of emissive poly(methyl methacrylate) films by the solution-doping technique.

  15. General three-state model with biased population replacement: Analytical solution and application to language dynamics

    Science.gov (United States)

    Colaiori, Francesca; Castellano, Claudio; Cuskley, Christine F.; Loreto, Vittorio; Pugliese, Martina; Tria, Francesca

    2015-01-01

    Empirical evidence shows that the rate of irregular usage of English verbs exhibits discontinuity as a function of their frequency: the most frequent verbs tend to be totally irregular. We aim to qualitatively understand the origin of this feature by studying simple agent-based models of language dynamics, where each agent adopts an inflectional state for a verb and may change it upon interaction with other agents. At the same time, agents are replaced at some rate by new agents adopting the regular form. In models with only two inflectional states (regular and irregular), we observe that either all verbs regularize irrespective of their frequency, or a continuous transition occurs between a low-frequency state, where the lemma becomes fully regular, and a high-frequency one, where both forms coexist. Introducing a third (mixed) state, wherein agents may use either form, we find that a third, qualitatively different behavior may emerge, namely, a discontinuous transition in frequency. We introduce and solve analytically a very general class of three-state models that allows us to fully understand these behaviors in a unified framework. Realistic sets of interaction rules, including the well-known naming game (NG) model, result in a discontinuous transition, in agreement with recent empirical findings. We also point out that the distinction between speaker and hearer in the interaction has no effect on the collective behavior. The results for the general three-state model, although discussed in terms of language dynamics, are widely applicable.

  16. 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)

  17. Ergodicity, configurational entropy and free energy in pigment solutions and plant photosystems: influence of excited state lifetime.

    Science.gov (United States)

    Jennings, Robert C; Zucchelli, Giuseppe

    2014-01-01

    We examine ergodicity and configurational entropy for a dilute pigment solution and for a suspension of plant photosystem particles in which both ground and excited state pigments are present. It is concluded that the pigment solution, due to the extreme brevity of the excited state lifetime, is non-ergodic and the configurational entropy approaches zero. Conversely, due to the rapid energy transfer among pigments, each photosystem is ergodic and the configurational entropy is positive. This decreases the free energy of the single photosystem pigment array by a small amount. On the other hand, the suspension of photosystems is non-ergodic and the configurational entropy approaches zero. The overall configurational entropy which, in principle, includes contributions from both the single excited photosystems and the suspension which contains excited photosystems, also approaches zero. Thus the configurational entropy upon photon absorption by either a pigment solution or a suspension of photosystem particles is approximately zero. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Links between soil properties and steady-state solute transport through cultivated topsoil at the field scale

    Science.gov (United States)

    Koestel, J. K.; Norgaard, T.; Luong, N. M.; Vendelboe, A. L.; Moldrup, P.; Jarvis, N. J.; Lamandé, M.; Iversen, B. V.; Wollesen de Jonge, L.

    2013-02-01

    It is known that solute transport through soil is heterogeneous at all spatial scales. However, little data are available to allow quantification of these heterogeneities at the field scale or larger. In this study, we investigated the spatial patterns of soil properties, hydrologic state variables, and tracer breakthrough curves (BTCs) at the field scale for the inert solute transport under a steady-state irrigation rate which produced near-saturated conditions. Sixty-five undisturbed soil columns approximately 20 cm in height and diameter were sampled from the loamy topsoil of an agricultural field site in Silstrup (Denmark) at a sampling distance of approximately 15 m (with a few exceptions), covering an area of approximately 1 ha (60 m × 165 m). For 64 of the 65 investigated soil columns, we observed BTC shapes indicating a strong preferential transport. The strength of preferential transport was positively correlated with the bulk density and the degree of water saturation. The latter suggests that preferential macropore transport was the dominating transport process. Increased bulk densities were presumably related with a decrease in near-saturated hydraulic conductivities and as a consequence to larger water saturation and the activation of larger macropores. Our study provides further evidence that it should be possible to estimate solute transport properties from soil properties such as soil texture or bulk density. We also demonstrated that estimation approaches established for the column scale have to be upscaled when applied to the field scale or larger.

  19. States and transport of hydrogen in the corrosion process of an AZ91 magnesium alloy in aqueous solution

    International Nuclear Information System (INIS)

    Chen Jian; Wang Jianqiu; Han Enhou; Dong Junhua; Ke Wei

    2008-01-01

    Mott-Schottky measurement and secondary ion mass spectroscopy (SIMS) were used to investigate the states and transport of hydrogen during the corrosion behavior of an AZ91 magnesium alloy in 0.1 M sodium sulfate solution. The results showed that when samples were immersed or charged in solution, hydrogen atoms diffused into the film and reacted with vacancy to cause the increases of the carrier concentration (excess electron or hole carrier) and diffusion rate of hydrogen. Some hydrogen atoms diffused to interior of matrix and enriched in β phase while others resorted in the corrosive film. With the increase of immersion or charging time, magnesium hydride would be brittle fractured when the inner stress caused by hydrogen pressure and expansion stress of formation of magnesium hydride was above the fracture strength, which provided the direct experimental evidence of the hydrogen embrittlement (HE) mechanism of magnesium and its alloys. After immersion in solution, the transfer of excess electrons to the interfaces of corrosion film and solution would destroy the charge equilibrium in the film and stimulate the adsorption of SO 4 2- , which resulted in the initiation of localized corrosion; after cathodic charging and then immersion, the enrichment of hydrogen atoms at interior of corrosion film would combine into hydrogen gas to form high pressure and result in the rupture of corrosion film, and localized corrosion initiated and developed at surface. Therefore, localized corrosion nucleated earlier on the charged samples than on the uncharged samples. Hydrogen invasion accelerated the corrosion of matrix

  20. The welfare state and its distributive effects: part of the problem or part of the solution?

    Science.gov (United States)

    Navarro, V

    1987-01-01

    In the first part of this article, the author presents (1) a discussion of some of the major arguments against the welfare state put forward by neoliberal forces on both sides of the Atlantic, and (2) empirical information that shows the ideological rather than scientific nature of those arguments. The author also questions the widely held belief among European neoliberal (and even on occasion progressive) forces that the Reagan Administration policies have been (1) very successful in stimulating employment and economic growth, and (2) neoliberal rather than Keynesian. The empirical information presented in this article shows that these Reagan Administration policies have followed a military Keynesianism rather than social Keynesianism, which is responsible for a rather poor economic and social performance. In the second part, the author presents alternatives to the austerity policies advocated by the anti-welfare state forces, policies based on an expansion of the universalist character of the welfare state and its democratization, with active participation of the municipalities in the administration of the welfare state services and in the development of reflationary policies aimed at guiding production and stimulating consumption. The author also shows that the full development of the welfare state is a precondition for the needed restructuring of the economy, labor mobility, and technological innovation. The welfare state, rather than being the cause of the economic crisis, is part of the resolution of this crisis. The article ends with a discussion of the political conditions for the expansion of the welfare state and for the resolution of the economic crisis.

  1. ASYMPTOTIC STEADY-STATE SOLUTION TO A BOW SHOCK WITH AN INFINITE MACH NUMBER

    Energy Technology Data Exchange (ETDEWEB)

    Yalinewich, Almog; Sari, Re’em [Racah Institute of Physics, the Hebrew University, 91904, Jerusalem (Israel)

    2016-08-01

    The problem of a cold gas flowing past a stationary obstacle is considered. We study the bow shock that forms around the obstacle and show that at large distances from the obstacle the shock front forms a parabolic solid of revolution. The profiles of the hydrodynamic variables in the interior of the shock are obtained by solution of the hydrodynamic equations in parabolic coordinates. The results are verified with a hydrodynamic simulation. The drag force on the obstacle is also calculated. Finally, we use these results to model the bow shock around an isolated neutron star.

  2. Asymmetric transfer hydrogenation of ketones in aqueous solution catalyzed by Rhodium(III) complexes with C2-symmetric fluorene-ligands containing chiral (1R,2R)-cyclohexane-1,2-diamine

    Energy Technology Data Exchange (ETDEWEB)

    Montalvo-Gonzalez, Ruben [Universidad Autonoma de Nayarit, Tepic, Nay (Mexico). Unidad Academica de Ciencias Quimico Biologicas y Farmaceuticas; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy, E-mail: somanatha@sundown.sdsu.ed [Instituto Tecnologico de Tijuana, B.C. (Mexico). Centro de Graduados e Investigacion

    2010-07-01

    Two C{sub 2}-symmetric bis(sulfonamide) ligands containing fluorene-chiral (1R, 2R)-cyclohexane-1,2-diamine were complexed to Rh{sup III}(Cp{sup *}) and used as catalyst to reduce aromatic ketones. The corresponding chiral secondary alcohols were obtained in 87-100% ee and 85-99% yield, under asymmetric transfer hydrogenation (ATH) conditions using aqueous sodium formate as the hydride source. With acetophenone, 94% ee and 86-97% yield was achieved with substrate/catalyst (S/C) ratio of 10,000. (author)

  3. Asymmetric transfer hydrogenation of ketones in aqueous solution catalyzed by Rhodium(III) complexes with C2-symmetric fluorene-ligands containing chiral (1R,2R)-cyclohexane-1,2-diamine

    International Nuclear Information System (INIS)

    Montalvo-Gonzalez, Ruben; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy

    2010-01-01

    Two C 2 -symmetric bis(sulfonamide) ligands containing fluorene-chiral (1R, 2R)-cyclohexane-1,2-diamine were complexed to Rh III (Cp * ) and used as catalyst to reduce aromatic ketones. The corresponding chiral secondary alcohols were obtained in 87-100% ee and 85-99% yield, under asymmetric transfer hydrogenation (ATH) conditions using aqueous sodium formate as the hydride source. With acetophenone, 94% ee and 86-97% yield was achieved with substrate/catalyst (S/C) ratio of 10,000. (author)

  4. The present state of research on the vitrification of concentrated solutions of fission products (1962)

    International Nuclear Information System (INIS)

    Bonniaud, R.; Sombret, C.

    1961-01-01

    The present report gives the actual point of studies on vitrification of concentrated solutions of fission products. An active cell, giving glasses in crucibles, permitted to study various glass compositions. The leaching rate from the glass raises 1 to 2 10 -7 g of glass/cm 2 /day. Activity loss by volatility during vitrification remains weak and often below 0.1 per cent of total activity. Off gas cleaning is made easier by presence of filter which is compound of granules including iron oxide. After saturation the content of this filter can be melt. Moreover different processes are in experimentation for a more important production. Daily 72 liters of solution containing tracer activity are treated in a continuous calcination and vitrification plant. The loss in 106 Ru is still important and a modification of installation has been necessary. A pot vitrification plant is in study. In order to reduce cost of processing the possibility to pour glass after melting is actuality in study. A production set of very active glass is also in project. (authors) [fr

  5. Mixed-ligand complexes of ruthenium(II) incorporating a diazo ...

    Indian Academy of Sciences (India)

    Unknown

    Dedicated to the memory of the late Professor Bhaskar G Maiya. *For correspondence. Mixed-ligand complexes of ruthenium(II) incorporating a diazo ligand: Synthesis .... water (1 : 1) for 5 h to give a dark red solution. The solution was cooled to room temperature. After eva- poration of the solvent, the solid was collected,.

  6. Analytic solution of the BCS gap equation with a logarithmic singularity in the density of states

    International Nuclear Information System (INIS)

    Bhardwaj, A.; Muthu, S.K.

    1999-01-01

    The Bardeen-Cooper-Schrieffer (BCS) gap equation is solved analytically for a density of states function with a logarithmic singularity. It is an extension of our earlier work where we had assumed a constant density of states. We continue to work in the weak-coupling limit and consider both phononic and non-phononic pairings. Expressions are obtained for T c , Δ 0 (the gap at T=0), and the jump in the electronic specific heat at T=T c . We also calculate the isotope exponent and show that it is possible to reproduce the broad features of the experimental results in this framework. (orig.)

  7. cis-Thioindigo (TI) - a new ligand with accessible radical anion and dianion states. Strong magnetic coupling in the {[TI-(μ2-O),(μ-O)]Cp*Cr}2 dimers.

    Science.gov (United States)

    Konarev, Dmitri V; Khasanov, Salavat S; Shestakov, Alexander F; Fatalov, Alexey M; Batov, Mikhail S; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N

    2017-10-24

    Reaction of decamethylchromocene (Cp* 2 Cr) with thioindigo (TI) yields a coordination complex {[TI-(μ 2 -O), (μ-O)]Cp*Cr} 2 ·C 6 H 14 (1) in which one Cp* ligand in Cp* 2 Cr is substituted by TI. TI adopts cis-conformation in 1 allowing the coordination of both carbonyl groups to chromium. Additionally, one oxygen atom of TI becomes a μ 2 -bridge for two chromium atoms to form {[TI-(μ 2 -O), (μ-O)]Cp*Cr} 2 dimers with a CrCr distance of 3.12 Å. According to magnetic data, diamagnetic TI 2- dianions and two Cr 3+ atoms with a high S = 3/2 spin state are present in a dimer allowing strong antiferromagnetic coupling between two Cr 3+ spins with an exchange interaction of -35.4 K and the decrease of molar magnetic susceptibility below 140 K. Paramagnetic TI˙ - radical anions with the S = 1/2 spin state have also been obtained and studied in crystalline {cryptand[2,2,2](Na + )}(TI˙ - ) (2) salt showing that both radical anion and dianion states are accessible for TI.

  8. Observation of glassy state relaxation during annealing of frozen sugar solutions by X-ray computed tomography.

    Science.gov (United States)

    Nakagawa, Kyuya; Tamiya, Shinri; Do, Gabsoo; Kono, Shinji; Ochiai, Takaaki

    2018-06-01

    Glassy phase formation in a frozen product determines various properties of the freeze-dried products. When an aqueous solution is subjected to freezing, a glassy phase forms as a consequence of freeze-concentration. During post-freezing annealing, the relaxation of the glassy phase and the ripening of ice crystals (i.e. Ostwald ripening) spontaneously occur, where the kinetics are controlled by the annealing and glass transition temperatures. This study was motivated to observe the progress of glassy state relaxation separate from ice coarsening during annealing. X-ray computed tomography (CT) was used to observe a frozen and post-freezing annealed solutions by using monochromatized X-ray from the synchrotron radiation. CT images were successfully obtained, and the frozen matrix were analyzed based on the gray level values that were equivalent to the linear X-ray attenuation coefficients of the observed matters. The CT images obtained from rapidly frozen sucrose and dextrin solutions with different concentrations gave clear linear relationships between the linear X-ray attenuation coefficients values and the solute concentrations. It was confirmed that the glassy state relaxation progressed as increasing annealing time, and this trend was larger in the order of the glass transition temperature of the maximally freeze-concentrated phase. The sucrose-water system required nearly 20 h of annealing time at -5 °C for the completion of the glassy phase relaxation, whereas dextrin-water systems required much longer periods because of their higher glass transition temperatures. The trends of ice coarsening, however, did not perfectly correspond to the trends of the relaxation, suggesting that the glassy phase relaxation and Ostwald ripening would jointly control the ice crystal growth/ripening kinetics, and the dominant mechanism differed by the annealing stage. Copyright © 2018 Elsevier B.V. All rights reserved.

  9. Numerical study on the convergence to steady state solutions of a new class of high order WENO schemes

    Science.gov (United States)

    Zhu, Jun; Shu, Chi-Wang

    2017-11-01

    A new class of high order weighted essentially non-oscillatory (WENO) schemes (Zhu and Qiu, 2016, [50]) is applied to solve Euler equations with steady state solutions. It is known that the classical WENO schemes (Jiang and Shu, 1996, [23]) might suffer from slight post-shock oscillations. Even though such post-shock oscillations are small enough in magnitude and do not visually affect the essentially non-oscillatory property, they are truly responsible for the residue to hang at a truncation error level instead of converging to machine zero. With the application of this new class of WENO schemes, such slight post-shock oscillations are essentially removed and the residue can settle down to machine zero in steady state simulations. This new class of WENO schemes uses a convex combination of a quartic polynomial with two linear polynomials on unequal size spatial stencils in one dimension and is extended to two dimensions in a dimension-by-dimension fashion. By doing so, such WENO schemes use the same information as the classical WENO schemes in Jiang and Shu (1996) [23] and yield the same formal order of accuracy in smooth regions, yet they could converge to steady state solutions with very tiny residue close to machine zero for our extensive list of test problems including shocks, contact discontinuities, rarefaction waves or their interactions, and with these complex waves passing through the boundaries of the computational domain.

  10. Functional Coherence in the State Education Agency: A Structure for Performance Management. Solutions. Issue No. 4

    Science.gov (United States)

    Redding, Sam; Nafziger, Dean

    2013-01-01

    The purpose of the state education agency (SEA) is to focus the entire education system on helping students become capable in college and career in an increasingly complex world. One of the most vexing problems facing SEAs today is how to meet increasing demands for performance while adjusting to significant resource reductions. Meeting that…

  11. A matrix product solution for a nonequilibrium steady state of an XX chain

    International Nuclear Information System (INIS)

    Znidaric, Marko

    2010-01-01

    A one-dimensional XX spin chain of finite length coupled to reservoirs at both ends is solved exactly in terms of a matrix product state ansatz. An explicit representation of matrices of fixed dimension 4 independent of the chain length is found. Expectations of all observables are evaluated, showing that all connected correlations, apart from the nearest neighbor z-z, are zero.

  12. Balancing conflicting values: ecosystem solutions in the Pacific Northwest of the United States and Canada.

    Science.gov (United States)

    Richard W. Haynes; Robert C. Szaro; Dennis P. Dykstra

    2005-01-01

    Ecosystem approaches to sustainable forest management in the Pacific Northwest of the United States and Canada have arisen in response to significant changes that have occurred in these societies over the past century or so (Interagency Ecosystem Management Task Force, 1995). One such change as been rapid population growth along the Pacific Coast, where the mild...

  13. State-space solutions to the h_inf/ltr design problem

    DEFF Research Database (Denmark)

    Niemann, Hans Henrik

    1993-01-01

    observer based approach is proposed, where the Z part of the controller is appended to a standard full-order observer. Second, allowing for general controllers, an JC state-space problem is formulated directly from the recovery errors. Both approaches lead to controller orders of at most 2n. In the minimum...

  14. AMPA receptor ligands

    DEFF Research Database (Denmark)

    Strømgaard, Kristian; Mellor, Ian

    2004-01-01

    Alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionic acid (AMPA) receptors (AMPAR), subtype of the ionotropic glutamate receptors (IGRs), mediate fast synaptic transmission in the central nervous system (CNS), and are involved in many neurological disorders, as well as being a key player in the f......Alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionic acid (AMPA) receptors (AMPAR), subtype of the ionotropic glutamate receptors (IGRs), mediate fast synaptic transmission in the central nervous system (CNS), and are involved in many neurological disorders, as well as being a key player...... in the formation of memory. Hence, ligands affecting AMPARs are highly important for the study of the structure and function of this receptor, and in this regard polyamine-based ligands, particularly polyamine toxins, are unique as they selectively block Ca2+ -permeable AMPARs. Indeed, endogenous intracellular...

  15. In silico analysis of the three-dimensional structures of the homodimer of uridine phosphorylase from Yersinia Pseudotuberculosis in the ligand-free state and in a complex with 5-fluorouracil

    Energy Technology Data Exchange (ETDEWEB)

    Lashkov, A. A., E-mail: alashkov83@gmail.com; Sotnichenko, S. E.; Mikhailov, A. M. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)

    2013-03-15

    Pseudotuberculosis is an acute infectious disease characterized by a lesion of the gastrointestinal tract. A positive therapeutic effect can be achieved by selectively suppressing the activity of uridine phosphorylase from the causative agent of the disease Yersinia pseudotuberculosis. The synergistic effect of a combination of the chemotherapeutic agent 5-fluorouracil and antimicrobial drugs, which block the synthesis of pyrimidine bases, on the cells of pathogenic protozoa and bacteria is described in the literature. The three-dimensional structures of uridine phosphorylase from Yersinia pseudotuberculosis (YptUPh) both in the ligand-free state and in complexes with pharmacological agents are unknown, which hinders the search for and design of selective inhibitors of YptUPh. The three-dimensional structure of the ligand-free homodimer of YptUPh was determined by homology-based molecular modeling. The three-dimensional structure of the subunit of the YptUPh molecule belongs to {alpha}/{beta} proteins, and its topology is a three-layer {alpha}/{beta}/{alpha} sandwich. The subunit monomer of the YptUPh molecule consists of 38% helices and 24% {beta} strands. A model of the homodimer structure of YptUPh in a complex with 5-FU was obtained by the molecular docking. The position of 5-FU in the active site of the molecule is very consistent with the known data on the X-ray diffraction structures of other bacterial uridine phosphorylases (the complex of uridine phosphorylase from Salmonella typhimurium (StUPh) with 5-FU, ID PDB: 4E1V and the complex of uridine phosphorylase from Escherichia coli (EcUPh) with 5-FU and ribose 1-phosphate, ID PDB: 1RXC).

  16. Complexation of f elements by tripodal ligands containing aromatic nitrogens. Application to the selective extraction of actinides(III)

    International Nuclear Information System (INIS)

    Wietzke, Raphael

    1999-01-01

    This work initiates a research project, whose aim is the actinides(lll)/lanthanides(III) separation by liquid-liquid extraction. We were interested in the study of the coordination chemistry of lanthanides(III) and uranium(III) (uranium(III) as model for the actinides(III)), with the aim to show differences between the two families and to better understand the coordination properties involved in the extraction process. We studied the lanthanide(III) and uranium(III) complexation with tripodal ligands containing aromatic nitrogens. Several tripodal ligands were synthesized varying the type and the number of the donor atoms. The lanthanide(III) complexes have been characterized in the solid state and in solution (by several techniques: "1H NMR, ESMS, luminescence, UV spectrophotometry, conductometry). Differences in the coordination were found depending on the nature of the donor atoms. The new ligands, tris(2-pyrazinylmethyl)amine (tpza) et tris(N,N-diethyl-2-carbamoyl-6- pyridylmethyl)amine (tpaa), have shown a selectivity for the actinides(III) with promising results in liquid-liquid extraction. The comparison between the lanthanum(III) and uranium(III) complexes with the ligand tpza showed differences in the bonding nature, which could be attributed to a covalent contribution to the metal-ligand bond. (author) [fr

  17. Radiobiology with DNA ligands

    International Nuclear Information System (INIS)

    Weinreich, R.; Argentini, M.; Guenther, I.; Koziorowski, J.; Larsson, B.; Nievergelt-Egido, M.C.; Salt, C.; Wyer, L.; Dos Santos, D.F.; Hansen, H.J.

    1997-01-01

    The paper deals with the following topics: labelling of DNA ligands and other tumour-affinic compounds with 4.15-d 124 I, radiotoxicity of Hoechst 33258 and 33342 and of iodinated Hoechst 33258 in cell cultures, preparation of 76 Br-, 123 I-, and 221 At-labelled 5-halo-2'-deoxyuridine, chemical syntheses of boron derivatives of Hoechst 33258.III., Gadolinium neutron capture therapy

  18. Electrolytic formation of technetium complexes with π-acceptor ligands

    International Nuclear Information System (INIS)

    Cerda, F.; Kremer, C.; Gambino, D.; Kremer, E.

    1994-01-01

    Electrolytic reduction of pertechnetate was performed in aqueous solution containing π-acceptor ligands. Cyanide and 1,10-phenanthroline were the selected ligands. In both cases, electrolyses produced a cathodic TcO 2 deposit and soluble Tc complexes. When cyanide was the ligand, the complexes formed were [Tc(CN) 6 ] 5- and [TcO 2 (CN) 4 ] 3- . When working with the amine, [Tc(phen) 3 ] 2+ and another positively charged species were found after reaction. Results are compared with previous studies with amines, and the usefulness of the electrolytic route to obtain Tc complexes is evaluated. (author) 11 refs.; 2 figs.; 1 tab

  19. Laminating solution-processed silver nanowire mesh electrodes onto solid-state dye-sensitized solar cells

    KAUST Repository

    Hardin, Brian E.

    2011-06-01

    Solution processed silver nanowire meshes (Ag NWs) were laminated on top of solid-state dye-sensitized solar cells (ss-DSCs) as a reflective counter electrode. Ag NWs were deposited in <1 min and were less reflective compared to evaporated Ag controls; however, AgNW ss-DSC devices consistently had higher fill factors (0.6 versus 0.69), resulting in comparable power conversion efficiencies (2.7%) compared to thermally evaporated Ag control (2.8%). Laminated Ag NW electrodes enable higher throughput manufacturing and near unity material usage, resulting in a cheaper alternative to thermally evaporated electrodes. © 2011 Elsevier B.V. All rights reserved.

  20. Shock Hugoniot and equations of states of water, castor oil, and aqueous solutions of sodium chloride, sucrose and gelatin

    Science.gov (United States)

    Gojani, A. B.; Ohtani, K.; Takayama, K.; Hosseini, S. H. R.

    2016-01-01

    This paper reports a result of experiments for the determination of reliable shock Hugoniot curves of liquids, in particular, at relatively low pressure region, which are needed to perform precise numerical simulations of shock wave/tissue interaction prior to the development of shock wave related therapeutic devices. Underwater shock waves were generated by explosions of laser ignited 10 mg silver azide pellets, which were temporally and spatially well controlled. Measuring temporal variation of shock velocities and over-pressures in caster oil, aqueous solutions of sodium chloride, sucrose and gelatin with various concentrations, we succeeded to determine shock Hugoniot curves of these liquids and hence parameters describing Tait type equations of state.

  1. Numerical solutions to the critical state in a magnet-high temperature superconductor interaction

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz-Alonso, D; Coombs, T A; Campbell, A M [Cambridge University Engineering Department, Trumpington Street, Cambridge CB2 1PZ (United Kingdom)

    2005-02-01

    This paper presents an algorithm to simulate the electromagnetic behaviour of devices containing high temperature superconductors in axially symmetric problems. The numerical method is built within the finite element method. The electromagnetic properties of HTSCs are described through the critical-state model. Measurements of the axial force between a permanent magnet and a melt-textured YBCO puck are obtained in order to validate the method. This simple system is modelled so that the proposed method obtains the current distribution and electromagnetic fields in the HTSC. The forces in the interaction between the magnet and the HTSC puck can then be calculated. A comparison between experimental and simulation results shows good matching. The simplification of using the critical-state model and ignoring flux creep in this type of configuration is also explored.

  2. Synthesis and binding studies of Alzheimer ligands on solid support.

    Science.gov (United States)

    Rzepecki, Petra; Geib, Nina; Peifer, Manuel; Biesemeier, Frank; Schrader, Thomas

    2007-05-11

    Aminopyrazole derivatives constitute the first class of nonpeptidic rationally designed beta-sheet ligands. Here we describe a double solid-phase protocol for both synthesis and affinity testing. The presented solid-phase synthesis of four types of hybrid compounds relies on the Fmoc strategy and circumvents subsequent HPLC purification by precipitating the final product from organic solution in pure form. Hexa- and octapeptide pendants with internal di- and tetrapeptide bridges are now amenable in high yields to combinatorial synthesis of compound libraries for high-throughput screening purposes. Solid-phase peptide synthesis (SPPS) on an acid-resistant PAM allows us, after PMB deprotection, to subject the free aminopyrazole binding sites in an immobilized state to on-bead assays with fluorescence-labeled peptides. From the fluorescence emission intensity decrease, individual binding constants can be calculated via reference curves by simple application of the law of mass action. Gratifyingly, host/guest complexation can be monitored quantitatively even for those ligands, which are almost insoluble in water.

  3. Kinetics of photochromic processes in substituted dihydropyridines in the solid state and in solution

    Czech Academy of Sciences Publication Activity Database

    Sworakowski, J.; Nešpůrek, Stanislav; Lipinski, J.; Lewanowicz, A.; Sliwinska, E.

    2001-01-01

    Roč. 356, - (2001), s. 163-173 ISSN 1058-725X. [International Conference on the Chemistry of the Organic Solid State /14./. Cambridge, 25.07.1999-30.07.1999] R&D Projects: GA AV ČR IAA1050901; GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : dihydropyridine * photochromism * reaction kinetics Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.457, year: 2001

  4. Bound state solution of the Grassmannian nonlinear sigma model with fermions

    International Nuclear Information System (INIS)

    Abdalla, E.; Lima-Santos, A.

    1987-11-01

    We construct the s matrix for bound state (gauge-invariant) scattering for nonlinear sigma models defined on the manifold SU(N)/S(U(p)x (lower casex)U(n-p)) with fermions. It is not possible to compute gauge non-singlet matrix elements. In the present language they are not submitted to sufficiently many constraints derived from higher conservation laws. (author) [pt

  5. The reactivities of furocoumarin excited states with DNA in solution. A laser flash photolysis and fluorescence study.

    Science.gov (United States)

    Beaumont, P C; Parsons, B J; Navaratnam, S; Phillips, G O; Allen, J C

    1980-07-29

    The effect of DNA on both the fluorescence emission spectra and yields and lifetimes of the triplet stae of psoralen and 8-methoxypsoralen in aqueous solution has been determined. The changes in the fluorescence spectra are similar in nature for both of these furocoumarins and are attributed to binding of the drug to DNA. The yield of the 8-methoxypsoralen triplet state when bound to DNA was found to be similar, if not identical, to that measured in the absence of DNA. This contrasts sharply with data obtained for psoralen from which it is concluded that either the yield of bound psoralen triplet states is very low, if not zero, or that the lifetime of such species is less than 50 ns. The relevance of this data to the molecular basis of skin photosensitisation by furocoumarins is discussed.

  6. A gradual update method for simulating the steady-state solution of stiff differential equations in metabolic circuits.

    Science.gov (United States)

    Shiraishi, Emi; Maeda, Kazuhiro; Kurata, Hiroyuki

    2009-02-01

    Numerical simulation of differential equation systems plays a major role in the understanding of how metabolic network models generate particular cellular functions. On the other hand, the classical and technical problems for stiff differential equations still remain to be solved, while many elegant algorithms have been presented. To relax the stiffness problem, we propose new practical methods: the gradual update of differential-algebraic equations based on gradual application of the steady-state approximation to stiff differential equations, and the gradual update of the initial values in differential-algebraic equations. These empirical methods show a high efficiency for simulating the steady-state solutions for the stiff differential equations that existing solvers alone cannot solve. They are effective in extending the applicability of dynamic simulation to biochemical network models.

  7. Electronic Excitations in Solution: The Interplay between State Specific Approaches and a Time-Dependent Density Functional Theory Description.

    Science.gov (United States)

    Guido, Ciro A; Jacquemin, Denis; Adamo, Carlo; Mennucci, Benedetta

    2015-12-08

    We critically analyze the performances of continuum solvation models when coupled to time-dependent density functional theory (TD-DFT) to predict solvent effects on both absorption and emission energies of chromophores in solution. Different polarization schemes of the polarizable continuum model (PCM), such as linear response (LR) and three different state specific (SS) approaches, are considered and compared. We show the necessity of introducing a SS model in cases where large electron density rearrangements are involved in the excitations, such as charge-transfer transitions in both twisted and quadrupolar compounds, and underline the very delicate interplay between the selected polarization method and the chosen exchange-correlation functional. This interplay originates in the different descriptions of the transition and ground/excited state multipolar moments by the different functionals. As a result, the choice of both the DFT functional and the solvent polarization scheme has to be consistent with the nature of the studied electronic excitation.

  8. Colloidal Quantum Dot Inks for Single-Step-Fabricated Field-Effect Transistors: The Importance of Postdeposition Ligand Removal.

    Science.gov (United States)

    Balazs, Daniel M; Rizkia, Nisrina; Fang, Hong-Hua; Dirin, Dmitry N; Momand, Jamo; Kooi, Bart J; Kovalenko, Maksym V; Loi, Maria Antonietta

    2018-02-14

    Colloidal quantum dots are a class of solution-processed semiconductors with good prospects for photovoltaic and optoelectronic applications. Removal of the surfactant, so-called ligand exchange, is a crucial step in making the solid films conductive, but performing it in solid state introduces surface defects and cracks in the films. Hence, the formation of thick, device-grade films have only been possible through layer-by-layer processing, limiting the technological interest for quantum dot solids. Solution-phase ligand exchange before the deposition allows for the direct deposition of thick, homogeneous films suitable for device applications. In this work, fabrication of field-effect transistors in a single step is reported using blade-coating, an upscalable, industrially relevant technique. Most importantly, a postdeposition washing step results in device properties comparable to the best layer-by-layer processed devices, opening the way for large-scale fabrication and further interest from the research community.

  9. Conformational dynamics of Escherichia coli flavodoxins in apo- and holo-states by solution NMR spectroscopy.

    Directory of Open Access Journals (Sweden)

    Qian Ye

    Full Text Available Flavodoxins are a family of small FMN-binding proteins that commonly exist in prokaryotes. They utilize a non-covalently bound FMN molecule to act as the redox center during the electron transfer processes in various important biological pathways. Although extensive investigations were performed, detailed molecular mechanisms of cofactor binding and electron transfer remain elusive. Herein we report the solution NMR studies on Escherichia coli flavodoxins FldA and YqcA, belonging to the long-chain and short-chain flavodoxin subfamilies respectively. Our structural studies demonstrate that both proteins show the typical flavodoxin fold, with extensive conformational exchanges observed near the FMN binding pocket in their apo-forms. Cofactor binding significantly stabilizes both proteins as revealed by the extension of secondary structures in the holo-forms, and the overall rigidity shown by the backbone dynamics data. However, the 50 s loops of both proteins in the holo-form still show conformational exchanges on the µs-ms timescales, which appears to be a common feature in the flavodoxin family, and might play an important role in structural fine-tuning during the electron transfer reactions.

  10. Thermodynamic Equations of State for Aqueous Solutions Applied to Deep Icy Satellite and Exoplanet Oceans

    Science.gov (United States)

    Vance, S.; Brown, J. M.; Bollengier, O.; Journaux, B.; Sotin, C.; Choukroun, M.; Barnes, R.

    2014-12-01

    Supporting life in icy world or exoplanet oceans may require global seafloor chemical reactions between water and rock. Such interactions have been regarded as limited in larger icy worlds such as Ganymede and Titan, where ocean depths approach 800 km and GPa pressures (>10katm). If the oceans are composed of pure water, such conditions are consistent with the presence of dense ice phases V and VI that cover the rocky seafloor. Exoplanets with oceans can obtain pressures sufficient to generate ices VII and VIII. We have previously demonstrated temperature gradients in such oceans on the order of 20 K or more, resulting from fluid compressibility in a deep adiabatic ocean based on our experimental work. Accounting for increases in density for highly saline oceans leads to the possibility of oceans perched under and between high pressure ices. Ammonia has the opposite effect, instead decreasing ocean density, as reported by others and confirmed by our laboratory measurements in the ammonia water system. Here we report on the completed equation of state for aqueous ammonia derived from our prior measurements and optimized global b-spline fitting methods We use recent diamond anvil cell measurements for water and ammonia to extend the equation of state to 400°C and beyond 2 GPa, temperatures and pressures applicable to icy worlds and exoplanets. Densities show much less temperature dependence but comparabe high-pressure derivatives to previously published ammonia-water properties derived for application to Titan (Croft et al. 1988). Thermal expansion is in better agreement with the more self-consistent equation of state of Tillner-Roth and Friend (1998). We also describe development of a planetary NaCl equation of state using recent measurements of phase boundaries and sound speeds. We examine implications of realistic ocean-ice thermodynamics for Titan and exoplanet interiors using the methodology recently applied to Ganymede for oceans dominated by MgSO4. High

  11. Investigation of solutions of state-dependent multi-impulsive boundary value problems

    Czech Academy of Sciences Publication Activity Database

    Rontó, András; Rachůnková, I.; Rontó, M.; Rachůnek, L.

    2017-01-01

    Roč. 24, č. 2 (2017), s. 287-312 ISSN 1072-947X R&D Projects: GA ČR(CZ) GA14-06958S Institutional support: RVO:67985840 Keywords : state-dependent multi-impulsive systems * non-linear boundary value problem * parametrization technique Subject RIV: BA - General Mathematics OBOR OECD: Applied mathematics Impact factor: 0.290, year: 2016 https://www.degruyter.com/view/j/gmj.2017.24.issue-2/gmj-2016-0084/gmj-2016-0084.xml

  12. Investigation of solutions of state-dependent multi-impulsive boundary value problems

    Czech Academy of Sciences Publication Activity Database

    Rontó, András; Rachůnková, I.; Rontó, M.; Rachůnek, L.

    2017-01-01

    Roč. 24, č. 2 (2017), s. 287-312 ISSN 1072-947X R&D Projects: GA ČR(CZ) GA14-06958S Institutional support: RVO:67985840 Keywords : state-dependent multi-impulsive systems * non-linear boundary value problem * parametrization technique Subject RIV: BA - General Mathematics OBOR OECD: Applied mathematics Impact factor: 0.290, year: 2016 https://www.degruyter.com/view/j/gmj.2017.24.issue-2/gmj-2016-0084/gmj-2016-0084. xml

  13. A maintenance policy for a system with multi-state components: an approximate solution

    International Nuclear Information System (INIS)

    Guerler, Uelkue; Kaya, Alev

    2002-01-01

    For maintenance and quality assessment purposes, various performance levels for both systems and components are identified, usually as a function of the deterioration. In this study, we consider a multicomponent system where the lifetime of each component is described by several stages, (0,...,S), which are further classified as good, doubtful, preventive maintenance due (PM due) and down. A control policy is suggested where the system is replaced when a component enters a PM due or a down state and the number of components in the doubtful states (K,...,S-2) is at least N. All maintenance activities are assumed to take negligible time. The exact description of the underlying stochastic model under the policy is very complicated. We therefore propose some approximations, which allow an explicit expression for the long run average cost function, which is minimized w.r.t. (K,N) by numerical methods. Sensitivity of the model to system parameters and the performance of the approximation are investigated through several examples

  14. A numerical solution to an inverse unsteady-state heat transfer problem involving the Trefftz functions

    Directory of Open Access Journals (Sweden)

    Maciejewska Beata

    2017-01-01

    Full Text Available This paper shows the results concerning flow boiling heat transfer in an asymmetrically heated vertical minichannel. The heated element for FC-72 Fluorinert flowing in that minichannel was a thin foil. The foil surface temperature was monitored continuously at 18 points by K-type thermocouples from the outer foil surface. Fluid temperature and pressure in the minichannel inlet and outlet, current supplied to the foil and voltage drop were also monitored. Measurements were carried out at 1 s intervals. The objective was to determine the heat transfer coefficient on the heated foil–fluid contact surface in the minichannel. It was obtained from the Robin boundary condition. The foil temperature was the result of solving the nonstationary two-dimensional inverse boundary problem in the heated foil. Using the FEM combined with Trefftz functions as basis functions solved the problem. The unknown temperature values at nodes were calculated by minimising the adequate functional. The values of local heat transfer coefficients were consistent with the results obtained by the authors in their previous studies when steady-state conditions were analysed. This time, however, these values were analysed as time dependent, which facilitated observation of coefficient changes that were impossible to observe under the steady-state conditions.

  15. Inclusion of Paracetamol into β-cyclodextrin nanocavities in solution and in the solid state

    Science.gov (United States)

    El-Kemary, Maged; Sobhy, Saffaa; El-Daly, Samy; Abdel-Shafi, Ayman

    2011-09-01

    We report on steady-state UV-visible absorption and emission characteristics of Paracetamol, drug used as antipyretic agent, in water and within cyclodextrins (CDs): β-CD, 2-hydroxypropyl- β-CD (HP- β-CD) and 2,6-dimethyl- β-CD (Me- β-CD). The results reveal that Paracetamol forms a 1:1 inclusion complex with CD. Upon encapsulation, the emission intensity enhances, indicating a confinement effect of the nanocages on the photophysical behavior of the drug. Due to its methyl groups, the Me- β-CD shows the largest effect for the drug. The observed binding constant showing the following trend: Me- β-CD > HP- β-CD > β-CD. The less complexing effectiveness of HP- β-CD is due to the steric effect of the hydroxypropyl-substituents, which can hamper the inclusion of the guest molecules. The solid state inclusion complex was prepared by co-precipitation method and its characterization was investigated by Fourier transform infrared spectroscopy, 1H NMR and X-ray diffractometry. These approaches indicated that Paracetamol was able to form an inclusion complex with CDs, and the inclusion compounds exhibited different spectroscopic features and properties from Paracetamol.

  16. An integrated low carbon energy solution to cooking fuel, tailored to Niger state's rural population

    Science.gov (United States)

    Carvell, Aaron; Price-Allison, Andrew; Birch, Calum; Green, Toby; Harijan, Khanji; Maihankuri, Sheidi; Raji, Abdulganiy; Uqaili, Mohammed; Dupont, Valerie

    2017-11-01

    Niger State (Nigeria) was selected as a case study of renewable, affordable and user friendly clean energy provision in remote areas of developing countries. Niger state has 80% of its 4.5 million population living in rural agrarian areas with low literacy rates, there is a lack of wind thus eliminating wind as widely available potential power source. Based on the assessment of the local large insolation, the type of agricultural, biomass and husbandry resources, this study selected the design of anaerobic digestion units processing mostly animal and human waste, and whose heating and power requirement would be entirely provided by solar photovoltaic/thermal to maintain optimum efficiency of the biogas production. The designs was carried out at the scale of up to 15 household demand (community scale). Volume and therefore the production of biogas maybe increased or decreased in the design considered, and local, low cost resilient material were proposed. The proposed system was costed for a community of 24 people, demonstrating the potential for clean and renewable gas production economically.

  17. Learning of state-space models with highly informative observations: A tempered sequential Monte Carlo solution

    Science.gov (United States)

    Svensson, Andreas; Schön, Thomas B.; Lindsten, Fredrik

    2018-05-01

    Probabilistic (or Bayesian) modeling and learning offers interesting possibilities for systematic representation of uncertainty using probability theory. However, probabilistic learning often leads to computationally challenging problems. Some problems of this type that were previously intractable can now be solved on standard personal computers thanks to recent advances in Monte Carlo methods. In particular, for learning of unknown parameters in nonlinear state-space models, methods based on the particle filter (a Monte Carlo method) have proven very useful. A notoriously challenging problem, however, still occurs when the observations in the state-space model are highly informative, i.e. when there is very little or no measurement noise present, relative to the amount of process noise. The particle filter will then struggle in estimating one of the basic components for probabilistic learning, namely the likelihood p (data | parameters). To this end we suggest an algorithm which initially assumes that there is substantial amount of artificial measurement noise present. The variance of this noise is sequentially decreased in an adaptive fashion such that we, in the end, recover the original problem or possibly a very close approximation of it. The main component in our algorithm is a sequential Monte Carlo (SMC) sampler, which gives our proposed method a clear resemblance to the SMC2 method. Another natural link is also made to the ideas underlying the approximate Bayesian computation (ABC). We illustrate it with numerical examples, and in particular show promising results for a challenging Wiener-Hammerstein benchmark problem.

  18. Combined solid state and solution NMR studies of {alpha},{epsilon}-{sup 15}N labeled bovine rhodopsin

    Energy Technology Data Exchange (ETDEWEB)

    Werner, Karla; Lehner, Ines [Johann Wolfgang Goethe-Universitaet Frankfurt, Center for Biomolecular Magnetic Resonance (Germany); Dhiman, Harpreet Kaur [University of Pittsburgh School of Medicine, Department of Structural Biology (United States); Richter, Christian; Glaubitz, Clemens; Schwalbe, Harald, E-mail: schwalbe@nmr.uni-frankfurt.de; Klein-Seetharaman, Judith [Johann Wolfgang Goethe-Universitaet Frankfurt, Center for Biomolecular Magnetic Resonance (Germany); Khorana, H. Gobind [Massachusetts Institute of Technology, Departments of Biology and Chemistry (United States)], E-mail: khorana@mit.edu

    2007-04-15

    Rhodopsin is the visual pigment of the vertebrate rod photoreceptor cell and is the only member of the G protein coupled receptor family for which a crystal structure is available. Towards the study of dynamics in rhodopsin, we report NMR-spectroscopic investigations of {alpha},{epsilon}-{sup 15}N-tryptophan labeled rhodopsin in detergent micelles and reconstituted in phospholipids. Using a combination of solid state {sup 13}C,{sup 15}N-REDOR and HETCOR experiments of all possible {sup 13}C'{sub i-1} carbonyl/{sup 15}N{sub i}-tryptophan isotope labeled amide pairs, and H/D exchange {sup 1}H,{sup 15}N-HSQC experiments conducted in solution, we assigned chemical shifts to all five rhodopsin tryptophan backbone {sup 15}N nuclei and partially to their bound protons. {sup 1}H,{sup 15}N chemical shift assignment was achieved for indole side chains of Trp35{sup 1.30} and Trp175{sup 4.65}. {sup 15}N chemical shifts were found to be similar when comparing those obtained in the native like reconstituted lipid environment and those obtained in detergent micelles for all tryptophans except Trp175{sup 4.65} at the membrane interface. The results suggest that the integrated solution and solid state NMR approach presented provides highly complementary information in the study of structure and dynamics of large membrane proteins like rhodopsin.

  19. Characterizing the hydration state of L-threonine in solution using terahertz time-domain attenuated total reflection spectroscopy

    Science.gov (United States)

    Huang, Huachuan; Liu, Qiao; Zhu, Liguo; Li, Zeren

    2018-01-01

    The hydration of biomolecules is closely related to the dynamic process of their functional expression, therefore, characterizing hydration phenomena is a subject of keen interest. However, direct measurements on the global hydration state of biomolecules couldn't have been acquired using traditional techniques such as thermodynamics, ultrasound, microwave spectroscopy or viscosity, etc. In order to realize global hydration characterization of amino acid such as L-threonine, terahertz time-domain attenuated total reflectance spectroscopy (THz-TDS-ATR) was adopted in this paper. By measuring the complex permittivity of L-threonine solutions with various concentrations in the THz region, the hydration state and its concentration dependence were obtained, indicating that the number of hydrous water decreased with the increase of concentration. The hydration number was evaluated to be 17.8 when the molar concentration of L-threonine was 0.34 mol/L, and dropped to 13.2 when the molar concentration increased to 0.84 mol/L, when global hydration was taken into account. According to the proposed direct measurements, it is believed that the THz-TDS-ATR technique is a powerful tool for studying the picosecond molecular dynamics of amino acid solutions.

  20. Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

    Science.gov (United States)

    Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

    2015-10-01

    We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

  1. C-H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst's activity and selectivity.

    Science.gov (United States)

    Shul'pin, Georgiy B

    2013-09-28

    This brief essay consists of a few "exciting stories" devoted to relations within a metal-complex catalyst between a metal ion and a coordinated ligand. When, as in the case of a human couple, the rapport of the partners is cordial and a love cements these relations, a chemist finds an ideal married couple, in other words he obtains a catalyst of choice which allows him to functionalize C-H bonds very efficiently and selectively. Examples of such lucky marriages in the catalytic world of ions and ligands are discussed here. Activity of the catalyst is characterized by turnover number (TON) or turnover frequency (TOF) as well as by yield of a target product. Introducing a chelating N,N- or N,O-ligand to the catalyst molecule (this can be an iron or manganese derivative) sharply enhances its activity. However, the activity of vanadium derivatives (with additionally added to the solution pyrazinecarboxylic acid, PCA) as well as of various osmium complexes does not dramatically depend on the nature of ligands surrounding metal ions. Complexes of these metals are very efficient catalysts in oxidations with H2O2. Osmium derivatives are record-holders exhibiting extremely high TONs whereas vanadium complexes are on the second position. Finally, elegant examples of alkane functionalization on the ions of non-transition metals (aluminium, gallium etc.) are described when one ligand within the metal complex (namely, hydroperoxyl ligand HOO(-)) helps other ligand of this complex (H2O2 molecule coordinated to the metal) to disintegrate into two species, generating very reactive hydroxyl radical. Hydrogen peroxide molecule, even ligated to the metal ion, is perfectly stable without the assistance of the neighboring HOO(-) ligand. This ligand can be easily oxidized donating an electron to its partner ligand (H2O2). In an analogous case, when the central ion in the catalyst is a transition metal, this ion changing its oxidation state can donate an electron to the coordinated H2O2

  2. Calculation of relative free energies for ligand-protein binding, solvation, and conformational transitions using the GROMOS software.

    Science.gov (United States)

    Riniker, Sereina; Christ, Clara D; Hansen, Halvor S; Hünenberger, Philippe H; Oostenbrink, Chris; Steiner, Denise; van Gunsteren, Wilfred F

    2011-11-24

    The calculation of the relative free energies of ligand-protein binding, of solvation for different compounds, and of different conformational states of a polypeptide is of considerable interest in the design or selection of potential enzyme inhibitors. Since such processes in aqueous solution generally comprise energetic and entropic contributions from many molecular configurations, adequate sampling of the relevant parts of configurational space is required and can be achieved through molecular dynamics simulations. Various techniques to obtain converged ensemble averages and their implementation in the GROMOS software for biomolecular simulation are discussed, and examples of their application to biomolecules in aqueous solution are given. © 2011 American Chemical Society

  3. Ground and excited state properties of high performance anthocyanidin dyes-sensitized solar cells in the basic solutions

    Energy Technology Data Exchange (ETDEWEB)

    Prima, Eka Cahya [Advanced Functional Material Laboratory, Engineering Physics, Institut Teknologi Bandung (Indonesia); Computational Material Design and Quantum Engineering Laboratory, Engineering Physics, Institut Teknologi Bandung (Indonesia); International Program on Science Education, Universitas Pendidikan Indonesia (Indonesia); Yuliarto, Brian; Suyatman, E-mail: yatman@tf.itb.ac.id [Advanced Functional Material Laboratory, Engineering Physics, Institut Teknologi Bandung (Indonesia); Dipojono, Hermawan Kresno [Computational Material Design and Quantum Engineering Laboratory, Engineering Physics, Institut Teknologi Bandung (Indonesia)

    2015-09-30

    The aglycones of anthocyanidin dyes were previously reported to form carbinol pseudobase, cis-chalcone, and trans-chalcone due to the basic levels. The further investigations of ground and excited state properties of the dyes were characterized using density functional theory with PCM(UFF)/B3LYP/6-31+G(d,p) level in the basic solutions. However, to the best of our knowledge, the theoretical investigation of their potential photosensitizers has never been reported before. In this paper, the theoretical photovoltaic properties sensitized by dyes have been successfully investigated including the electron injections, the ground and excited state oxidation potentials, the estimated open circuit voltages, and the light harvesting efficiencies. The results prove that the electronic properties represented by dyes’ LUMO-HOMO levels will affect to the photovoltaic performances. Cis-chalcone dye is the best anthocyanidin aglycone dye with the electron injection spontaneity of −1.208 eV, the theoretical open circuit voltage of 1.781 V, and light harvesting efficiency of 56.55% due to the best HOMO-LUMO levels. Moreover, the ethanol solvent slightly contributes to the better cell performance than the water solvent dye because of the better oxidation potential stabilization in the ground state as well as in the excited state. These results are in good agreement with the known experimental report that the aglycones of anthocyanidin dyes in basic solvent are the high potential photosensitizers for dye-sensitized solar cell.

  4. Controlling Metal/Ligand/Metal Oxidation State Combinations by Ancillary Ligand (L) Variation in the Redox Systems [L2Ru(.mu.boptz)RuL2]n, boptz=3, 6-bis(2-oxidophenyl)- 1,2,4,5 tetrazine and L=acetylacetonate, 2,2´-bipyridine, or 2-phenylazopyridine

    Czech Academy of Sciences Publication Activity Database

    Patra, S.; Sarkar, B.; Maji, S.; Fiedler, Jan; Urbanos, F. A.; Jimenez-Aparicio, R.; Kaim, W.; Lahiri, G. K.

    2006-01-01

    Roč. 12, č. 2 (2006), s. 489-498 ISSN 0947-6539 R&D Projects: GA AV ČR IAA400400505; GA MŠk LC510 Institutional research plan: CEZ:AV0Z40400503 Keywords : bridging ligands * EPR spectroscopy * magnetic properties * N,O ligands * ruthenium Subject RIV: CF - Physical ; The oretical Chemistry Impact factor: 5.015, year: 2006

  5. Modeling of Dielectric Properties of Aqueous Salt Solutions with an Equation of State

    DEFF Research Database (Denmark)

    Maribo-Mogensen, Bjørn; Kontogeorgis, Georgios; Thomsen, Kaj

    2013-01-01

    The static permittivity is the most important physical property for thermodynamic models that account for the electrostatic interactions between ions. The measured static permittivity in mixtures containing electrolytes is reduced due to kinetic depolarization and reorientation of the dipoles...... methodology for obtaining the static permittivity over wide ranges of temperatures, pressures, and compositions for use within an equation of state for mixed solvents containing salts. The static permittivity is calculated from a new extension of the framework developed by Onsager, Kirkwood, and Fröhlich...... to associating mixtures. Wertheim’s association model as formulated in the statistical associating fluid theory is used to account for hydrogen-bonding molecules and ion–solvent association. Finally, we compare the Debye–Hückel Helmholtz energy obtained using an empirical model with the new physical model...

  6. State-of-the-art in modeling solute and sediment transport in rivers

    International Nuclear Information System (INIS)

    Sayre, W.W.

    1980-01-01

    This overview is structured around a comprehensive general model based on the conservation of mass principle as applied to dissolved and particulate constituents in rivers, with a few restricted but more specific examples that illustrate the state-of-the-art in modeling typical physical, chemical, and biological processes undergone by selected constituents in rivers. These examples include: simplified one- and two-dimensional formulations focusing on the hydrodynamic advection and dispersion mechanisms; a two-dimensional biochemial oxygen demand-dissolved oxygen model; a one-dimensional polychlorinated biphenyl model that includes uptake and release of constituent by suspended sediment, and deposition and erosion of contaminated particles; and a one-dimensional sediment transport model that accounts for interactions between the flow and the bed, and is capable of tracking dispersing slugs of sediment through cycles of erosion, entrainment, transport in suspension and as bed load, and burial and storage in the bed

  7. Magnetic levitation as a platform for competitive protein-ligand binding assays.

    Science.gov (United States)

    Shapiro, Nathan D; Soh, Siowling; Mirica, Katherine A; Whitesides, George M

    2012-07-17

    This paper describes a method based on magnetic levitation (MagLev) that is capable of indirectly measuring the binding of unlabeled ligands to unlabeled protein. We demonstrate this method by measuring the affinity of unlabeled bovine carbonic anhydrase (BCA) for a variety of ligands (most of which are benzene sulfonamide derivatives). This method utilizes porous gel beads that are functionalized with a common aryl sulfonamide ligand. The beads are incubated with BCA and allowed to reach an equilibrium state in which the majority of the immobilized ligands are bound to BCA. Since the beads are less dense than the protein, protein binding to the bead increases the overall density of the bead. This change in density can be monitored using MagLev. Transferring the beads to a solution containing no protein creates a situation where net protein efflux from the bead is thermodynamically favorable. The rate at which protein leaves the bead for the solution can be calculated from the rate at which the levitation height of the bead changes. If another small molecule ligand of BCA is dissolved in the solution, the rate of protein efflux is accelerated significantly. This paper develops a reaction-diffusion (RD) model to explain both this observation, and the physical-organic chemistry that underlies it. Using this model, we calculate the dissociation constants of several unlabeled ligands from BCA, using plots of levitation height versus time. Notably, although this method requires no electricity, and only a single piece of inexpensive equipment, it can measure accurately the binding of unlabeled proteins to small molecules over a wide range of dissociation constants (K(d) values within the range from ~10 nM to 100 μM are measured easily). Assays performed using this method generally can be completed within a relatively short time period (20 min-2 h). A deficiency of this system is that it is not, in its present form, applicable to proteins with molecular weight greater

  8. Youth tobacco use in the United States--problem, progress, goals, and potential solutions.

    Science.gov (United States)

    Glynn, T J; Greenwald, P; Mills, S M; Manley, M W

    1993-07-01

    Efforts to control tobacco use and tobacco-related morbidity and mortality in the United States continue to be generally successful. In the quarter century since the publication of the first Surgeon General's Report on Tobacco and Health, adult smoking rates in the United States have been reduced by nearly 34%. Controlling tobacco use among our nation's youth, however, has not been as successful. Although there was considerable success in reducing adolescent tobacco use in the late 1970s and early 1980s, tobacco use among youth has remained essentially stable for the past decade. The health and economic burden of tobacco use, current knowledge about youth tobacco use, and youth-related national tobacco reduction goals for the Year 2000 are reviewed. Analysis of the research of the past two decades clearly indicates that there is no "magic bullet" in existence or in sight for the reduction of tobacco use, either among youth or among adults. This does not mean that opportunities for significant advances through, for example, pharmacological therapies or the broad application of media or policy strategies should not continue to be explored, but that for the moment no single approach appears to work best. Rather, a comprehensive approach that applies multiple prevention and cessation strategies simultaneously appears to be most effective in tobacco use control. Among youth, the combination of tobacco control strategies that may work best includes those that involve the family, primary care physicians, and other health professionals such as nurses and dentists; programs that are carried out in schools and/or through the media; and societal approaches such as access and advertising restrictions and increased taxes.

  9. Solution chemistry and separation of metal ions in leached solution

    International Nuclear Information System (INIS)

    Shibata, J.

    1991-01-01

    The method to presume a dissolved state of metal ions in an aqueous solution and the technology to separate and concentrate metal ions in a leached solution are described in this paper. It is very important for the separation of metal ions to know the dissolved state of metal ions. If we know the composition of an aqueous solution and the stability constants of metal-ligand complexes, we can calculate and estimate the concentration of each species in the solution. Then, we can decide the policy to separate and concentrate metal ions. There are several methods for separation and purification; hydroxide precipitation method, sulfide precipitation method, solvent extraction method and ion exchange resin method. Solvent extraction has been used in purification processes of copper refinery, uranium refinery, platinum metal refinery and rare earth metal refinery. Fundamental process of solvent extraction, a kind of commercial extractants, a way of determining a suitable extractant and an equipment are discussed. Finally, it will be emphasized how the separation of rare earths is improved in solvent extraction. (author) 21 figs., 8 tabs., 8 refs

  10. Bexarotene ligand pharmaceuticals.

    Science.gov (United States)

    Hurst, R E

    2000-12-01

    Bexarotene (LGD-1069), from Ligand, was the first retinoid X receptor (RXR)-selective, antitumor retinoid to enter clinical trials. The company launched the drug for the treatment of cutaneous T-cell lymphoma (CTCL), as Targretin capsules, in the US in January 2000 [359023]. The company filed an NDA for Targretin capsules in June 1999, and for topical gel in December 1999 [329011], [349982] specifically for once-daily oral administration for the treatment of patients with early-stage CTCL who have not tolerated other therapies, patients with refractory or persistent early stage CTCL and patients with refractory advanced stage CTCL. The FDA approved Targretin capsules at the end of December 1999 for once-daily oral treatment of all stages of CTCL in patients refractory to at least one prior systemic therapy, at an initial dose of 300 mg/m2/day. After an NDA was submitted in December 1999 for Targretin gel, the drug received Priority Review status for use as a treatment of cutaneous lesions in patients with stage IA, IB or IIA CTCL [354836]. The FDA issued an approvable letter in June 2000, and granted marketing clearance for CTCL in the same month [370687], [372768], [372769], [373279]. Ligand had received Orphan Drug designation for this indication [329011]. At the request of the FDA, Ligand agreed to carry out certain post-approval phase IV and pharmacokinetic studies [351604]. The company filed an MAA with the EMEA for Targretin Capsules to treat lymphoma in November 1999 [348944]. The NDA for Targretin gel is based on a multicenter phase III trial that was conducted in the US, Canada, Europe and Australia involving 50 patients and a multicenter phase I/II clinical program involving 67 patients. Targretin gel was evaluated for the treatment of patients with early stage CTCL (IA-IIA) who were refractory to, intolerant to, or reached a response plateau for at least 6 months on at least two prior therapies. Efficacy results exceeded the protocol-defined response

  11. Fluorescence and picosecond induced absorption from the lowest singlet excited states of quercetin in solutions and polymer films

    Science.gov (United States)

    Bondarev, S. L.; Tikhomirov, S. A.; Buganov, O. V.; Knyukshto, V. N.; Raichenok, T. F.

    2017-03-01

    The spectroscopic and photophysical properties of the biologically important plant antioxidant quercetin in organic solvents, polymer films of polyvinyl alcohol, and a buffer solution at pH 7.0 are studied by stationary luminescence and femtosecond laser spectroscopy at room temperature and 77 K. The large magnitude of the dipole moment of the quercetin molecule in the excited Franck-Condon state μ e FC = 52.8 C m indicates the dipolar nature of quercetin in this excited state. The transient induced absorption spectra S 1→ S n in all solvents are characterized by a short-wave band at λ abs max = 460 nm with exponential decay times in the range of 10.0-20.0 ps. In the entire spectral range at times of >100 ps, no residual induced absorption was observed that could be attributed to the triplet-triplet transitions T 1 → T k in quercetin. In polar solvents, two-band fluorescence was also recorded at room temperature, which is due to the luminescence of the initial enol form of quercetin ( 415 nm) and its keto form with a transferred proton (550 nm). The short-wave band is absent in nonpolar 2-methyltetrahydrofuran (2-MTHF). The spectra of fluorescence and fluorescence excitation exhibit a low dependence on the wavelength of excitation and detection, which may be related to the solvation and conformational changes in the quercetin molecule. Decreasing the temperature of a glassy-like freezing quercetin solution in ethanol and 2-MTHF to 77 K leads to a strong increase in the intensity (by a factor of 100) of both bands. The energy circuits for the proton transfer process are proposed depending on the polarity of the medium. The main channel for the exchange of electronic excitation energy in the quercetin molecule at room temperature is the internal conversion S 1 ⇝ S 0, induced by the state with a proton transfer.

  12. Creation of Novel Solid-Solution Alloy Nanoparticles on the Basis of Density-of-States Engineering by Interelement Fusion.

    Science.gov (United States)

    Kobayashi, Hirokazu; Kusada, Kohei; Kitagawa, Hiroshi

    2015-06-16

    Currently 118 known elements are represented in the periodic table. Of these 118 elements, only about 80 elements are stable, nonradioactive, and widely available for our society. From the viewpoint of the "elements strategy", we need to make full use of the 80 elements to bring out their latent ability and create innovative materials. Furthermore, there is a strong demand that the use of rare or toxic elements be reduced or replaced while their important properties are retained. Advanced science and technology could create higher-performance materials even while replacing or reducing minor or harmful elements through the combination of more abundant elements. The properties of elements are correlated directly with their electronic states. In a solid, the magnitude of the density of states (DOS) at the Fermi level affects the physical and chemical properties. In the present age, more attention has been paid to improving the properties of materials by means of alloying elements. In particular, the solid-solution-type alloy is advantageous because the properties can be continuously controlled by tuning the compositions and/or combinations of the constituent elements. However, the majority of bulk alloys are of the phase-separated type under ambient conditions, where constituent elements are immiscible with each other. To overcome the challenge of the bulk-phase metallurgical aspects, we have focused on the nanosize effect and developed methods involving "nonequilibrium synthesis" or "a process of hydrogen absorption/desorption". We propose a new concept of "density-of-states engineering" for the design of materials having the most desirable and suitable properties by means of "interelement fusion". In this Account, we describe novel solid-solution alloys of Pd-Pt, Ag-Rh, and Pd-Ru systems in which the constituent elements are immiscible in the bulk state. The homogeneous solid-solution alloys of Pd and Pt were created from Pd core/Pt shell nanoparticles using a

  13. Depoliticising the political: Market solutions and the retreat of Swedish institutional drug treatment from state management.

    Science.gov (United States)

    Edman, Johan

    2016-06-01

    This article examines developments in the Swedish drug treatment services in 1982-2000 and explores the ways in which political initiatives and the state administration's management have contributed to the major privatisations of institutional drug treatment during this period. The empirical basis for the textual analysis lies in official reports, parliamentary material and archived records from the Stockholm County Administrative Board's management of treatment facilities. The major privatisations of drug treatment services in the 1980s were both unintentional and unwanted and mainly arose from a lack of bureaucratic control and ideological anchorage. The privatisations were, however, reinforced by ideologically driven NPM-oriented political initiatives in the 1990s. The market-oriented treatment services have failed to fulfil the needs for diversity and availability within a publicly financed sector, which deals with unevenly informed and often socio-economically weak citizens. New management models in this field must ensure that ideological considerations are taken into account to meet politically decided goals and means. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Let Me Relax: Toward Automated Sedentary State Recognition and Ubiquitous Mental Wellness Solutions

    Directory of Open Access Journals (Sweden)

    Vijay Rajanna

    2018-12-01

    Full Text Available Advances in ubiquitous computing technology improve workplace productivity, reduce physical exertion, but ultimately result in a sedentary work style. Sedentary behavior is associated with an increased risk of stress, obesity, and other health complications. Let Me Relax is a fully automated sedentary-state recognition framework using a smartwatch and smartphone, which encourages mental wellness through interventions in the form of simple relaxation techniques. The system was evaluated through a comparative user study of 22 participants split into a test and a control group. An analysis of NASA Task Load Index pre- and post- study survey revealed that test subjects who followed relaxation methods, showed a trend of both increased activity as well as reduced mental stress. Reduced mental stress was found even in those test subjects that had increased inactivity. These results suggest that repeated interventions, driven by an intelligent activity recognition system, is an effective strategy for promoting healthy habits, which reduce stress, anxiety, and other health risks associated with sedentary workplaces.

  15. Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M-S bonding for MS4(2-) (M = Cr, Mo, W) dianions.

    Science.gov (United States)

    Olson, Angela C; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Daly, Scott R; Kozimor, Stosh A; MacInnes, Molly M; Martin, Richard L; Scott, Brian L

    2014-12-14

    Herein, we have evaluated relative changes in M-S electronic structure and orbital mixing in Group 6 MS4(2-) dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as (1)A1 → (1)T2 transitions. For MoS4(2-), both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS4(2-), solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO4(2-) dianions, which allowed M-S and M-O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M-E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M-S bonds, but increased appreciably for M-O interactions. For the t orbitals (σ* + π*), mixing decreased slightly for M-S bonding and increased only slightly for the M-O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME4(2-) (E = O, S) dianions.

  16. Achieving universal health coverage in small island states: could importing health services provide a solution?

    Science.gov (United States)

    Walls, Helen; Smith, Richard

    2018-01-01

    Background Universal health coverage (UHC) is difficult to achieve in settings short of medicines, health workers and health facilities. These characteristics define the majority of the small island developing states (SIDS), where population size negates the benefits of economies of scale. One option to alleviate this constraint is to import health services, rather than focus on domestic production. This paper provides empirical analysis of the potential impact of this option. Methods Analysis was based on publicly accessible data for 14 SIDS, covering health-related travel and health indicators for the period 2003–2013, together with in-depth review of medical travel schemes for the two highest importing SIDS—the Maldives and Tuvalu. Findings Medical travel from SIDS is accelerating. The SIDS studied generally lacked health infrastructure and technologies, and the majority of them had lower than the recommended number of physicians in a country, which limits their capacity for achieving UHC. Tuvalu and the Maldives were the highest importers of healthcare and notably have public schemes that facilitate medical travel and help lower the out-of-pocket expenditure on medical travel. Although different in approach, design and performance, the medical travel schemes in Tuvalu and the Maldives are both examples of measures used to increase access to health services that cannot feasibly be provided in SIDS. Interpretation Our findings suggest that importing health services (through schemes to facilitate medical travel) is a potential mechanism to help achieve universal healthcare for SIDS but requires due diligence over cost, equity and quality control. PMID:29527349

  17. Synthesis, spectral, thermal, potentiometric and antimicrobial studies of transition metal complexes of tridentate ligand

    Directory of Open Access Journals (Sweden)

    Sarika M. Jadhav

    2014-01-01

    Full Text Available A series of metal complexes of Cu(II, Ni(II, Co(II, Fe(III and Mn(II have been synthesized with newly synthesized biologically active tridentate ligand. The ligand was synthesized by condensation of dehydroacetic acid (3-acetyl-6-methyl-(2H pyran-2,4(3H-dione or DHA, o-phenylene diamine and fluoro benzaldehyde and characterized by elemental analysis, molar conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, 1H-NMR, UV–Vis spectroscopy and mass spectra. From the analytical data, the stoichiometry of the complexes was found to be 1:2 (metal:ligand with octahedral geometry. The molar conductance values suggest the non-electrolyte nature of metal complexes. The IR spectral data suggest that the ligand behaves as a dibasic tridentate ligand with ONN donor atoms sequence towards central metal ion. Thermal behaviour (TG/DTA and kinetic parameters calculated by the Coats–Redfern and Horowitz–Metzger method suggest more ordered activated state in complex formation. To investigate the relationship between stability constants of metal complexes and antimicrobial activity, the dissociation constants of Schiff bases and stability constants of their binary metal complexes have been determined potentiometrically in THF–water (60:40% solution at 25 ± 1 °C and at 0.1 M NaClO4 ionic strength. The potentiometric study suggests 1:1 and 1:2 complexation. Antibacterial and antifungal activities in vitro were performed against Staphylococcus aureus, Escherichia coli and Aspergillus niger, Trichoderma, respectively. The stability constants of the metal complexes were calculated by the Irving–Rosotti method. A relation between the stability constant and antimicrobial activity of complexes has been discussed. It is observed that the activity enhances upon complexation and the order of antifungal activity is in accordance with stability order of metal ions.

  18. Synthesis and evaluation structure/extracting and complexing properties of new bi-topic ligands for group actinides extraction

    International Nuclear Information System (INIS)

    Bisson, J.

    2011-01-01

    The aim of this project is to design and study new extractants for spent nuclear fuel reprocessing. To decrease the long-term radiotoxicity of the waste, the GANEX process is an option to homogeneously recycle actinides. All actinides (U, Np, Pu, Am, Cm) would be extracted together from a highly acidic media and separated from fission products (especially from lanthanides). In this context, fourteen new bi-topic ligands constituted of a nitrogen poly-aromatic unit from the dipyridyl-phenanthroline and dipyridyl-1,3,5-triazine families and functionalized by amid groups were synthesized. Extraction studies performed with some of these ligands confirmed their interest to selectively separate actinides at different oxidation states from an aqueous solution 3M HNO 3 . To determine the influence of ligands structure on cation complexation, a study in a homogenous media (MeOH/H 2 O) has been carried out. Electro-spray ionization mass spectrometry have been used to characterize the complexes stoichiometries formed with several cations (Eu 3+ , Nd 3+ , Am 3+ , Pu 4+ and NpO 2 + ). Stability constants, evaluated by UV-Visible spectrophotometry, confirm the selectivity of these ligands toward actinides. Lanthanides and actinides complexes have also been characterized in the solid state by infra-red spectroscopy and X-Ray diffraction. Associated to nuclear magnetic resonance experiments and DFT calculations (Density Functional Theory), a better knowledge of their coordination mode was achieved. (author) [fr

  19. Changes in magnetic properties from solid state to solution in a trinuclear linear copper(II) complex

    NARCIS (Netherlands)

    Koval, I.A.; Akhideno, H.; Tanase, S.; Belle, C.; Duboc, C.; Saint-Aman, E.; Gamez, P.; Tooke, D.M.; Spek, A.L.; Pierre, J.-L.; Reedijk, J.

    2007-01-01

    A linear trinuclear copper(II) complex containing phenoxido- and alkoxido-bridges between the metal centers has been isolated and structurally characterized. The complex cation consists of a linear array of three copper ions, assembled by means of two doubly deprotonated ligands. The octahedral

  20. A correspondence between solution-state dynamics of an individual protein and the sequence and conformational diversity of its family.

    Directory of Open Access Journals (Sweden)

    Gregory D Friedland

    2009-05-01

    Full Text Available Conformational ensembles are increasingly recognized as a useful representation to describe fundamental relationships between protein structure, dynamics and function. Here we present an ensemble of ubiquitin in solution that is created by sampling conformational space without experimental information using "Backrub" motions inspired by alternative conformations observed in sub-Angstrom resolution crystal structures. Backrub-generated structures are then selected to produce an ensemble that optimizes agreement with nuclear magnetic resonance (NMR Residual Dipolar Couplings (RDCs. Using this ensemble, we probe two proposed relationships between properties of protein ensembles: (i a link between native-state dynamics and the conformational heterogeneity observed in crystal structures, and (ii a relation between dynamics of an individual protein and the conformational variability explored by its natural family. We show that the Backrub motional mechanism can simultaneously explore protein native-state dynamics measured by RDCs, encompass the conformational variability present in ubiquitin complex structures and facilitate sampling of conformational and sequence variability matching those occurring in the ubiquitin protein family. Our results thus support an overall relation between protein dynamics and conformational changes enabling sequence changes in evolution. More practically, the presented method can be applied to improve protein design predictions by accounting for intrinsic native-state dynamics.

  1. Solution and solid state NMR studies of the structure and dynamics of C60 and C70

    International Nuclear Information System (INIS)

    Johnson, R.D.; Yannoni, C.S.; Salem, J.; Meijer, G.; Bethune, D.S.

    1991-01-01

    This paper investigates the structure and dynamics of C 60 and C 70 with 13 C NMR spectroscopy. In solution, high-resolution spectra reveal that C 60 has a single resonance at 143 ppm, indicating a strained, aromatic system with high symmetry. This is strong evidence for a C 60 soccer ball geometry. A 2D NMR INADEQUATE experiment on 13 C-enriched C 70 reveals the bonding connectivity to be a linear string, in firm support of the proposed rugby ball structure with D 5h symmetry, and furnishes resonance assignments. Solid state NMR spectra of C 60 at ambient temperatures yield a narrow resonance, indicative of rapid molecular reorientation. Variable temperature T 1 measurements show that the rotational correlation time is ∼ 10 - 9 s at 230 K. At 77 K, this time increases to more than 1 ms, and the 13 C NMR spectrum of C 60 is a powder pattern due to chemical shift anisotropy (tensor components 220, 186, 40 ppm). At intermediate temperatures a narrow peak is superimposed on the powder pattern, suggesting a distribution of barriers to molecular motion in the sample, or the presence of an additional phase in the solid state. A Carr-Purcell dipolar experiment on C 60 in the solid state allows the first precise determination of the C 60 bond lengths: 1.45 and 1.40 Angstrom

  2. Fluorescence ratiometric sensing of polyols by phenylboronic acid complexes with ligands exhibiting excited-state intramolecular proton transfer in aqueous micellar media

    Energy Technology Data Exchange (ETDEWEB)

    Trejo-Huizar, Karla Elisa; Jiménez-Sánchez, Arturo; Martínez-Aguirre, Mayte A.; Yatsimirsky, Anatoly K., E-mail: anatoli@unam.mx

    2016-11-15

    2-Phenyl-3-hydroxy-4(1H)-quinolone possessing dual fluorescence due to excited-state intramolecular proton transfer (ESIPT) forms stable complex with phenylboronic acid with blue shifted emission maximum in micellar medium of a cationic surfactant even though the compound lacks required for complexation with boronic acids cis-diol structure. No complexation is observed in the presence of neutral or anionic surfactants. Titrations of this complex with polyols including sugars and nucleotides at pH 8 displace free quinolone showing ratiometric response, which allows determination of polyols with detection limits 0.05–1 mM and unusually wide linear dynamic ranges. Another ESIPT dye 2-(2′-hydroxyphenyl)−1H-benzimidazole also lacking cis-diol structure forms equally stable complex with phenylboronic acid and allows ratiometric determination of polyols with similar characteristics. The results of this study demonstrate that blocking ESIPT of signaling molecule by complexation of the receptor with the proton donor group eliminates the low energy emission from tautomeric form but strongly enhances the high energy emission typical for “normal” form of signaling molecule creating a possibility of ratiometric sensing.

  3. The affinity plutonium(IV) for nitrogen donor ligands

    International Nuclear Information System (INIS)

    Jarvis, N.V.; Hancock, R.D.

    1994-01-01

    Established ligand design principles are used to predict the solution chemistry of Pu(IV) with nitrogen donor ligands which do not contain carboxylate donors. pK a 's of the nitrogen donors are lowered by addition of hydroxyalkyl groups causing Pu(IV) to have a greater affinity for these ligands than for hydroxide. Potentiometric studies using the ligands N,N,N'N',N''-pentakis(2-hydroxypropyl)-1,4,7-triazaheptane; N,N,N',N',N''-pentakis(2-hydroxyethyl)-1,4,7-triazaheptane; N,N,N',N',N'-tetrakis(2-hydroxyethyl)-1,2-diaminoethane; N,N,N',N'-tetrakis(2-hydroxyethyl)-trans-1,2-diaminocyclohexane; 1,4,8,11-tetrakis(2-hydroxyethyl)-1,4,8,11-tetraazacyclotetradecane and N,N-bis(2-hydroxyethyl)glycine with Pu(IV) showed that Pu(IV) has a considerable aqueous solution chemistry with these ligands. Data were processed by the ESTA library of programs and stability constants for all the systems are reported. Implications for selective ligand design for Pu(IV) are discussed. (orig.)

  4. An implicit scheme with memory reduction technique for steady state solutions of DVBE in all flow regimes

    Science.gov (United States)

    Yang, L. M.; Shu, C.; Yang, W. M.; Wu, J.

    2018-04-01

    High consumption of memory and computational effort is the major barrier to prevent the widespread use of the discrete velocity method (DVM) in the simulation of flows in all flow regimes. To overcome this drawback, an implicit DVM with a memory reduction technique for solving a steady discrete velocity Boltzmann equation (DVBE) is presented in this work. In the method, the distribution functions in the whole discrete velocity space do not need to be stored, and they are calculated from the macroscopic flow variables. As a result, its memory requirement is in the same order as the conventional Euler/Navier-Stokes solver. In the meantime, it is more efficient than the explicit DVM for the simulation of various flows. To make the method efficient for solving flow problems in all flow regimes, a prediction step is introduced to estimate the local equilibrium state of the DVBE. In the prediction step, the distribution function at the cell interface is calculated by the local solution of DVBE. For the flow simulation, when the cell size is less than the mean free path, the prediction step has almost no effect on the solution. However, when the cell size is much larger than the mean free path, the prediction step dominates the solution so as to provide reasonable results in such a flow regime. In addition, to further improve the computational efficiency of the developed scheme in the continuum flow regime, the implicit technique is also introduced into the prediction step. Numerical results showed that the proposed implicit scheme can provide reasonable results in all flow regimes and increase significantly the computational efficiency in the continuum flow regime as compared with the existing DVM solvers.

  5. HEXNOD23, 2-D, 3-D Coarse Mesh Solution of Steady State Diffusion Equation in Hexagonal Geometry

    International Nuclear Information System (INIS)

    Grundmann, Ulrich

    1986-01-01

    1 - Description of program or function: Two- or three dimensional coarse mesh solution of steady state two group neutron diffusion equation in arrays of regular hexagons or hexagonal subassemblies. 2 - Method of solution: The neutron flux in a hexagonal node is expanded in a series of Bessel functions in the hexagonal plane. Polynomials up to the 4. order are used for the approximation of neutron flux in axial direction of three dimensional cases. Resulting relations between node averaged fluxes and mean partial currents of node faces in connection with the neutron balance of nodes are used to calculate the eigenvalue Keff, mean fluxes and mean powers of nodes. The iterations process is divided into inner and outer iterations. The iterations are accelerated by Ljusternik and Tschebyscheff extrapolation schemes. The power densities in the nodes and subassembly powers are computed for given reactor power in three dimensional cases. 30 degree reflectional, 60 and 120 degree rotational core symmetry and the whole core can be treated. 3 - Restrictions on the complexity of the problem: If the problem size designated by LIAR and LRAR exceeds 3000 and 50000 respectively, the lengths of the working array MIAR and MRAR in the main program can be increased. External sources are not permitted

  6. Complete conformal classification of the Friedmann–Lemaître–Robertson–Walker solutions with a linear equation of state

    Science.gov (United States)

    Harada, Tomohiro; Carr, B. J.; Igata, Takahisa

    2018-05-01

    We completely classify Friedmann–Lemaître–Robertson–Walker solutions with spatial curvature and equation of state , according to their conformal structure, singularities and trapping horizons. We do not assume any energy conditions and allow , thereby going beyond the usual well-known solutions. For each spatial curvature, there is an initial spacelike big-bang singularity for w  >  ‑1/3 and , while there is no big-bang singularity for w  big-bang singularity. For each spatial curvature, there is a final spacelike future big-rip singularity for w  big-rip singularity, then bounces and blows up at a final spacelike future big-rip singularity. For w    ‑1/3, the universe contracts from infinity, then bounces and expands to infinity; for  ‑1  big-bang singularity and contracts to a big-crunch singularity; for w  <  ‑1, it expands from a regular null hypersurface and contracts to another regular null hypersurface.

  7. Signatures of Quantized Energy States in Solution-Processed Ultrathin Layers of Metal-Oxide Semiconductors and Their Devices

    KAUST Repository

    Labram, John G.

    2015-02-13

    Physical phenomena such as energy quantization have to-date been overlooked in solution-processed inorganic semiconducting layers, owing to heterogeneity in layer thickness uniformity unlike some of their vacuum-deposited counterparts. Recent reports of the growth of uniform, ultrathin (<5 nm) metal-oxide semiconductors from solution, however, have potentially opened the door to such phenomena manifesting themselves. Here, a theoretical framework is developed for energy quantization in inorganic semiconductor layers with appreciable surface roughness, as compared to the mean layer thickness, and present experimental evidence of the existence of quantized energy states in spin-cast layers of zinc oxide (ZnO). As-grown ZnO layers are found to be remarkably continuous and uniform with controllable thicknesses in the range 2-24 nm and exhibit a characteristic widening of the energy bandgap with reducing thickness in agreement with theoretical predictions. Using sequentially spin-cast layers of ZnO as the bulk semiconductor and quantum well materials, and gallium oxide or organic self-assembled monolayers as the barrier materials, two terminal electronic devices are demonstrated, the current-voltage characteristics of which resemble closely those of double-barrier resonant-tunneling diodes. As-fabricated all-oxide/hybrid devices exhibit a characteristic negative-differential conductance region with peak-to-valley ratios in the range 2-7.

  8. Compromise solution in the problem of change state control for the material body exposed to the external medium

    Science.gov (United States)

    Malafeyev, O. A.; Redinskikh, N. D.

    2018-05-01

    The problem of finding optimal temperature control of the material body state under the unknown in advance parameters of the external medium is formalized and studied in this paper. The problems of this type arise frequently in the real life. An optimal thermal regime is necessary to apply at the soil thawing or freezing, drying the building materials, heating the concrete to obtain the required strength, and so on. Problems of such type one can analyze making use the apparatus and methods of game theory. For describing the influence of external medium on the characteristics of different materials we make use the many-step two person zero-sum game in this paper. The compromise solution is taken as the optimality principle. The numerical example is given.

  9. Three-Dimensional Elasticity Solutions for Sound Radiation of Functionally Graded Materials Plates considering State Space Method

    Directory of Open Access Journals (Sweden)

    Tieliang Yang

    2016-01-01

    Full Text Available This paper presents an analytical study for sound radiation of functionally graded materials (FGM plate based on the three-dimensional theory of elasticity. The FGM plate is a mixture of metal and ceramic, and its material properties are assumed to have smooth and continuous variation in the thickness direction according to a power-law distribution in terms of volume fractions of the constituents. Based on the three-dimensional theory of elasticity and state space method, the governing equations with variable coefficients of the FGM plate are derived. The sound radiation of the vibration plate is calculated with Rayleigh integral. Comparisons of the present results with those of solutions in the available literature are made and good agreements are achieved. Finally, some parametric studies are carried out to investigate the sound radiation properties of FGM plates.

  10. 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.

  11. Identification of aquatically available carbon from algae through solution-state NMR of whole (13)C-labelled cells.

    Science.gov (United States)

    Akhter, Mohammad; Dutta Majumdar, Rudraksha; Fortier-McGill, Blythe; Soong, Ronald; Liaghati-Mobarhan, Yalda; Simpson, Myrna; Arhonditsis, George; Schmidt, Sebastian; Heumann, Hermann; Simpson, André J

    2016-06-01

    Green algae and cyanobacteria are primary producers with profound impact on food web functioning. Both represent key carbon sources and sinks in the aquatic environment, helping modulate the dissolved organic matter balance and representing a potential biofuel source. Underlying the impact of algae and cyanobacteria on an ecosystem level is their molecular composition. Herein, intact (13)C-labelled whole cell suspensions of Chlamydomonas reinhardtii, Chlorella vulgaris and Synechocystis were studied using a variety of 1D and 2D (1)H/(13)C solution-state nuclear magnetic resonance (NMR) spectroscopic experiments. Solution-state NMR spectroscopy of whole cell suspensions is particularly relevant as it identifies species that are mobile (dissolved or dynamic gels), 'aquatically available' and directly contribute to the aquatic carbon pool upon lysis, death or become a readily available food source on consumption. In this study, a wide range of metabolites and structural components were identified within the whole cell suspensions. In addition, significant differences in the lipid/triacylglyceride (TAG) content of green algae and cyanobacteria were confirmed. Mobile species in algae are quite different from those in abundance in 'classic' dissolved organic matter (DOM) indicating that if algae are major contributors to DOM, considerable selective preservation of minor components (e.g. sterols) or biotransformation would have to occur. Identifying the metabolites and dissolved components within algal cells by NMR permits future studies of carbon transfer between species and through the food chain, whilst providing a foundation to better understand the role of algae in the formation of DOM and the sequestration/transformation of carbon in aquatic environments.

  12. Ligand Depot: a data warehouse for ligands bound to macromolecules.

    Science.gov (United States)

    Feng, Zukang; Chen, Li; Maddula, Himabindu; Akcan, Ozgur; Oughtred, Rose; Berman, Helen M; Westbrook, John

    2004-09-01

    Ligand Depot is an integrated data resource for finding information about small molecules bound to proteins and nucleic acids. The initial release (version 1.0, November, 2003) focuses on providing chemical and structural information for small molecules found as part of the structures deposited in the Protein Data Bank. Ligand Depot accepts keyword-based queries and also provides a graphical interface for performing chemical substructure searches. A wide variety of web resources that contain information on small molecules may also be accessed through Ligand Depot. Ligand Depot is available at http://ligand-depot.rutgers.edu/. Version 1.0 supports multiple operating systems including Windows, Unix, Linux and the Macintosh operating system. The current drawing tool works in Internet Explorer, Netscape and Mozilla on Windows, Unix and Linux.

  13. The LiBH4-LiI Solid Solution as an Electrolyte in an All-Solid-State Battery

    DEFF Research Database (Denmark)

    Sveinbjörnsson, Dadi Þorsteinn; Christiansen, Ane Sælland; Viskinde, Rasmus

    2014-01-01

    The charge and discharge performance of an all-solid-state lithium battery with the LiBH4-LiI solid solution as an electrolyte is reported. Lithium titanate (Li4Ti5O12) was used as the positive electrode and lithium metal as the negative electrode. The performance of the all-solid-state cell...

  14. Metal-ligand interactions

    Science.gov (United States)

    Ervin, Kent M.

    Experimental studies of the interactions of small transition-metal cluster anions with carbonyl ligands are reviewed and compared with neutral and cationic clusters. Under thermal conditions, the reaction rates of transition-metal clusters with carbon monoxide are measured as a function of cluster size. Saturation limits for carbon monoxide addition can be related to the geometric structures of the clusters. Both energy-resolved threshold collision-induced dissociation experiments and time-resolved photodissociation experiments are used to measure metal-carbonyl binding energies. For platinum and palladium trimer anions, the carbonyl binding energies are assigned to different geometric binding sites. Platinum and palladium cluster anions catalyse the oxidation of carbon monoxide to carbon dioxide in a full catalytic cycle at thermal energies.

  15. Melatonin: functions and ligands.

    Science.gov (United States)

    Singh, Mahaveer; Jadhav, Hemant R

    2014-09-01

    Melatonin is a chronobiotic substance that acts as synchronizer by stabilizing bodily rhythms. Its synthesis occurs in various locations throughout the body, including the pineal gland, skin, lymphocytes and gastrointestinal tract (GIT). Its synthesis and secretion is controlled by light and dark conditions, whereby light decreases and darkness increases its production. Thus, melatonin is also known as the 'hormone of darkness'. Melatonin and analogs that bind to the melatonin receptors are important because of their role in the management of depression, insomnia, epilepsy, Alzheimer's disease (AD), diabetes, obesity, alopecia, migraine, cancer, and immune and cardiac disorders. In this review, we discuss the mechanism of action of melatonin in these disorders, which could aid in the design of novel melatonin receptor ligands. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Structure and Dynamics of the Metal Site of Cadmium-Substituted Carboxypeptidase A in Solution and Crystalline States and under Steady-State peptide Catalysis

    DEFF Research Database (Denmark)

    Bauer, R.; Danielsen, E.; Hemmingsen, L.

    1997-01-01

    are consistent with an intact scissile peptide bond in the enzyme-substrate complex of Bz-Gly-L-Phe and Bz-Gly-Gly-L-Phe. A single nuclear quadrupole interaction (NQI) is observed for the crystalline state of the enzyme between pH 5.7 and pH 9.4. This NQI agrees with calculations based on the metal coordination...... geometry for cadmium in crystalline CPD derived from X-ray diffraction studies. A single broad distribution of NQIs is observed for CPD in sucrose solutions and 0.1 M NaCl at pH values below 6.5. This NQI (NQI-1') has parameters very close to those for the crystalline state. The enzyme metal site......, characterized by this NQI, is converted into two new enzyme metal sites over the pH range of 6.5-8.3. The metal coordination sphere of one of these has a NQI (NQI-1) with parameters similar to those at lower pH values (NQI-1') while the other NQI (NQI-2) is characterized by markedly different NQI parameters...

  17. Resonance Raman scattering of β-carotene solution excited by visible laser beams into second singlet state.

    Science.gov (United States)

    Lu, Luyao; Shi, Lingyan; Secor, Jeff; Alfano, Robert

    2018-02-01

    This study aimed to use self-absorption correction to determine the Raman enhancement of β-carotene. The Raman spectra of β-carotene solutions were measured using 488nm, 514nm, 532nm and 633nm laser beams, which exhibited significant resonance Raman (RR) enhancement when the laser energy approaches the electronic transition energy from S 0 to S 2 state. The Raman intensity and the actual resonance Raman gain without self-absorption from S 2 state by β-carotene were also obtained to evaluate the effect of self-absorption on RR scattering. Moreover, we observed the Raman intensity strength followed the absorption spectra. Our study found that, although 488nm and 514nm pumps seemed better for stronger RR enhancement, 532nm would be the optimum Raman pump laser with moderate RR enhancement due to reduced fluorescence and self-absorption. The 532nm excitation will be helpful for applying resonance Raman spectroscopy to investigate biological molecules in tissues. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Macrocyclic G-quadruplex ligands

    DEFF Research Database (Denmark)

    Nielsen, M C; Ulven, Trond

    2010-01-01

    are macrocyclic structures which have been modeled after the natural product telomestatin or from porphyrin-based ligands discovered in the late 1990s. These two structural classes of G-quadruplex ligands are reviewed here with special attention to selectivity and structure-activity relationships, and with focus...

  19. Two-state solutions

    Index Scriptorium Estoniae

    2011-01-01

    16. detsembril Tartus toimunud Eesti-Läti koostöökonverentsist võtsid osa ka mõlema riigi peaministrid Andrus Ansip ja Valdis Dombrovskis. Kohal olid ka haridusministrid Jaak Aaviksoo ja Roberts Kilis

  20. New Ru(II) Complexes for Dual Photoreactivity: Ligand Exchange and 1O2 Generation

    OpenAIRE

    Knoll, Jessica D.; Albani, Bryan A.; Turro, Claudia

    2015-01-01

    Uncovering the factors that govern the electronic structure of Ru(II)–polypyridyl complexes is critical in designing new compounds for desired photochemical reactions, and strategies to tune excited states for ligand dissociation and 1O2 production are discussed herein. The generally accepted mechanism for photoinduced ligand dissociation proposes that population of the dissociative triplet ligand field (3LF) state proceeds through thermal population from the vibrationally cooled triplet meta...

  1. Bond Shortening (1.4 Å) in the Singlet and Triplet Excited States of [Ir2(dimen)4]2+ in Solution Determined by Time-Resolved X-ray Scattering

    DEFF Research Database (Denmark)

    Haldrup, Martin Kristoffer; Harlang, Tobias; Christensen, Morten

    2011-01-01

    Ground- and excited-state structures of the bimetallic, ligand-bridged compound Ir2(dimen)42+ are investigated in acetonitrile by means of time-resolved X-ray scattering. Following excitation by 2 ps laser pulses at 390 nm, analysis of difference scattering patterns obtained at eight different ti...

  2. Optimization of moistening solution concentration on xylanase activity in solid state fermentation from oil palm empty fruit bunches

    Science.gov (United States)

    Mardawati, Efri; Parlan; Rialita, Tita; Nurhadi, Bambang

    2018-03-01

    Xylanase is an enzyme used in the industrial world, including food industry. Xylanase can be utilized as a 1,4-β-xylosidic endo-hydrolysis catalyst of xylanase, a hemicellulose component for obtaining a xylose monomer. This study aims to determine the optimum concentration of the fermentation medium using Response Surface Method (RSM) in the production of xylanase enzyme from oil palm empty fruit bunches (OPEFB) through solid state fermentation process. The variables varied in this study used factor A (ammonium sulphate concentration 1.0-2.0 g/L), B (concentration of potassium dihydrogen phosphate 1.5-2.5 g/L) and C (urea concentration 0.2 – 0.5 g/L). The data was analysed by using Design Expert version 10.0.1.0 especially CCD with total 17 running including 3 times replicated of canter point. Trichoderma viride was used for the process production of xylanase enzyme. The ratio between substrate and moistening solution used was 0.63 g / mL with temperature of 32.80C, 60 h incubation time. The analysis of enzyme activity was done by DNS method with 1% xylan as substrate. Analysis of protein content in enzyme was done by Bradford method. The optimum of moistening solution concentration in this fermentation was obtained. They are, the ammonium sulphate concentration of 1.5 g/L, potassium dihydrogen phosphate 2.0 g/L and urea 0.35 g/L with activity of 684.70 U/mL, specific activity enzyme xylanase 6261.58 U/mg, protein content 0.1093 U/mg, the model was validated using experiment design with perfect reliability value 0.96.

  3. Extent and effects of recurrent shortages of purified-protein derivative tuberculin skin test antigen solutions - United States, 2013.

    Science.gov (United States)

    2013-12-13

    Two purified-protein derivative (PPD) tuberculin skin test (TST) antigen solutions are approved by the U.S. Food and Drug Administration (FDA): Tubersol (Sanofi Pasteur Limited) and Aplisol (JHP Pharmaceuticals, LLC). Tubersol was out of production in late 2012 through April 2013. Shortages of Aplisol have resulted from increased demand as practitioners have sought a substitute for Tubersol. Tubersol production resumed in May 2013, and supplies had been nearly restored by early June. However, in mid-July, state tuberculosis (TB) control officials notified CDC of difficulty obtaining Tubersol and Aplisol. Sanofi Pasteur notified FDA of a temporary delay in the availability of tuberculin in the 10-dose and 50-dose presentations. In mid-October, the 10-dose presentation was being returned to market, on allocation, which means that historical purchasing practices determine the amount that customers are allotted. In late October, the 50-dose presentation was being returned to market, also on allocation, one vial per historical customer per month. Supplies are forecast to approach normal during January 2014, after distributors have restored their supply chains. A compensatory surge in testing after deferment of testing during the periods of shortage might cause further temporary instability of supplies. In mid-August 2013, officials in 29 of 52 U.S. jurisdictions noted a shortage of at least one PPD TST antigen solution in health departments to the extent that it interrupted activities. This report includes a summary of the extent and effects of the shortages and a reiteration of advice on how to adapt to them.

  4. Synthesis, spectroscopic studies and reactivity of triphenylphosphine ruthenium (II) complexes with N-heterocyclic ligands

    International Nuclear Information System (INIS)

    Rivera, A.B.

    1989-01-01

    Reported is the chemistry of triphenylphosphine ruthenium (II) complexes of general formula RuCl 2 (PPh 3 ) 2 L 2 and RuCl 2 (PPh 3 ) 2 A, obtained from the reaction of RuCl 2 (PPh 3 ) 3 with N-heterocyclic ligands L, or A (of ambidentate nature). The electronic spectra exhibit two strong metal-to-ligand charge-transfer bands, ascribed to the b 1 (dxz)->b 1 (pi) and a 2 (dxy)->a 2 (pi) transitions, and a third, weak band ascribed to the b 2 (dyz)->a 2 (pi) transition. The electronic states and the vibrational modes of the complexes were characterized by means of their resonance Raman and infrared absorption spectra. Thermogravimetric and thermodifferential analysis indicated that the melting process is succeeded by an exothermic reaction, and that the weigh loss starts to occur only after this step. The complexes dissociated in CHCl 3 solution, showing preferential labilization of the phosphine ligands, as in the case of the hydrogenation catalyst Ru(PPh 3 ) 3 Cl 2 . In the presence of CO, RuCl 2 (CO) 2 L 2 complexes were gennerated. Several derivatives were isolated and characterized. (author) [pt

  5. Application of X-ray single crystal diffractometry to investigation of Np(5) complexes with n-donor ligands

    International Nuclear Information System (INIS)

    Andreev, G.

    2007-01-01

    Full text of publication follows. We present here some results of application of conventional X-ray single crystal diffractometry to the research on the interaction of Np(V) with N-donor ligands. Compounds that can coordinate to actinides through one or several nitrogen atoms are of a great variety and occur widely in the biosphere. For example, imidazole, pyridine and their derivatives are the building blocks of many biologically important molecules; triazines are known to occur in some aquatic plants. The presence of anthropogenic organic agents like amine-N-carboxylic acids in surface waters has the potential to re-mobilize metals from sediments and aquifers and to influence their bioavailability. The interaction of radionuclides with such ligands needs to be studied in detail to give fundamental understanding the conditions of the incorporation of long lived a-emitters (Np and Pu primarily) into the food chain. Another aspect of the same problem is the design of new chelating ligands for selective co-ordination of actinide ions as an alternative to the traditional sequestering agents. The problem of the separation of long-lived minor actinides and their transmutation also calls for design of new highly selective ligands for solvent extraction. Polydentate N-donor ligands are now considered to be very promising. A detailed study of structural chemistry is crucial for understanding the relationship between the architecture of the ligands and their binding affinity for actinides. The X-ray single crystal diffractometry became conventional technique as applied to the investigation of actinides in spite of difficulties regarding safe handling of radionuclides. This technique provides unambiguous information about modes of the ligand co-ordination to the metal ion and geometrical parameters of complexes. Moreover, the employment of a synchrotron radiation shows considerable promise for determination of solid state structures as well as obtaining structural

  6. Nonlinear absorbing cationic iridium(III) complexes bearing benzothiazolylfluorene motif on the bipyridine (N∧N) ligand: synthesis, photophysics and reverse saturable absorption.

    Science.gov (United States)

    Li, Yuhao; Dandu, Naveen; Liu, Rui; Hu, Lei; Kilina, Svetlana; Sun, Wenfang

    2013-07-24

    Four new heteroleptic cationic Ir(III) complexes bearing benzothiazolylfluorene motif on the bipyridine (N∧N) (1 and 2) and phenylpyridine (C∧N) (3 and 4) ligands are synthesized and characterized. The influence of the position of the substituent and the extent of π-conjugation on the photophysics of these complexes is systematically investigated by spectroscopic methods and simulated by time-dependent density functional theory (TDDFT). The complexes exhibit ligand-centered (1)π,π* transitions with admixtures of (1)ILCT (π(benzothiazolylfluorene) → π*(bpy)) and (1)MLCT (metal-to-ligand charge transfer) characters below 475 nm, and very weak (1,3)MLCT and (1,3)LLCT (ligand-to-ligand charge transfer) transitions above 475 nm. The emission of these complexes at room temperature in CH2Cl2 solutions is ascribed to be predominantly from the (3)MLCT/(3)LLCT states for 1 and from the (3)π,π* state for 2, while the emitting state of 3 and 4 are assigned to be an admixture of (3)MLCT, (3)LLCT, and (3)π,π* characters. The variations of the photophysical properties of 1-4 are attributed to different degrees of π-conjugation in the bipyridine and phenylpyridine ligands induced by different positions of the benzothiazolylfluorenyl substituents on the bipyridine ligand and different extents of π-conjugation in the phenylpyridine ligands, which alters the energy and lifetime of the lowest singlet and triplet excited states. 1-4 all possess broadband transient absorption (TA) upon nanosecond laser excitation, which extends from the visible to the NIR region. Therefore, 1-4 all exhibit strong reverse saturable absorption (RSA) at 532 nm for ns laser pulses. However, the TA of complexes 1, 2, and 3 are much stronger than that of 4. This feature, combined with the difference in ground-state absorption and triplet excited-state quantum yield, result in the difference in RSA strength, which follows this trend: 1 ≈ 2 ≈ 3 > 4. Therefore, complexes 1-3 are strong

  7. Contribution to research on the metabolism of fission product. Studies on the physico-chemical state and the metabolic fate of radio-cerium solution

    International Nuclear Information System (INIS)

    Aeberhardt, A.

    1961-01-01

    This paper describes a study of the physico-chemical state of radio-cerium in dilute solutions on the tracer scale, as a function of the pH of the solution. The way in which this radioelement is transported in the blood is studied in vitro and in vivo, with reference to the ionic or colloidal state of the radio-cerium used. The distribution of cerium amongst the various components of the blood is studied by a new method of blood fractionation and by paper electrophoresis. Evidence of a cerium globulin connection is shown in the case of ionic cerium. A study of the initial distribution of radio-cerium in rats, after intravenous administration of ionic or colloidal solutions, shows considerable differences according to the physico-chemical state of the cerium injected. (author) [fr

  8. Ambient Mechanochemical Solid-State Reactions of Carbon Nanotubes and Their Reactions via Covalent Coordinate Bond in Solution

    Science.gov (United States)

    Kabbani, Mohamad A.

    In its first part, this thesis deals with ambient mechanochemical solid-state reactions of differently functionalized multiple walled carbon nanotubes (MWCNTs) while in its second part it investigates the cross-linking reactions of CNTs in solution via covalent coordinate bonds with transitions metals and carboxylate groups decorating their surfaces. In the first part a series of mechanochemical reactions involving different reactive functionalities on the CNTs such as COOH/OH, COOH/NH2 and COCl/OH were performed. The solid-state unzipping of CNTs leading to graphene formation was confirmed using spectroscopic, thermal and electron microscopy techniques. The non-grapheme products were established using in-situ quadruple mass spectroscopy. The experimental results were confirmed by theoretical simulation calculations using the 'hot spots' protocol. The kinetics of the reaction between MWCNT-COOH and MWCNT-OH was monitored using variable temperature Raman spectroscopy. The low activation energy was discussed in terms of hydrogen bond mediated proton transfer mechanism. The second part involves the reaction of MWCNTII COOH with Zn (II) and Cu (II) to form CNT metal-organic frame (MOFs) products that were tested for their effective use as counter-electrodes in dyes sensitized solar cells (DSSC). The thesis concludes by the study of the room temperature reaction between the functionalized graphenes, GOH and G'-COOH followed by the application of compressive loads. The 3D solid graphene pellet product ( 0.6gm/cc) is conductive and reflective with a 35MPa ultimate strength as compared to 10MPa strength of graphite electrode ( 2.2gm/cc).

  9. Two novel mixed-ligand complexes containing organosulfonate ligands.

    Science.gov (United States)

    Li, Mingtian; Huang, Jun; Zhou, Xuan; Fang, Hua; Ding, Liyun

    2008-07-01

    The structures reported herein, viz. bis(4-aminonaphthalene-1-sulfonato-kappaO)bis(4,5-diazafluoren-9-one-kappa(2)N,N')copper(II), [Cu(C(10)H(8)NO(3)S)(2)(C(11)H(6)N(2)O)(2)], (I), and poly[[[diaquacadmium(II)]-bis(mu-4-aminonaphthalene-1-sulfonato)-kappa(2)O:N;kappa(2)N:O] dihydrate], {[Cd(C(10)H(8)NO(3)S)(2)(H(2)O)(2)].2H(2)O}(n), (II), are rare examples of sulfonate-containing complexes where the anion does not fulfill a passive charge-balancing role, but takes an active part in coordination as a monodentate and/or bridging ligand. Monomeric complex (I) possesses a crystallographic inversion center at the Cu(II) atom, and the asymmetric unit contains one-half of a Cu atom, one complete 4-aminonaphthalene-1-sulfonate (ans) ligand and one 4,5-diazafluoren-9-one (DAFO) ligand. The Cu(II) atom has an elongated distorted octahedral coordination geometry formed by two O atoms from two monodentate ans ligands and by four N atoms from two DAFO molecules. Complex (II) is polymeric and its crystal structure is built up by one-dimensional chains and solvent water molecules. Here also the cation (a Cd(II) atom) lies on a crystallographic inversion center and adopts a slightly distorted octahedral geometry. Each ans anion serves as a bridging ligand linking two Cd(II) atoms into one-dimensional infinite chains along the [010] direction, with each Cd(II) center coordinated by four ans ligands via O and N atoms and by two aqua ligands. In both structures, there are significant pi-pi stacking interactions between adjacent ligands and hydrogen bonds contribute to the formation of two- and three-dimensional networks.

  10. 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.

  11. Design of a new peptidomimetic agonist for the melanocortin receptors based on the solution structure of the peptide ligand, Ac-Nle-cyclo[Asp-Pro-DPhe-Arg-Trp-Lys]-NH(2).

    Science.gov (United States)

    Fotsch, Christopher; Smith, Duncan M; Adams, Jeffrey A; Cheetham, Janet; Croghan, Michael; Doherty, Elizabeth M; Hale, Clarence; Jarosinski, Mark A; Kelly, Michael G; Norman, Mark H; Tamayo, Nuria A; Xi, Ning; Baumgartner, James W

    2003-07-21

    The solution structure of a potent melanocortin receptor agonist, Ac-Nle-cyclo[Asp-Pro-DPhe-Arg-Trp-Lys]-NH(2) (1) was calculated using distance restraints determined from 1H NMR spectroscopy. Eight of the lowest energy conformations from this study were used to identify non-peptide cores that mimic the spatial arrangement of the critical tripeptide region, DPhe-Arg-Trp, found in 1. From these studies, compound 2a, containing the cis-cyclohexyl core, was identified as a functional agonist of the melanocortin-4 receptor (MC4R) with an IC(50) and EC(50) below 10 nM. Compound 2a also showed 36- and 7-fold selectivity over MC3R and MC1R, respectively, in the binding assays. Subtle changes in cyclohexane stereochemistry and removal of functional groups led to analogues with lower affinity for the MC receptors.

  12. The affinity of the uranyl ion for nitrogen donor ligands

    Energy Technology Data Exchange (ETDEWEB)

    Jarvis, N.V. (Atomic Energy Corp. of South Africa Ltd., Pretoria (South Africa). Dept. of Process Technology); De Sousa, A.S.; Hancock, R.D. (Univ. of the Witwatersrand, Johannesburg (South Africa). Centre for Molecular Design)

    1992-01-01

    Established ligand design principles are used to predict the solution chemistry of UO[sub 2][sup 2+] with nitrogen donor ligands which do not contain carboxylate donors. pK[sub a]'s of the nitrogen donors are lowered by addition of hydroxylalkyl groups causing UO[sub 2][sup 2+] to have a greater affinity for these ligands than for hydroxide. Potentiometric studies using the ligands N,N,N',N',N''-pentakis(2-hydroxypropyl)-1,4,7-triazaheptane; N,N,N',N',N''-pentakis(2-hydroxyethyl)-1,4,7-triazaheptane; N,N,N',N'-tetrakis(2-hydroxypropyl)1,2-diaminoethane, N,N,N',N'-tetrakis(2-hydroxyethyl)-trans-1,2-diaminocyclohexane; 1,4,8,11-tetrakis(2-hydroxyethyl)-1,4,8,11-tetraazacyclotetradecane and N,N-bis(2-hydroxyethyl)glycine with UO[sub 2][sup 2+] showed that UO[sub 2][sup 2+] has a considerable aqueous solution chemistry with these ligands. (orig.).

  13. Correcting ligands, metabolites, and pathways

    NARCIS (Netherlands)

    Ott, M.A.; Vriend, G.

    2006-01-01

    BACKGROUND: A wide range of research areas in bioinformatics, molecular biology and medicinal chemistry require precise chemical structure information about molecules and reactions, e.g. drug design, ligand docking, metabolic network reconstruction, and systems biology. Most available databases,

  14. Silver colloidal effects on excited-state structure and intramolecular charge transfer of p-N, N-dimethylaminobenzoic acid in aqueous cyclodextrin solutions

    International Nuclear Information System (INIS)

    Choi, Jung Kwon; Kim, Yang Hee; Yoon, Min Joong; Lee, Seung Joon; Kim, Kwan; Jeoung, Sae Chae

    2001-01-01

    The silver colloidal effects on the excited-state structure and intramolecular charge transfer (ICT) of p-N,N-dimethylaminobenzoic acid (DMABA) in aqueous cyclodextrin (CD) solutions have been investigated by UV-VIS absorption, steady-state and time-resolved fluorescence, and transient Raman spectroscopy. As the concentration of silver colloids increases, the ratio of the ICT emission to the normal emission (I a /I b ) of DMABA in the aqueous α-CD solutions are greatly decreased while the I a /I b values in the aqueous β-CD solutions are significantly enhanced. It is also noteworthy that the ICT emission maxima are red-shifted by 15-40 nm upon addition of silver colloids, implying that DMABA encapsulated in α-CD or β-CD cavity is exposed to more polar environment. The transient resonance Raman spectra of DMABA in silver colloidal solutions demonstrate that DMABA in the excited-state is desorbed from silver colloidal surfaces as demonstrated by the disappearance of v s (CO 2 - )(1380 cm -1 ) with appearance of v (C-OH)(1280 cm -1 ) band, respectively. Thus, in the aqueous β-CD solutions the carboxylic acid group of DMABA in the excited-state can be readily hydrogen bonded with the secondary hydroxyl group of β-CD while in aqueous and α-CD solutions the carboxylic acid group of DMABA has the hydrogen-bonding interaction with water. Consequently, in the aqueous β-CD solutions the enhancement of the I a /I b value arises from the intermolecular hydrogen-bonding interaction between DMABA and the secondary hydroxyl group of β-CD as well as the lower polarity of the rim of the β-CD cavity compared to bulk water. This is also supported by the increase of the association constant for DMABA/β-CD complex in the presence of silver colloids

  15. Synthesis and self-organization of zinc β-(dialkoxyphosphoryl)porphyrins in the solid state and in solution.

    Science.gov (United States)

    Vinogradova, Ekaterina V; Enakieva, Yulia Y; Nefedov, Sergey E; Birin, Kirill P; Tsivadze, Aslan Y; Gorbunova, Yulia G; Bessmertnykh Lemeune, Alla G; Stern, Christine; Guilard, Roger

    2012-11-19

    The first synthesis and self-organization of zinc β-phosphorylporphyrins in the solid state and in solution are reported. β-Dialkoxyphosphoryl-5,10,15,20-tetraphenylporphyrins and their Zn(II) complexes have been synthesized in good yields by using Pd- and Cu-mediated carbon-phosphorous bond-forming reactions. The Cu-mediated reaction allowed to prepare the mono-β-(dialkoxyphosphoryl)porphyrins 1 Zn-3 Zn starting from the β-bromo-substituted zinc porphyrinate ZnTPPBr (TPP = tetraphenylporphyrin) and dialkyl phosphites HP(O)(OR)(2) (R = Et, iPr, nBu). The derivatives 1 Zn-3 Zn were obtained in good yields by using one to three equivalents of CuI. When the reaction was carried out in the presence of catalytic amounts of palladium complexes in toluene, the desired zinc derivative 1 Zn was obtained in up to 72% yield. The use of a Pd-catalyzed C-P bond-forming reaction was further extended to the synthesis of β-poly(dialkoxyphosphoryl)porphyrins. An unprecedented one-pot sequence involving consecutive reduction and phosphorylation of H(2)TPPBr(4) led to the formation of a mixture of the 2,12- and 2,13-bis(dialkoxy)phosphorylporphyrins 5 H(2) and 6 H(2) in 81% total yield. According to the X-ray diffraction studies, 1 Zn and 3 Zn are partially overlapped cofacial dimers formed through the coordination of two Zn centers by two phosphoryl groups belonging to the adjacent molecules. The equilibrium between the monomeric and the dimeric species exists in solutions of 1 Zn and 3 Zn in weakly polar solvents according to spectroscopic data (UV/Vis absorption and NMR spectroscopy). The ratio of each form is dependent on the concentration, temperature, and traces of water or methanol. These features demonstrated that zinc β-phosphorylporphyrins can be regarded as new model compounds for the weakly coupled chlorophyll pair in the photosynthesis process. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Tuning Confinement in Colloidal Silicon Nanocrystals with Saturated Surface Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Neale, Nathan R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Carroll, Gerard [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Limpens, Rens [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

    2018-04-16

    The optical properties of silicon nanocrystals (Si NCs) are a subject of intense study and continued debate. In particular, Si NC photoluminescence (PL) properties are known to depend strongly on the surface chemistry, resulting in electron-hole recombination pathways derived from the Si NC band-edge, surface-state defects, or combined NC-conjugated ligand hybrid states. In this Letter, we perform a comparison of three different saturated surface functional groups - alkyls, amides, and alkoxides - on nonthermal plasma-synthesized Si NCs. We find a systematic and size-dependent high-energy (blue) shift in the PL spectrum of Si NCs with amide and alkoxy functionalization relative to alkyl. Time-resolved photoluminescence and transient absorption spectroscopies reveal no change in the excited-state dynamics between Si NCs functionalized with alkyl, amide, or alkoxide ligands, showing for the first time that saturated ligands - not only surface-derived charge-transfer states or hybridization between NC and low-lying ligand orbitals - are responsible for tuning the Si NC optical properties. To explain these PL shifts we propose that the atom bound to the Si NC surface strongly interacts with the Si NC electronic wave function and modulates the Si NC quantum confinement. These results reveal a potentially broadly applicable correlation between the optoelectronic properties of Si NCs and related quantum-confined structures based on the interaction between NC surfaces and the ligand binding group.

  17. Tuning Confinement in Colloidal Silicon Nanocrystals with Saturated Surface Ligands.

    Science.gov (United States)

    Carroll, Gerard M; Limpens, Rens; Neale, Nathan R

    2018-05-09

    The optical properties of silicon nanocrystals (Si NCs) are a subject of intense study and continued debate. In particular, Si NC photoluminescence (PL) properties are known to depend strongly on the surface chemistry, resulting in electron-hole recombination pathways derived from the Si NC band-edge, surface-state defects, or combined NC-conjugated ligand hybrid states. In this Letter, we perform a comparison of three different saturated surface functional groups-alkyls, amides, and alkoxides-on nonthermal plasma-synthesized Si NCs. We find a systematic and size-dependent high-energy (blue) shift in the PL spectrum of Si NCs with amide and alkoxy functionalization relative to alkyl. Time-resolved photoluminescence and transient absorption spectroscopies reveal no change in the excited-state dynamics between Si NCs functionalized with alkyl, amide, or alkoxide ligands, showing for the first time that saturated ligands-not only surface-derived charge-transfer states or hybridization between NC and low-lying ligand orbitals-are responsible for tuning the Si NC optical properties. To explain these PL shifts we propose that the atom bound to the Si NC surface strongly interacts with the Si NC electronic wave function and modulates the Si NC quantum confinement. These results reveal a potentially broadly applicable correlation between the optoelectronic properties of Si NCs and related quantum-confined structures based on the interaction between NC surfaces and the ligand binding group.

  18. Strong ligand field effects of blue phosphorescent mono-cyclometalated iridium(III) complexes

    International Nuclear Information System (INIS)

    Ham, Ho Wan; Jung, Kyung Yoon; Kim, Young Sik

    2010-01-01

    A series of mono-cyclometalated blue phosphorescent iridium(III) complexes with two phosphines trans to each other and two cis-ancillary ligands, such as Ir(F 2 Meppy)(PPhMe 2 ) 2 (H)(Cl), [Ir(F 2 Meppy)(PPhMe 2 ) 2 (H)(NCMe)] + and Ir(F 2 Meppy)(PPhMe 2 ) 2 -(H)(CN), [F 2 Meppy = 2-(2',4'-difluorophenyl)-4-methyl-pyridine] were synthesized and studied to tune the phosphorescence wavelength to the deep blue region and to enhance the luminescence efficiencies. We investigate the electron-withdrawing capabilities of ancillary ligands using the DFT and TD-DFT calculations on the ground and excited states of the three complexes to gain insight into the factors responsible for the emission color change and the different luminescence efficiency. Reducing the molecular weight of phosphine ligand with PPhMe 2 leads to a strategy of the efficient deep blue organic light-emitting devices (OLED) by thermal processing instead of the solution processing. The electron-withdrawing difluoro group substituted on the phenyl ring and the cyano strong field ancillary ligand in the trans position to the carbon atom of phenyl ring increased HOMO-LUMO gap and achieved the hypsochromic shift in emission color. As a result, the maximum emission spectra of Ir(F 2 Meppy)(PPhMe 2 ) 2 (H)(Cl), [Ir(F 2 Meppy)(PPhMe 2 ) 2 (H)-(NCMe)] + and Ir(F 2 Meppy)(PPh-Me 2 ) 2 (H)(CN) were in the ranges of 446, 440, 439 nm, respectively.

  19. Strong ligand field effects of blue phosphorescent mono-cyclometalated iridium(III) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Ham, Ho Wan [Department of Information Display, Hongik University, Seoul, 121-791 (Korea, Republic of); Jung, Kyung Yoon [International Design School for Advanced Studies, Hongik University, Seoul 121-791 (Korea, Republic of); Kim, Young Sik, E-mail: youngkim@hongik.ac.k [Department of Information Display, Hongik University, Seoul, 121-791 (Korea, Republic of)

    2010-09-01

    A series of mono-cyclometalated blue phosphorescent iridium(III) complexes with two phosphines trans to each other and two cis-ancillary ligands, such as Ir(F{sub 2}Meppy)(PPhMe{sub 2}){sub 2}(H)(Cl), [Ir(F{sub 2}Meppy)(PPhMe{sub 2}){sub 2}(H)(NCMe)]{sup +} and Ir(F{sub 2}Meppy)(PPhMe{sub 2}){sub 2}-(H)(CN), [F{sub 2}Meppy = 2-(2',4'-difluorophenyl)-4-methyl-pyridine] were synthesized and studied to tune the phosphorescence wavelength to the deep blue region and to enhance the luminescence efficiencies. We investigate the electron-withdrawing capabilities of ancillary ligands using the DFT and TD-DFT calculations on the ground and excited states of the three complexes to gain insight into the factors responsible for the emission color change and the different luminescence efficiency. Reducing the molecular weight of phosphine ligand with PPhMe{sub 2} leads to a strategy of the efficient deep blue organic light-emitting devices (OLED) by thermal processing instead of the solution processing. The electron-withdrawing difluoro group substituted on the phenyl ring and the cyano strong field ancillary ligand in the trans position to the carbon atom of phenyl ring increased HOMO-LUMO gap and achieved the hypsochromic shift in emission color. As a result, the maximum emission spectra of Ir(F{sub 2}Meppy)(PPhMe{sub 2}){sub 2}(H)(Cl), [Ir(F{sub 2}Meppy)(PPhMe{sub 2}){sub 2}(H)-(NCMe)]{sup +} and Ir(F{sub 2}Meppy)(PPh-Me{sub 2}){sub 2} (H)(CN) were in the ranges of 446, 440, 439 nm, respectively.

  20. Speciation of Pu(4) complexes with weak ligands from visible spectra

    International Nuclear Information System (INIS)

    Berg, J.M.; Veirs, D.K.

    2001-01-01

    Stoichiometries of early actinide metal ion complexes in solution equilibrium can sometimes be determined by modelling the dependence of a species-sensitive measurement on ligand concentration. Weak ligands present the additional problem that these measurements cannot be made in the simplifying limiting case of low ligand concentration relative to the background electrolyte. At high ligand concentrations, constant ionic strength no longer implies constant activity coefficients. Additional parameters must be included in the equilibrium model to account for the variation of activity coefficients with ligand concentration as well as with overall ionic strength. We present the formalism of such a model based on SIT theory and its implementation for simultaneous fitting of spectra over a wide range of ionic strengths. As a test case, we analyse a subset of the spectra we have collected on complexation of Pu(IV) by nitrate in aqueous acid solutions. (authors)

  1. Structural and dynamical characterization of the Miz-1 zinc fingers 5-8 by solution-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Bernard, David; Bedard, Mikaeel; Bilodeau, Josee; Lavigne, Pierre, E-mail: pierre.lavigne@usherbrooke.ca [Universite de Sherbrooke, Departement de Biochimie, Faculte de Medecine et des Sciences de la Sante, Institut de Pharmacologie de Sherbrooke (Canada)

    2013-10-15

    Myc-interacting zinc finger protein-1 (Miz-1) is a BTB/POZ transcription factor that activates the transcription of cytostatic genes, such as p15{sup INK4B} or p21{sup CIP1}. The C-terminus of Miz-1 contains 13 consensus C{sub 2}H{sub 2} zinc finger domains (ZF). ZFs 1-4 have been shown to interact with SMAD3/4, while the remaining ZFs are expected to bind the promoters of target genes. We have noted unusual features in ZF 5 and the linker between ZFs 5 and 6. Indeed, a glutamate is found instead of the conserved basic residue two positions before the second zinc-coordinating histidine on the ZF 5 helix, and the linker sequence is DTDKE in place of the classical TGEKP sequence. In a canonical {beta}{beta}{alpha} fold, such unusual primary structure elements should cause severe electrostatic repulsions. In this context, we have characterized the structure and the dynamics of a Miz-1 construct comprising ZFs 5-8 (Miz 5-8) by solution-state NMR. Whilst ZFs 5, 7 and 8 were shown to adopt the classical {beta}{beta}{alpha} fold for C{sub 2}H{sub 2} ZFs, the number of long-range NOEs was insufficient to define a classical fold for ZF 6. We show by using {sup 15}N-relaxation dispersion experiments that this lack of NOEs is due to the presence of extensive motions on the {mu}s-ms timescale. Since this negatively charged region would have to be located near the phosphodiester backbone in a DNA complex, we propose that in addition to promoting conformational searches, it could serve as a hinge region to keep ZFs 1-4 away from DNA.

  2. Solution of the transport equation in stationary state and X Y geometry, using continuous and discontinuous hybrid nodal schemes

    International Nuclear Information System (INIS)

    Xolocostli M, V.; Valle G, E. del; Alonso V, G.

    2003-01-01

    In this work it is described the development and the application of the NH-FEM schemes, Hybrid Nodal schemes using the Finite Element method in the solution of the neutron transport equation in stationary state and X Y geometry, of which two families of schemes were developed, one of which corresponds to the continuous and the other to the discontinuous ones, inside those first its are had the Bi-Quadratic Bi Q, and to the Bi-cubic BiC, while for the seconds the Discontinuous Bi-lineal DBiL and the Discontinuous Bi-quadratic DBiQ. These schemes were implemented in a program to which was denominated TNHXY, Transport of neutrons with Hybrid Nodal schemes in X Y geometry. One of the immediate applications of the schemes NH-FEM it will be in the analysis of assemblies of nuclear fuel, particularly of the BWR type. The validation of the TNHXY program was made with two test problems or benchmark, already solved by other authors with numerical techniques and to compare results. The first of them consists in an it BWR fuel assemble in an arrangement 7x7 without rod and with control rod providing numerical results. The second is a fuel assemble of mixed oxides (MOX) in an arrangement 10x10. This last problem it is known as the Benchmark problem WPPR of the NEA Data Bank and the results are compared with those of other commercial codes as HELIOS, MCNP-4B and CPM-3. (Author)

  3. EPR of gamma irradiated solid sucrose and UV spectra of its solution. An attempt for calibration of solid state/EPR dosimetry

    International Nuclear Information System (INIS)

    Yordanov, N.D.; Karakirova, Y.

    2007-01-01

    A simple new approach for independent calibration of solid state/EPR (SS/EPR) dosimetry system is reported. It is based on the fact that: (i) gamma-irradiation of solid sucrose (sugar) induces stable EPR detectable free radicals accompanied by UV detectable brown colour stable in the solid state and in solution; (ii) both the EPR intensity of gamma-irradiated solid sucrose and its solution UV absorbance linearly depend on the absorbed dose high energy radiation and may be independently used for dosimetric purpose; (iii) UV spectrometers are calibrated. The correlation between EPR response and absorbed dose radiation of solid sucrose and UV absorption of its solutions is used in the present communication for calibration purpose. The procedure of sucrose extraction from sucrose-paraffin dosimeters is described. The calibration procedure may be applied to any other (alanine, self-calibrated, etc.) SS/EPR dosimeters, simultaneously irradiated with sucrose

  4. Structure characterization of the central repetitive domain of high molecular weight gluten proteins .2. Characterization in solution and in the dry state

    NARCIS (Netherlands)

    van Dijk, A.A.; De Boef, E.; Bekkers, A.; van Wijk, L.L.; van Swieten, E.; Hamer, R.J.; Robillard, G.T.

    The structure of the central repetitive domain of high molecular weight (HMW) wheat gluten proteins was characterized in solution and in the dry state using HMW proteins Bx6 and Bx7 and a subcloned, bacterially expressed part of the repetitive domain of HMW Dx5. Model studies of the HMW consensus

  5. Delineating pMDI model reactions with loblolly pine via solution-state NMR spectroscopy. Part 2, Non-catalyzed reactions with the wood cell wall

    Science.gov (United States)

    Daniel J. Yelle; John Ralph; Charles R. Frihart

    2011-01-01

    Solution-state NMR provides a powerful tool to observe the presence or absence of covalent bonds between wood and adhesives. Finely ground wood can be dissolved in an NMR compatible solvent system containing dimethylsulfoxide-d6 and N-methylimidazole-d6, in which the wood polymers remain largely intact. High-resolution...

  6. Delineating pMDI model reactions with loblolly pine via solution-state NMR spectroscopy. Part 1, Catalyzed reactions with wood models and wood polymers

    Science.gov (United States)

    Daniel J. Yelle; John Ralph; Charles R. Frihart

    2011-01-01

    To better understand adhesive interactions with wood, reactions between model compounds of wood and a model compound of polymeric methylene diphenyl diisocyanate (pMDI) were characterized by solution-state NMR spectroscopy. For comparison, finely ground loblolly pine sapwood, milled-wood lignin and holocellulose from the same wood were isolated and derivatized with...

  7. Chemical state analysis of iron(III) compounds precipitated homogeneously from solutions containing urea by means of Moessbauer spectrometry and x-ray diffractometry

    International Nuclear Information System (INIS)

    Ujihira, Yusuke; Ohyabu, Matashige; Murakami, Tetsuro; Horie, Tsuyoshi.

    1978-01-01

    Chemical states of iron(III) compounds, precipitated homogeneously by heating the iron(III) salt solution at 363 K in the presence of urea, was studied by means of Moessbauer spectrometry and X-ray diffractometry. The pH-time relation of urea hydrolysis revealed that the precipitation process from homogeneous solution is identical to the hydrolysis of iron(III) ion at pH around 2 under the homogeneous supply of OH - ion, which is generated by hydrolysis of urea. Accordingly, iron(III) oxide hydroxide or similar compounds to the hydrolysis products of iron(III) ion was precipitated by the precipitation from homogeneous solution methods. Akaganeite (β-FeOOH) was crystallized from 0.1 M iron(III) chloride solution. Goethite(α-FeOOH) and hematite(α-Fe 2 O 3 ) was precipitated from 0.1 M iron(III) nitrate solution, vigorous liberation of OH - ion favoring the crystallization of hematite. The addition of chloride ion to the solution resulted in the formation of akaganeite. Basic salt of iron sulfate[NH 4 Fe 3 (OH) 6 (SO 4 ) 2 ] and goethite were formed from 0.1 M iron(III) sulfate solution, the former being obtained in the more moderate condition of the urea hydrolysis ( 363 K). (author)

  8. 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

  9. Prediction of ligand effects in platinum-amyloid-β coordination.

    Science.gov (United States)

    Turner, Matthew; Deeth, Robert J; Platts, James A

    2017-08-01

    Ligand field molecular mechanics (LFMM) and semi-empirical Parametric Model 7 (PM7) methods are applied to a series of six Pt II -Ligand systems binding to the N-terminal domain of the amyloid-β (Aβ) peptide. Molecular dynamics using a combined LFMM/Assisted Model Building with Energy Refinement (AMBER) approach is used to explore the conformational freedom of the peptide fragment, and identifies favourable platinum binding modes and peptide conformations for each ligand investigated. Platinum coordination is found to depend on the nature of the ligand, providing evidence that binding mode may be controlled by suitable ligand design. Boltzmann populations at 310K indicate that each Pt-Aβ complex has a small number of thermodynamically accessible states. Ramachandran maps are constructed for the sampled Pt-Aβ conformations and secondary structural analysis of the obtained complex structures is performed and contrasted with the free peptide; coordination of these platinum complexes disrupts existing secondary structure in the Aβ peptide and promotes formation of ligand-specific turn-type secondary structure. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Predicting Efficient Antenna Ligands for Tb(III) Emission

    Energy Technology Data Exchange (ETDEWEB)

    Samuel, Amanda P.S.; Xu, Jide; Raymond, Kenneth

    2008-10-06

    A series of highly luminescent Tb(III) complexes of para-substituted 2-hydroxyisophthalamide ligands (5LI-IAM-X) has been prepared (X = H, CH{sub 3}, (C=O)NHCH{sub 3}, SO{sub 3}{sup -}, NO{sub 2}, OCH{sub 3}, F, Cl, Br) to probe the effect of substituting the isophthalamide ring on ligand and Tb(III) emission in order to establish a method for predicting the effects of chromophore modification on Tb(III) luminescence. The energies of the ligand singlet and triplet excited states are found to increase linearly with the {pi}-withdrawing ability of the substituent. The experimental results are supported by time-dependent density functional theory (TD-DFT) calculations performed on model systems, which predict ligand singlet and triplet energies within {approx}5% of the experimental values. The quantum yield ({Phi}) values of the Tb(III) complex increases with the triplet energy of the ligand, which is in part due to the decreased non-radiative deactivation caused by thermal repopulation of the triplet. Together, the experimental and theoretical results serve as a predictive tool that can be used to guide the synthesis of ligands used to sensitize lanthanide luminescence.

  11. Isotopic Ligand Exchange of Some Hexa-Coordinated Inorganic Complexes with Halide Ions in Solution and in Crystals; Echanges Isotopiques de Coordinats de Complexes Inorganiques Hexacoordonnes Avec des Ions Halogenures en Solution et dans les Cristaux; Izotopnyj obmen ligand v nekotorykh geksakoordinirovannykh ne- organicheskikh kompleksakh s ionami galoidov v rastvore i kristallakh; Intercambio Isotopico de Ligandos de Complejos Inorganicos Hexacoordinados y Iones Haluro en Solucion y en Cristales

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, G. B. [Institut fuer Kernchemie der Universitaet Koeln, Cologne, Federal Republic of Germany (Germany)

    1965-10-15

    The kinetics of isotopic exchange reactions give information about the lability of complexes in solution and about the mechanisms of substitution. The exchange of {sup 82}Br-labelled [Rh(NH{sub 3}){sub 5}Br]{sup 2+} and [Ii(NH{sub 3}){sub 5}Br]{sup 2+} complexes with Br{sup -} ions, of trans-[Rh(en){sub 2}Cl{sub 2}]{sup +} and trans- [Co(en){sub 2} Cl{sub 2}]{sup +}]+ with Cl{sup -} ions, of trans- [Co(en){sub 2}Br{sub 2}]{sup +} with Br{sup -} and of [OSCl{sub 6}]{sup 2-} and [OsI{sub 6}]{sup 2-} with Cl{sup -} and I{sup -} ions, respectively, was investigated in acid solutions. The iridium pentamminebromo complex exchanges about 60 times slower than the corresponding rhodium pentamminebromo complex. The rate constant for the Rh- complex was found to be k = (1.03 {+-} 0,02) x 10{sup -2} min{sup -1} at 100 Degree-Sign C, for the Ir-complex k{sub 100 Degree-Sign C} = 1.7 x 10{sup -4} min{sup -1}. For both complexes the exchange rate R is first-order in the complex concentration; in acid solution R is nearly independent of the bromide and hydrogen concentration as well as of the ionic strength. This indicates that the exchange takes place by a dissociation mechanism. Activation energies of 24 and 23 kcal/ mole forthe Rh- and Ir-complex, respectively, were calculated. Rate constants of the {sup 36}Cl isotopic exchange between 60 and 100 Degree-Sign C were measured for the trans- [Rh(en){sub 2} Cl{sub 2}]{sup +} complex and an Arrhenius activation energy of 25 kcal/mole was determined. Here again the increase of the rate R is of first order in the complex concentration; but it is only slightly dependent on the hydrogen and chloride concentration. The exchange seems to occur by aquation. In methanolic HCl solution the exchange rate of this complex is immeasurably slow at 60 Degree-Sign C. The halide exchanges of trans-[Co(en){sub 2} Cl{sub 2}]{sup +} and trans [Co(en){sub 2} Br{sub 2}]{sup +} were measured in methanolic solutions between 30 and 60 Degree-Sign C. Further

  12. Lanthanide and actinide complexation studies with tetradentate 'N' donor ligands

    International Nuclear Information System (INIS)

    Bhattacharyya, A.; Mohapatra, M.; Mohapatra, P.K.; Rawat, N.; Tomar, B.S.; Gadly, T.; Ghosh, S.K.; Manna, D.; Ghanty, T.K.

    2014-01-01

    Because of their similar charge and chemical behaviour separation of trivalent actinides and lanthanides is an important and challenging task in nuclear fuel cycle. Soft (S,N) donor ligands show selectivity towards the trivalent actinides over the lanthanides. Out of various 'N' donor ligands studied, bis(1,2,4)triazinyl bipyridine (BTBP) and bis(1,2,4)triazinyl phenanthroline (BTPhen) were found to be most promising. In order to understand the separation behaviour of these ligands, their complexation studies with these 'f' block elements are essential. In the present work, complexation studies of various lanthanide ions (La 3+ , Eu 3+ and Er 3+ ) was studied with ethyl derivatives of BTBP (C 2 BTBP) and BTBPhen (C 2 BTPhen) and pentyl derivative of BTBP (C 5 BTBP) in acetonitrile medium using UV-Vis spectrophotometry, fluorescence spectroscopy and solution calorimetry. Computational studies were also carried out to understand the experimental results

  13. BREIT code: Analytical solution of the balance rate equations for charge-state evolutions of heavy-ion beams in matter

    Energy Technology Data Exchange (ETDEWEB)

    Winckler, N., E-mail: n.winckler@gsi.de [GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Rybalchenko, A. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Shevelko, V.P. [P.N. Lebedev Physical Institute, 119991 Moscow (Russian Federation); Al-Turany, M. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); CERN, European Organization for Nuclear Research, 1211 Geneve 23 (Switzerland); Kollegger, T. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Stöhlker, Th. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Helmholtz-Institute Jena, D-07743 Jena (Germany); Institut für Optik und Quantenelektronik, Friedrich-Schiller-Universität, D-07743 Jena (Germany)

    2017-02-01

    A detailed description of a recently developed BREIT computer code (Balance Rate Equations of Ion Transportation) for calculating charge-state fractions of ion beams passing through matter is presented. The code is based on the analytical solutions of the differential balance equations for the charge-state fractions as a function of the target thickness and can be used for calculating the ion evolutions in gaseous, solid and plasma targets. The BREIT code is available on-line and requires the charge-changing cross sections and initial conditions in the input file. The eigenvalue decomposition method, applied to obtain the analytical solutions of the rate equations, is described in the paper. Calculations of non-equilibrium and equilibrium charge-state fractions, performed by the BREIT code, are compared with experimental data and results of other codes for ion beams in gaseous and solid targets. Ability and limitations of the BREIT code are discussed in detail.

  14. submitter BREIT code: Analytical solution of the balance rate equations for charge-state evolutions of heavy-ion beams in matter

    CERN Document Server

    Winckler, N; Shevelko, V P; Al-Turany, M; Kollegger, T; Stöhlker, Th

    2017-01-01

    A detailed description of a recently developed BREIT computer code (Balance Rate Equations of Ion Transportation) for calculating charge-state fractions of ion beams passing through matter is presented. The code is based on the analytical solutions of the differential balance equations for the charge-state fractions as a function of the target thickness and can be used for calculating the ion evolutions in gaseous, solid and plasma targets. The BREIT code is available on-line and requires the charge-changing cross sections and initial conditions in the input file. The eigenvalue decomposition method, applied to obtain the analytical solutions of the rate equations, is described in the paper. Calculations of non-equilibrium and equilibrium charge-state fractions, performed by the BREIT code, are compared with experimental data and results of other codes for ion beams in gaseous and solid targets. Ability and limitations of the BREIT code are discussed in detail.

  15. on the properties of solutions and some applications on the TOV differential equation with a model of nuclear equation of state

    International Nuclear Information System (INIS)

    Esmail, S.F.H.

    2006-01-01

    the mathematical formulation of numerous physical problems results in differential equations actually non-linear differential equations . in our study we are interested in solutions of differential equations which describe the structure of neutron star in non-relativistic and relativistic cases. the aim of this work is to determine the mass and the radius of a neutron star, by solving the tolmann-oppenheimer-volkoff (TOV) differential equation using different models of the nuclear equation of state (EOS). analytically solutions are obtained for a simple form of the nuclear equation of state of Clayton model and poly trope model. for a more realistic equation of state the TOV differential equation is solved numerically using rung -Kutta method

  16. Synthesis and characterisation of luminescent rhenium tricarbonyl complexes with axially coordinated 1,2,3-triazole ligands.

    Science.gov (United States)

    Uppal, Baljinder S; Booth, Rebecca K; Ali, Noreen; Lockwood, Cindy; Rice, Craig R; Elliott, Paul I P

    2011-08-07

    A series of 1-alkyl-4-aryl-1,2,3-triazoles (1-methyl-4-phenyl-1,2,3-triazole (1a); 1-propyl-4-phenyl-1,2,3-triazole (1b); 1-benzyl-4-phenyl-1,2,3-triazole (1c); 1-propyl-4-p-tolyl-1,2,3-triazole (1d)) have been prepared through a one-pot procedure involving in situ generation of the alkyl azide from a halide precursor followed by copper catalysed alkyne/azide cycloaddition (CuAAC) with the appropriate aryl alkyne. Cationic Re(I) complexes [Re(bpy)(CO)(3)(1a-d)]PF(6) (2a-d) were then prepared by stirring [Re(bpy)(CO)(3)Cl] with AgPF(6) in dichloromethane in the presence of ligands 1a-d. X-ray crystal structures were obtained for 2a and 2b. In the solid state, 2a adopts a highly distorted geometry, which is not seen for 2b, in which the plane of the triazole ligand tilts by 13° with respect to the Re-N bond as a result of a π-stacking interaction between the Ph substituent and one of the rings of the bpy ligand. This π-stacking interaction also results in severe twisting of the bpy ligand. Infrared spectra of 2a-d exhibit ν(CO) bands at ∼2035 and ∼1926 cm(-1) suggesting that these ligands are marginally better donors than pyridine (ν(CO) = 2037, 1932 cm(-1)). The complexes are luminescent in aerated dichloromethane at room temperature with emission maxima at 542 to 552 nm comparable to that of the pyridine analogue (549 nm) and blue shifted relative to the parent chloride complex. Long luminescent lifetimes are observed for the triazole complexes (475 to 513 ns) in aerated dichloromethane solutions at room temperature.

  17. Formation of mixed ligand complexes of UO22+ involving some nitrogen and oxygen donor ligands

    International Nuclear Information System (INIS)

    Singh, Mamta; Ram Nayan

    1996-01-01

    The complexation reactions of UO 2 2+ ion with nitrogen and oxygen donor ligands, 1-amino-2-naphthol-4-sulphonic acid, o-aminophenol (ap), 2-hydroxybenzoic acid (sa), 3-carboxy-4-hydroxybenzenesulphonic acid (ss) and 1,2-dihydroxybenzene (ca) have been investigated in aqueous solution employing the pH-titration technique. Analysis of the experimental data recorded at 25 degC and at an ionic strength of 0.10 M KNO 3 indicates formation of binary, hydroxo and ternary complexes of uranium. Formation constant values of the existing species have been evaluated and the results have been discussed. (author). 21 refs., 2 figs., 2 tabs

  18. Functionalization of Cadmium Selenide Quantum Dots with Poly(ethylene glycol): Ligand Exchange, Surface Coverage, and Dispersion Stability.

    Science.gov (United States)

    Wenger, Whitney Nowak; Bates, Frank S; Aydil, Eray S

    2017-08-22

    Semiconductor quantum dots synthesized using rapid mixing of precursors by injection into a hot solution of solvents and surfactants have surface ligands that sterically stabilize the dispersions in nonpolar solvents. Often, these ligands are exchanged to disperse the quantum dots in polar solvents, but quantitative studies of quantum dot surfaces before and after ligand exchange are scarce. We studied exchanging trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO) ligands on as-synthesized CdSe quantum dots dispersed in hexane with a 2000 g/mol thiolated poly(ethylene glycol) (PEG) polymer. Using infrared spectroscopy we quantify the absolute surface concentration of TOP/TOPO and PEG ligands per unit area before and after ligand exchange. While 50-85% of the TOP/TOPO ligands are removed upon ligand exchange, only a few are replaced with PEG. Surprisingly, the remaining TOP/TOPO ligands outnumber the PEG ligands, but these few PEG ligands are sufficient to disperse the quantum dots in polar solvents such as chloroform, tetrahydrofuran, and water. Moreover, as-synthesized quantum dots once easily dispersed in hexane are no longer dispersible in nonpolar solvents after ligand exchange. A subtle coverage-dependent balance between attractive PEG-solvent interactions and repulsive TOP/TOPO-solvent interactions determines the dispersion stability.

  19. Signatures of Quantized Energy States in Solution-Processed Ultrathin Layers of Metal-Oxide Semiconductors and Their Devices

    KAUST Repository

    Labram, John G.; Lin, Yenhung; Zhao, Kui; Li, Ruipeng; Thomas, Stuart R.; Semple, James; Androulidaki, Maria; Sygellou, Lamprini; McLachlan, Martyn A.; Stratakis, Emmanuel; Amassian, Aram; Anthopoulos, Thomas D.

    2015-01-01

    reports of the growth of uniform, ultrathin (<5 nm) metal-oxide semiconductors from solution, however, have potentially opened the door to such phenomena manifesting themselves. Here, a theoretical framework is developed for energy quantization

  20. Exact partial solution to the steady-state, compressible fluid flow problems of jet formation and jet penetration

    International Nuclear Information System (INIS)

    Karpp, R.R.

    1980-10-01

    This report treats analytically the problem of the symmetric impact of two compressible fluid streams. The flow is assumed to be steady, plane, inviscid, and subsonic and that the compressible fluid is of the Chaplygin (tangent gas) type. In the analysis, the governing equations are first transformed to the hodograph plane where an exact, closed-form solution is obtained by standard techniques. The distributions of fluid properties along the plane of symmetry as well as the shapes of the boundary streamlines are exactly determined by transforming the solution back to the physical plane. The problem of a compressible fluid jet penetrating into an infinite target of similar material is also exactly solved by considering a limiting case of this solution. This new compressible flow solution reduces to the classical result of incompressible flow theory when the sound speed of the fluid is allowed to approach infinity. Several illustrations of the differences between compressible and incompressible flows of the type considered are presented

  1. Determination of the thermodynamic state of concentrated hemoglobin solutions by means of small angle X-ray scattering

    International Nuclear Information System (INIS)

    Zinke, M.

    1979-01-01

    Exemplified by hemoglobin, the thermodynamic equilibrium properties of the dissolved macromolecular system could be determined solely from the small angle X-ray scattering of concentrated macromolecular solutions via the intermolecular structure of the dissolved macromolecules and their intermolecular potentials. From the scattering experiment on concentrated Hb solutions the concentration dependence of the following properties of the dissolved Hb system were determined: fluctuation, isothermic compressibility, internal energy, surface tension, and osmotic pressure. (author)

  2. Structure characterization of the central repetitive domain of high molecular weight gluten proteins. II. Characterization in solution and in the dry state

    OpenAIRE

    Dijk, Alard A. van; Boef, Esther de; Bekkers, August; Wijk, Lourens L. van; Swieten, Eric van; Hamer, Rob J.; Robillard, George T.

    1997-01-01

    The structure of the central repetitive domain of high molecular weight HMW) wheat gluten proteins was characterized in solution and in the dry state using HMW proteins Bx6 and Bx7 and a subcloned, bacterially expressed part of the repetitive domain of HMW Dx5. Model studies of the HMW consensus peptides PGQGQQ and GYYPTSPQQ formed the basis for the data analysis (van Dijk AA et al., 1997, Protein Sci 6:637-648). In solution, the repetitive domain contained a continuous nonoverlapping series ...

  3. In situ monitoring the effects of a magnetic field on the open-circuit corrosion states of iron in acidic and neutral solutions

    International Nuclear Information System (INIS)

    Lu Zhanpeng; Yang Wu

    2008-01-01

    The effects of a 0.4 T horizontal magnetic field (HMF) on the open-circuit corrosion states of iron in static aqueous solutions are studied by in situ monitoring the responses of two electrochemical parameters to the applied magnetic field, i.e. the open-circuit potential (OCP) and the current under potentiostatic polarization. The applied magnetic field makes the OCP shift in the noble direction. Withdrawing the magnetic field causes a negative shift of the OCP in acidic solutions, but it does not cause any significant change of OCP in neutral solutions. Imposing a magnetic field induces a cathodic current for iron that was previously potentiostatically polarized at the OCP without magnetic field. Withdrawing the magnetic field induces an anodic current for iron that was previously potentiostatically polarized at the OCP with the magnetic field. The magnetic field effect is more significant in the acid solutions than in the salt solutions. The magnetic field effects on the oxygen reduction and on the activation-controlled iron dissolution reaction are found to be insignificant. The magnetic field effect on the hydrogen reduction reaction on iron in acidic solutions is demonstrated. Results show the possibility that a magnetic field would affect the hydrogen evolution by enhancing the electron-transfer process that has been categorized in the classical electrochemistry kinetics to be the rate-determining process. The memory effect of the magnetic field on the electrochemical reaction is identified and discussed

  4. Quantitative analysis of protein-ligand interactions by NMR.

    Science.gov (United States)

    Furukawa, Ayako; Konuma, Tsuyoshi; Yanaka, Saeko; Sugase, Kenji

    2016-08-01

    Protein-ligand interactions have been commonly studied through static structures of the protein-ligand complex. Recently, however, there has been increasing interest in investigating the dynamics of protein-ligand interactions both for fundamental understanding of the underlying mechanisms and for drug development. NMR is a versatile and powerful tool, especially because it provides site-specific quantitative information. NMR has widely been used to determine the dissociation constant (KD), in particular, for relatively weak interactions. The simplest NMR method is a chemical-shift titration experiment, in which the chemical-shift changes of a protein in response to ligand titration are measured. There are other quantitative NMR methods, but they mostly apply only to interactions in the fast-exchange regime. These methods derive the dissociation constant from population-averaged NMR quantities of the free and bound states of a protein or ligand. In contrast, the recent advent of new relaxation-based experiments, including R2 relaxation dispersion and ZZ-exchange, has enabled us to obtain kinetic information on protein-ligand interactions in the intermediate- and slow-exchange regimes. Based on R2 dispersion or ZZ-exchange, methods that can determine the association rate, kon, dissociation rate, koff, and KD have been developed. In these approaches, R2 dispersion or ZZ-exchange curves are measured for multiple samples with different protein and/or ligand concentration ratios, and the relaxation data are fitted to theoretical kinetic models. It is critical to choose an appropriate kinetic model, such as the two- or three-state exchange model, to derive the correct kinetic information. The R2 dispersion and ZZ-exchange methods are suitable for the analysis of protein-ligand interactions with a micromolar or sub-micromolar dissociation constant but not for very weak interactions, which are typical in very fast exchange. This contrasts with the NMR methods that are used

  5. LigandRFs: random forest ensemble to identify ligand-binding residues from sequence information alone

    KAUST Repository

    Chen, Peng; Huang, Jianhua Z; Gao, Xin

    2014-01-01

    Protein-ligand binding is important for some proteins to perform their functions. Protein-ligand binding sites are the residues of proteins that physically bind to ligands. Despite of the recent advances in computational prediction

  6. pH-specific hydrothermal assembly of binary and ternary Pb(II)-(O,N-carboxylic acid) metal organic framework compounds: correlation of aqueous solution speciation with variable dimensionality solid-state lattice architecture and spectroscopic signatures.

    Science.gov (United States)

    Gabriel, C; Perikli, M; Raptopoulou, C P; Terzis, A; Psycharis, V; Mateescu, C; Jakusch, T; Kiss, T; Bertmer, M; Salifoglou, A

    2012-09-03

    Hydrothermal pH-specific reactivity in the binary/ternary systems of Pb(II) with the carboxylic acids N-hydroxyethyl-iminodiacetic acid (Heida), 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid (Dpot), and 1,10-phenanthroline (Phen) afforded the new well-defined crystalline compounds [Pb(Heida)](n)·nH(2)O(1), [Pb(Phen)(Heida)]·4H(2)O(2), and [Pb(3)(NO(3))(Dpot)](n)(3). All compounds were characterized by elemental analysis, FT-IR, solution or/and solid-state NMR, and single-crystal X-ray diffraction. The structures in 1-2 reveal the presence of a Pb(II) center coordinated to one Heida ligand, with 1 exhibiting a two-dimensional (2D) lattice extending to a three-dimensional (3D) one through H-bonding interactions. The concurrent aqueous speciation study of the binary Pb(II)-Heida system projects species complementing the synthetic efforts, thereby lending credence to a global structural speciation strategy in investigating binary/ternary Pb(II)-Heida/Phen systems. The involvement of Phen in 2 projects the significance of nature and reactivity potential of N-aromatic chelators, disrupting the binary lattice in 1 and influencing the nature of the ultimately arising ternary 3D lattice. 3 is a ternary coordination polymer, where Pb(II)-Dpot coordination leads to a 2D metal-organic-framework material with unique architecture. The collective physicochemical properties of 1-3 formulate the salient features of variable dimensionality metal-organic-framework lattices in binary/ternary Pb(II)-(hydroxy-carboxylate) structures, based on which new Pb(II) materials with distinct architecture and spectroscopic signature can be rationally designed and pursued synthetically.

  7. Singular Value Decomposition and Ligand Binding Analysis

    Directory of Open Access Journals (Sweden)

    André Luiz Galo

    2013-01-01

    Full Text Available Singular values decomposition (SVD is one of the most important computations in linear algebra because of its vast application for data analysis. It is particularly useful for resolving problems involving least-squares minimization, the determination of matrix rank, and the solution of certain problems involving Euclidean norms. Such problems arise in the spectral analysis of ligand binding to macromolecule. Here, we present a spectral data analysis method using SVD (SVD analysis and nonlinear fitting to determine the binding characteristics of intercalating drugs to DNA. This methodology reduces noise and identifies distinct spectral species similar to traditional principal component analysis as well as fitting nonlinear binding parameters. We applied SVD analysis to investigate the interaction of actinomycin D and daunomycin with native DNA. This methodology does not require prior knowledge of ligand molar extinction coefficients (free and bound, which potentially limits binding analysis. Data are acquired simply by reconstructing the experimental data and by adjusting the product of deconvoluted matrices and the matrix of model coefficients determined by the Scatchard and McGee and von Hippel equation.

  8. Monitoring the solid-state electrochemistry of Cu(2,7-AQDC) (AQDC = anthraquinone dicarboxylate) in a lithium battery: coexistence of metal and ligand redox activities in a metal-organic framework.

    Science.gov (United States)

    Zhang, Zhongyue; Yoshikawa, Hirofumi; Awaga, Kunio

    2014-11-19

    By adopting a facile synthetic strategy, we obtained a microporous redox-active metal-organic framework (MOF), namely, Cu(2,7-AQDC) (2,7-H2AQDC = 2,7-anthraquinonedicarboxylic acid) (1), and utilized it as a cathode active material in lithium batteries. With a voltage window of 4.0-1.7 V, both metal clusters and anthraquinone groups in the ligands exhibited reversible redox activity. The valence change of copper cations was clearly evidenced by in situ XANES analysis. By controlling the voltage window of operation, extremely high recyclability of batteries was achieved, suggesting the framework was robust. This MOF is the first example of a porous material showing independent redox activity on both metal cluster nodes and ligand sites.

  9. What a Difference Ancillary Thienyl Makes: Unexpected Additional Stabilization of the Diruthenium(III,II) but Not the Diosmium(III,II) Mixed-Valent State in Tetrazine Ligand-Bridged Complexes

    Czech Academy of Sciences Publication Activity Database

    Sarkas, B.; Kaim, W.; Klein, A.; Schwederski, B.; Fiedler, Jan; Duboc-Toia, C.; Lahiri, G. K.

    2003-01-01

    Roč. 42, č. 20 (2003), s. 6172-6174 ISSN 0020-1669 R&D Projects: GA MŠk OC D15.10; GA MŠk OC D14.20 Institutional research plan: CEZ:AV0Z4040901 Keywords : donor ligand s * Ru * dimers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.389, year: 2003

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  11. Organic ligand-induced dissolution kinetics of antimony trioxide

    Institute of Scientific and Technical Information of China (English)

    Xingyun Hu; Mengchang He

    2017-01-01

    The influence of low-molecular-weight dissolved organic matter (LMWDOM) on the dissolution rate of Sb2O3 was investigated.Some representative LMWDOMs with carboxyl,hydroxyl,hydrosulfuryl and amidogen groups occurring naturally in the solution were chosen,namely oxalic acid,citric acid,tartaric acid,EDTA,salicylic acid,phthalandione,glycine,thiolactic acid,xylitol,glucose and catechol.These LMWDOMs were dissolved in inert buffers at pH =3.7,6.6 and 8.6 and added to powdered Sb2O3 in a stirred,thermostatted reactor (25℃).The addition of EDTA,tartaric acid,thiolactic acid,citric acid and oxalic acid solutions at pH 3.7 and catechol at pH 8.6 increased the rate of release of antimony.In the 10 mmol/L thiolactic acid solution,up to 97% by mass of the antimony was released after 120 min reaction.There was no effect on the dissolution of Sb2O3 for the other ligands.A weak correlation between dissolution rate with the dissociation constant of ligands and the stability of the dissolved complex was also found.All the results showed that the extent of the promoting effect of ligands on the dissolution of Sb2O3 was not determined by the stability of the dissolved complex,but by the dissociation constant of ligands and detachment rate of surface chelates from the mineral surface.This study can not only help in further understanding the effect of individual low-molecular-weight organic ligands,but also provides a reference to deduce the effect of natural organic matters with oxygen-bearing functional groups on the dissolution of antimony oxide minerals.

  12. Organic ligand-induced dissolution kinetics of antimony trioxide.

    Science.gov (United States)

    Hu, Xingyun; He, Mengchang

    2017-06-01

    The influence of low-molecular-weight dissolved organic matter (LMWDOM) on the dissolution rate of Sb 2 O 3 was investigated. Some representative LMWDOMs with carboxyl, hydroxyl, hydrosulfuryl and amidogen groups occurring naturally in the solution were chosen, namely oxalic acid, citric acid, tartaric acid, EDTA, salicylic acid, phthalandione, glycine, thiolactic acid, xylitol, glucose and catechol. These LMWDOMs were dissolved in inert buffers at pH=3.7, 6.6 and 8.6 and added to powdered Sb 2 O 3 in a stirred, thermostatted reactor (25°C). The addition of EDTA, tartaric acid, thiolactic acid, citric acid and oxalic acid solutions at pH3.7 and catechol at pH8.6 increased the rate of release of antimony. In the 10mmol/L thiolactic acid solution, up to 97% by mass of the antimony was released after 120min reaction. There was no effect on the dissolution of Sb 2 O 3 for the other ligands. A weak correlation between dissolution rate with the dissociation constant of ligands and the stability of the dissolved complex was also found. All the results showed that the extent of the promoting effect of ligands on the dissolution of Sb 2 O 3 was not determined by the stability of the dissolved complex, but by the dissociation constant of ligands and detachment rate of surface chelates from the mineral surface. This study can not only help in further understanding the effect of individual low-molecular-weight organic ligands, but also provides a reference to deduce the effect of natural organic matters with oxygen-bearing functional groups on the dissolution of antimony oxide minerals. Copyright © 2016. Published by Elsevier B.V.

  13. Potent inhibition of tau fibrillization with a multivalent ligand

    International Nuclear Information System (INIS)

    Honson, Nicolette S.; Jensen, Jordan R.; Darby, Michael V.; Kuret, Jeff

    2007-01-01

    Small-molecule inhibitors of tau fibrillization are under investigation as tools for interrogating the tau aggregation pathway and as potential therapeutic agents for Alzheimer's disease. Established inhibitors include thiacarbocyanine dyes, which can inhibit recombinant tau fibrillization in the presence of anionic surfactant aggregation inducers. In an effort to increase inhibitory potency, a cyclic bis-thiacarbocyanine molecule containing two thiacarbocyanine moieties was synthesized and characterized with respect to tau fibrillization inhibitory activity by electron microscopy and ligand aggregation state by absorbance spectroscopy. Results showed that the inhibitory activity of the bis-thiacarbocyanine was qualitatively similar to a monomeric cyanine dye, but was more potent with 50% inhibition achieved at ∼80 nM concentration. At all concentrations tested in aqueous solution, the bis-thiacarbocyanine collapsed to form a closed clamshell structure. However, the presence of tau protein selectively stabilized the open conformation. These results suggest that the inhibitory activity of bis-thiacarbocyanine results from multivalency, and reveal a route to more potent tau aggregation inhibitors

  14. Rosetta Ligand docking with flexible XML protocols.

    Science.gov (United States)

    Lemmon, Gordon; Meiler, Jens

    2012-01-01

    RosettaLigand is premiere software for predicting how a protein and a small molecule interact. Benchmark studies demonstrate that 70% of the top scoring RosettaLigand predicted interfaces are within 2Å RMSD from the crystal structure [1]. The latest release of Rosetta ligand software includes many new features, such as (1) docking of multiple ligands simultaneously, (2) representing ligands as fragments for greater flexibility, (3) redesign of the interface during docking, and (4) an XML script based interface that gives the user full control of the ligand docking protocol.

  15. Charge-Transfer Effects in Ligand Exchange Reactions of Au25 Monolayer-Protected Clusters.

    Science.gov (United States)

    Carducci, Tessa M; Blackwell, Raymond E; Murray, Royce W

    2015-04-16

    Reported here are second-order rate constants of associative ligand exchanges of Au25L18 nanoparticles (L = phenylethanethiolate) of various charge states, measured by proton nuclear magnetic resonance at room temperature and below. Differences in second-order rate constants (M(-1) s(-1)) of ligand exchange (positive clusters ∼1.9 × 10(-5) versus negative ones ∼1.2 × 10(-4)) show that electron depletion retards ligand exchange. The ordering of rate constants between the ligands benzeneselenol > 4-bromobenzene thiol > benzenethiol reveals that exchange is accelerated by higher acidity and/or electron donation capability of the incoming ligand. Together, these observations indicate that partial charge transfer occurs between the nanoparticle and ligand during the exchange and that this is a rate-determining effect in the process.

  16. Ligand-dependent exciton dynamics and photovoltaic properties of PbS quantum dot heterojunction solar cells.

    Science.gov (United States)

    Chang, Jin; Ogomi, Yuhei; Ding, Chao; Zhang, Yao Hong; Toyoda, Taro; Hayase, Shuzi; Katayama, Kenji; Shen, Qing

    2017-03-01

    The surface chemistry of colloidal quantum dots (QDs) plays an important role in determining the photoelectric properties of QD films and the corresponding quantum dot heterojunction solar cells (QDHSCs). To investigate the effects of the ligand structure on the photovoltaic performance and exciton dynamics of QDHSCs, PbS QDHSCs were fabricated by the solid state ligand exchange method with mercaptoalkanoic acid as the cross-linking ligand. Temperature-dependent photoluminescence and ultrafast transient absorption spectra show that the electronic coupling and charge transfer rate within QD ensembles were monotonically enhanced as the ligand length decreased. However, in practical QDHSCs, the second shortest ligand 3-mercaptopropionic acid (MPA) showed higher power conversion efficiency than the shortest ligand thioglycolic acid (TGA). This could be attributed to the difference in their surface trap states, supported by thermally stimulated current measurements. Moreover, compared with the non-conjugated ligand MPA, the conjugated ligand 4-mercaptobenzoic acid (MBA) introduces less trap states and has a similar charge transfer rate in QD ensembles, but has poor photovoltaic properties. This unexpected result could be contributed by the QD-ligand orbital mixing, leading to the charge transfer from QDs to ligands instead of charge transfer between adjacent QDs. This work highlights the significant effects of ligand structures on the photovoltaic properties and exciton dynamics of QDHSCs, which would shed light on the further development of QD-based photoelectric devices.

  17. The role of ligands in the optical and electronic spectra of CdSe nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Kilina, Svletana [Los Alamos National Laboratory; Sergei, Ivanov A [Los Alamos National Laboratory; Victor, Klimov I [Los Alamos National Laboratory; Sergei, Tretiak [Los Alamos National Laboratory

    2008-01-01

    We investigate the impact of ligands on morphology, electronic structure, and optical response of the Cd33Se33 cluster, which already overlapps in size with the smallest synthesized CdSe quantum dots (QDs). Our Density Functional Theory (DFT) calculations demonstrate significant surface reorganization both for the bare cluster and for the cluster capped by amine and phosphine oxide ligand models. We observe strong surface-ligand interactions leading to substantial charge redistribution and polarization effects on the surface. This effect results in the appearance of hybridized states, where the electronic density is spread over the cluster and the ligands. Neither the ligand's nor hybridized molecular orbitals appear as trap states inside or near the band gap of the QD. Instead, being optically dark, dense hybridized states from the edges of the valence and the conduction bands could open new relaxation channels for high energy photoexcitations. Comparing quantum dots passivated by different ligands, we found that hybridized states are denser in at the edge of the conduction band of the cluster ligated with phosphine oxide molecules than that with primary amines. Such a different manifestation of ligand binding may potentially lead to the faster electron relaxation in dots passivated by phosphine oxide than by amine ligands, which is in agreement with experimental data.

  18. Excited-state dynamics of a ruthenium(II) catalyst studied by transient photofragmentation in gas phase and transient absorption in solution

    Energy Technology Data Exchange (ETDEWEB)

    Imanbaew, D.; Nosenko, Y. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Kerner, C. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Chevalier, K.; Rupp, F. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Riehn, C., E-mail: riehn@chemie.uni-kl.de [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Thiel, W.R. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Diller, R. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany)

    2014-10-17

    Graphical abstract: - Highlights: • Ultrafast dynamics of new Ru(II) catalysts investigated in gas phase and solution. • Catalyst activation (HCl loss) achieved in ion trap by UV photoexcitation. • Electronic relaxation proceeds by IVR and IC followed by ground state dissociation. • No triplet formation in contrast to other Ru-polypyridine complexes. • Solvent prohibits catalyst activation in solution by fast vibrational cooling. - Abstract: We report studies on the excited state dynamics of new ruthenium(II) complexes [(η{sup 6}-cymene)RuCl(apypm)]PF{sub 6} (apypm=2-NR{sub 2}-4-(pyridine-2-yl)-pyrimidine, R=CH{sub 3} (1)/H (2)) which, in their active form [1{sup +}-HCl] and [2{sup +}-HCl], catalyze the transfer hydrogenation of arylalkyl ketones in the absence of a base. The investigations encompass femtosecond pump–probe transient mass spectrometry under isolated conditions and transient absorption spectroscopy in acetonitrile solution, both on the cations [(η{sup 6}-cymene)RuCl(apypm)]{sup +} (1{sup +}, 2{sup +}). Gas phase studies on mass selected ions were performed in an ESI ion trap mass spectrometer by transient photofragmentation, unambiguously proving the formation of the activated catalyst species [1{sup +}-HCl] or [2{sup +}-HCl] after photoexcitation being the only fragmentation channel. The primary excited state dynamics in the gas phase could be fitted to a biexponential decay, yielding time constants of <100 fs and 1–3 ps. Transient absorption spectroscopy performed in acetonitrile solution using femtosecond UV/Vis and IR probe laser pulses revealed additional deactivation processes on longer time scales (∼7–12 ps). However, the formation of the active catalyst species after photoexcitation could not be observed in solution. The results from both studies are compared to former CID investigations and DFT calculations concerning the activation mechanism.

  19. Speciation of Zinc Mixed Ligand Complexes in Salt Water Systems ...

    African Journals Online (AJOL)

    Speciation of Zinc Mixed Ligand Complexes in Salt Water Systems. ... method has been used to study heavy metal interaction in model lake water in KNO3 ... is of no consequential effect because in its normal state, the [OH-] of the lake water is ...

  20. An excited state underlies gene regulation of a transcriptional riboswitch

    Science.gov (United States)

    Zhao, Bo; Guffy, Sharon L.; Williams, Benfeard; Zhang, Qi

    2017-01-01

    Riboswitches control gene expression through ligand-dependent structural rearrangements of the sensing aptamer domain. However, we found that the Bacillus cereus fluoride riboswitch aptamer adopts identical tertiary structures in solution with and without ligand. Using chemical exchange saturation transfer (CEST) NMR spectroscopy, we revealed that the structured ligand-free aptamer transiently accesses a low-populated (~1%) and short-lived (~3 ms) excited conformational state that unravels a conserved ‘linchpin’ base pair to signal transcription termination. Upon fluoride binding, this highly localized fleeting process is allosterically suppressed to activate transcription. We demonstrated that this mechanism confers effective fluoride-dependent gene activation over a wide range of transcription rates, which is essential for robust toxicity response across diverse cellular conditions. These results unveil a novel switching mechanism that employs ligand-dependent suppression of an aptamer excited state to coordinate regulatory conformational transitions rather than adopting distinct aptamer ground-state tertiary architectures, exemplifying a new mode of ligand-dependent RNA regulation. PMID:28719589

  1. 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.

  2. What a difference a 5f element makes: trivalent and tetravalent uranium halide complexes supported by one and two bis[2-(diisopropylphosphino)-4-methylphenyl]amido (PNP) ligands.

    Science.gov (United States)

    Cantat, Thibault; Scott, Brian L; Morris, David E; Kiplinger, Jaqueline L

    2009-03-02

    The coordination behavior of the bis[2-(diisopropylphosphino)-4-methylphenyl]amido ligand (PNP) toward UI3(THF)4 and UCl4 has been investigated to access new uranium(III) and uranium(IV) halide complexes supported by one and two PNP ligands. The reaction between (PNP)K (6) and 1 equiv of UI3(THF)4 afforded the trivalent halide complex (PNP)UI2(4-tBu-pyridine)2 (7) in the presence of 4-tert-butylpyridine. The same reaction carried out with UCl4 and no donor ligand gave [(PNP)UCl3]2 (8), in which the uranium coordination sphere in the (PNP)UCl3 unit is completed by a bridging chloride ligand. When UCl4 is reacted with 1 equiv (PNP)K (6) in the presence of THF, trimethylphosphine oxide (TMPO), or triphenylphosphineoxide (TPPO), the tetravalent halide complexes (PNP)UCl3(THF) (9), (PNP)UCl3(TMPO)2 (10), and (PNP)UCl3(TPPO) (11), respectively, are formed in excellent yields. The bis(PNP) complexes of uranium(III), (PNP)2UI (12), and uranium(IV), (PNP)2UCl2 (13), were easily isolated from the analogous reactions between 2 equiv of 6 and UI3(THF)4 or UCl4, respectively. Complexes 12 and 13 represent the first examples of complexes featuring two PNP ligands coordinated to a single metal center. Complexes 7-13 have been characterized by single-crystal X-ray diffraction and 1H and 31P NMR spectroscopy. The X-ray structures demonstrate the ability of the PNP ligand to adopt new coordination modes upon coordination to uranium. The PNP ligand can adopt both pseudo-meridional and pseudo-facial geometries when it is kappa3-(P,N,P) coordinated, depending on the steric demand at the uranium metal center. Additionally, its hemilabile character was demonstrated with an unusual kappa2-(P,N) coordination mode that is maintained in both the solid-state and in solution. Comparison of the structures of the mono(PNP) and bis(PNP) complexes 7, 9, 11-13 with their respective C5Me5 analogues 1-4 undoubtedly show that a more sterically congested environment is provided by the PNP ligand. The

  3. Valence states of cobalt and crystal structure peculiarities of solid solution YBa2Cu3-xCoxO6+σ

    International Nuclear Information System (INIS)

    Voronin, V.I.; Goshchinskij, B.N.; Mitberg, Eh.B.; Leonidov, I.A.; Kozhevnikov, V.L.

    2000-01-01

    Crystal structure of solid solution YBa 2 Cu 3-x Co x O 6+σ , where x = 0.2, 0.4, 0.6 and 0.8, is studied by the method of powder neutron diffraction. Charge states of the cation are calculated using the interatomic distances obtained. It is shown that cobalt in Cu1 position has valency 3 + and octahedral coordination at x = 0.2 and 0.4. Increase in doping degree involves both transition of a portion of cobalt ions in the positions mentioned to the state with valence 4 + and tetrahedral coordination and partial substitution of copper in Cu2 position [ru

  4. Structure of the sporulation histidine kinase inhibitor Sda from Bacillus subtilis and insights into its solution state

    Energy Technology Data Exchange (ETDEWEB)

    Jacques, David A.; Streamer, Margaret [School of Molecular and Microbial Biosciences, University of Sydney (Australia); Rowland, Susan L.; King, Glenn F. [Institute of Molecular Biology, University of Queensland (Australia); Guss, J. Mitchell; Trewhella, Jill; Langley, David B., E-mail: d.langley@usyd.edu.au [School of Molecular and Microbial Biosciences, University of Sydney (Australia)

    2009-06-01

    The crystal structure of Sda, a DNA-replication/damage checkpoint inhibitor of sporulation in B. subtilis, has been solved via the MAD method. The subunit arrangement in the crystal has enabled a reappraisal of previous biophysical data, resulting in a new model for the behaviour of the protein in solution. The crystal structure of the DNA-damage checkpoint inhibitor of sporulation, Sda, from Bacillus subtilis, has been solved by the MAD technique using selenomethionine-substituted protein. The structure closely resembles that previously solved by NMR, as well as the structure of a homologue from Geobacillus stearothermophilus solved in complex with the histidine kinase KinB. The structure contains three molecules in the asymmetric unit. The unusual trimeric arrangement, which lacks simple internal symmetry, appears to be preserved in solution based on an essentially ideal fit to previously acquired scattering data for Sda in solution. This interpretation contradicts previous findings that Sda was monomeric or dimeric in solution. This study demonstrates the difficulties that can be associated with the characterization of small proteins and the value of combining multiple biophysical techniques. It also emphasizes the importance of understanding the physical principles behind these techniques and therefore their limitations.

  5. Steady-state solution of the semi-empirical diffusion equation for area sources. [air pollution studies

    Science.gov (United States)

    Lebedeff, S. A.; Hameed, S.

    1975-01-01

    The problem investigated can be solved exactly in a simple manner if the equations are written in terms of a similarity variable. The exact solution is used to explore two questions of interest in the modelling of urban air pollution, taking into account the distribution of surface concentration downwind of an area source and the distribution of concentration with height.

  6. Marriage, Abortion, or Unwed Motherhood? How Women Evaluate Alternative Solutions to Premarital Pregnancies in Japan and the United States

    Science.gov (United States)

    Hertog, Ekaterina; Iwasawa, Miho

    2011-01-01

    In this article, the authors argue that to understand the very low incidence of outside-of-marriage childbearing in contemporary Japan one needs to take into account perceptions of all possible solutions to a premarital pregnancy: marriage, abortion, and childbearing outside wedlock. To demonstrate the particular impact of these perceptions in…

  7. Steric and electronic effects of 1,3-disubstituted cyclopentadienyl ligands on metallocene derivatives of Cerium, Titanium, Manganese, and Iron

    Energy Technology Data Exchange (ETDEWEB)

    Sofield, Chadwick Dean [Univ. of California, Berkeley, CA (United States)

    2000-05-01

    Sterically demanding 1,3-disubstituted cyclopentadienyl ligands were used to modify the physical properties of the corresponding metallocenes. Sterically demanding ligands provided kinetic stabilization for trivalent cerium compounds. Tris(di-t-butylcyclopentadienyl)cerium was prepared and anion competition between halides and cyclopentadienyl groups which had complicated synthesis of the tris(cyclopentadienyl)compound was qualitatively examined. Bis(di-t-butylcyclopentadienyl)cerium methyl was prepared and its rate of decomposition, by ligand redistribution, to tris(di-t-butylcyclopentadienyl)cerium was shown to be slower than the corresponding rate for less sterically demanding ligands. Asymmetrically substituted ligands provided a symmetry label for examination of chemical exchange processes. Tris[trimethylsilyl(t-butyl)cyclopentadienyl]cerium was prepared and the rate of interconversion between the C1 and C3 isomers was examined. The enthalpy difference between the two distereomers is 7.0 kJ/mol. The sterically demanding cyclopentadienyl ligands ansa-di-t-butylcyclopentadiene (Me2Si[(Me3C)2C5H3]2), ansa-bis(trimethylsilyl)cyclopentadiene (Me2Si[(Me3Si)2C5H3]2) and tetra-t-butylfulvalene and metallocene derivatives of the ligands were prepared and their structures were examined by single crystal X-ray crystallography. The effect that substituents on the cyclopentadienyl ring have on the pi-electron system of the ligand was examined through interaction between ligand and metal orbitals. A series of 1,3-disubstituted manganocenes was prepared and their electronic states were determined by solid-state magnetic susceptibility, electron paramagnetic resonance, X-ray crystallography, and variable temperature UV-vis spectroscopy. Spin-equilibria in [(Me3C)2C5H3]2Mn and [(Me3

  8. Effect of molecular weight on radiation chemical degradation yield of chain scission of γ-irradiated chitosan in solid state and in aqueous solution

    International Nuclear Information System (INIS)

    Tahtat, Djamel; Mahlous, Mohamed; Benamer, Samah; Nacer Khodja, Assia; Larbi Youcef, Souad

    2012-01-01

    Chitosan A 1 , A 2 and A 3 with molecular weight of 471, 207 and 100 kDa respectively, produced from squid pen chitin was degraded by gamma rays in the solid state and in aqueous solution with various doses in air at ambient temperature. Effect of molecular weight on radiation chemical degradation yield of chain scission and degradation rate constants of γ-irradiated chitosan in solid state and in aqueous solution was investigated. The radiation chemical degradation yield G (s) and degradation rate values were calculated. The molecular weight changes were monitored by capillary viscometry method and the chemical structure changes were followed by UV analysis. The results showed that, the degradation of chitosan was faster in solution, than in solid state. The values of G (s) in solid state and in aqueous solution were respectively 1.1×10 −8 mol/J and 0.074×10 −7 mol/J for A 1 , 4.42×10 −8 mol/J and 0.28×10 −7 mol/J for A 2 and 6.08×10 −8 mol/J and 0.38×10 −7 mol/J for A 3 . Degradation rate constants values ranged from 0.41×10 −5 to 2.1×10 −5 kGy −1 in solid state, whereas in solution they ranged from 13×10 −5 to 68×10 −5 kGy −1 . The chitosan A 3 was more sensitive to radiolysis than A 1 and A 2 . The chain scission yield, G (s) and degradation rate constants seems to be greatly influenced by the initial molecular weight of the chitosan. Structural changes in irradiated chitosan are revealed by the apparition of absorption peaks at 261 and 295 nm, which could be attributed to the formation of carbonyl groups. In both conditions the peak intensity was higher in chitosan A 3 than in A 1 and A 2 , the oxidative products decreased with increasing molecular weight of chitosan. - Highlights: ► We investigated the effects of MW on G (s) value of γ-irradiated chitosan in solid and aqueous state. ► Chitosan with low molecular weight was more sensitive to radiolysis than high molecular weight. ► G (s) value and degradation rate

  9. Speciation of the oxidation states of plutonium in aqueous solutions by UV/Vis spectroscopy, CE-ICP-MS and CE-RIMS

    International Nuclear Information System (INIS)

    Buerger, S.; Banik, N.L.; Buda, R.A.; Kratz, J.V.; Kuczewski, B.; Trautmann, N.

    2007-01-01

    For the speciation of the plutonium oxidation states in aqueous solutions, the online coupling of capillary electrophoresis (CE) with inductively coupled plasma mass spectrometry (ICP-MS) has been developed. Depending on the radius/electrical charge ratio, the oxidation states III, IV, V, and VI of plutonium are separated by CE, based on the different migration times through the capillary and are detected by ICP-MS. The detection limit is 20 ppb, i.e. 10 9 -10 10 atoms (10 -12 -10 -13 g) for one oxidation state with an uncertainty of the reproducibility of the migration times of ≤ 1% and ≤ 5% for the peak area. The redox kinetics of the different plutonium oxidation states in the presence of humic substances (humic and fulvic acid) have been studied. A relatively rapid reduction of Pu(VI) (10 to 1000 h) in contact with Gorleben fulvic or Aldrich humic acid could be observed, depending on the pH of the solution. Furthermore, at pH=1, a reduction to Pu(III) and Pu(IV) in a mixture of all four oxidation states in contact with Gorleben fulvic acid after one month has been observed. In order to improve the sensitivity of the CE method, the offline coupling of CE to resonance ionization mass spectrometry (RIMS) has been explored. First applications of this new speciation method are presented. (orig.)

  10. Spectroscopic study of cadmium (II) complexes with heterocyclic dithiocarbamate ligands

    International Nuclear Information System (INIS)

    Garcia-Fontan, S.; Rodriguez-Seoane, P.; Casas, J.S.; Sordo, J.; Jones, M.M.

    1993-01-01

    Cadmium(II) dithiocarbamates [Cd(dtc) 2 ] (dtc=4-carboxamidopiperidine-1-carbodithioate, morpholine-1-carbodithioate or 4-(2-hydroxyethyl)piperazine-1-carbodithioate) and [Cd(dtc) 2 ].H 2 O (dtc=4-hydroxypiperidine-1-carbodithioate} have been prepared and characterized by thermal analysis and IR and NMR ( 13 C, 113 Cd) spectrometry. Two of these ligands have previously been shown capable of removing cadmium from its aged in vivo storage sites. The use of solid state 13 C NMR measurements to establish the coordination mode of the dithiocarbomate ligands is also examined and the difficulties which arise are discussed. (orig.)

  11. Crystallization of protein–ligand complexes

    International Nuclear Information System (INIS)

    Hassell, Anne M.; An, Gang; Bledsoe, Randy K.; Bynum, Jane M.; Carter, H. Luke III; Deng, Su-Jun J.; Gampe, Robert T.; Grisard, Tamara E.; Madauss, Kevin P.; Nolte, Robert T.; Rocque, Warren J.; Wang, Liping; Weaver, Kurt L.; Williams, Shawn P.; Wisely, G. Bruce; Xu, Robert; Shewchuk, Lisa M.

    2007-01-01

    Methods presented for growing protein–ligand complexes fall into the categories of co-expression of the protein with the ligands of interest, use of the ligands during protein purification, cocrystallization and soaking the ligands into existing crystals. Obtaining diffraction-quality crystals has long been a bottleneck in solving the three-dimensional structures of proteins. Often proteins may be stabilized when they are complexed with a substrate, nucleic acid, cofactor or small molecule. These ligands, on the other hand, have the potential to induce significant conformational changes to the protein and ab initio screening may be required to find a new crystal form. This paper presents an overview of strategies in the following areas for obtaining crystals of protein–ligand complexes: (i) co-expression of the protein with the ligands of interest, (ii) use of the ligands during protein purification, (iii) cocrystallization and (iv) soaks

  12. Equilibrium studies on mixed ligand complexes of some tripositive rare earth ions

    International Nuclear Information System (INIS)

    Vimal, Rashmi; Singh, Mamta; Ram Nayan

    1996-01-01

    Interaction of the rare earth ions, La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ and Eu 3+ with the pair of ligands 1-amino-2-naphthol-4-sulphonic acid (an, H 2 A) and o-aminophenol (ap, HB) have been studied in aqueous solution at 25 degC (μ=0.1 M KNO 3 /NaCl). Equilibrium constants of the reactions involving the formations of the mixed ligand species MAB, MA 2 B 2- , MB 2 A - (M = metal ion) and the binary complexes containing up to three ligand molecules have been evaluated from the pH-metric data, and coordinating behaviour of the ligands in the formation of the mixed ligand complexes has been discussed. (author). 10 refs., 1 tab., 1 fig

  13. Surface-Bound Ligands Modulate Chemoselectivity and Activity of a Bimetallic Nanoparticle Catalyst

    KAUST Repository

    Vu, Khanh B.

    2015-04-03

    "Naked" metal nanoparticles (NPs) are thermodynamically and kinetically unstable in solution. Ligands, surfactants, or polymers, which adsorb at a particle\\'s surface, can be used to stabilize NPs; however, such a mode of stabilization is undesirable for catalytic applications because the adsorbates block the surface active sites. The catalytic activity and the stability of NPs are usually inversely correlated. Here, we describe an example of a bimetallic (PtFe) NP catalyst stabilized by carboxylate surface ligands that bind preferentially to one of the metals (Fe). NPs stabilized by fluorous ligands were found to be remarkably competent in catalyzing the hydrogenation of cinnamaldehyde; NPs stabilized by hydrocarbon ligands were significantly less active. The chain length of the fluorous ligands played a key role in determining the chemoselectivity of the FePt NP catalysts. (Chemical Presented). © 2015 American Chemical Society.

  14. The influences of sensitivity of ligand in determination of fluors with LaF3

    International Nuclear Information System (INIS)

    Muzakky; Lahagu, F.; Djawahiri, H.M.; Susiaturi, E.

    1996-01-01

    The influences of acetate and carbonate ligand as a binder of uranium in uranium-tetra fluoride solution, with 0,1 M HNO 3 acid condition was been studied. The aim of binding is to looses of uranium from UO 2 (F 4 ) 2- compound, so the free of fluoride were able detected with LaF 3 membrane electrode on potentiometric method. Base on the free of Fluoride, acetate ligand was more sensitive than carbonate ligand. The addition method was able to prevented influent of HF species in high acidity was realized. The method was use to determination of Fluoride in C oncentrated Uranium , and yield are 1,215x10 -5 M±1,957x10 -4 in acetate ligand and 3,957x10 -5 M±2,57x10 -4 in carbonate ligand. (author)

  15. Polycomplexes of Hyaluronic Acid and Borates in a Solid State and Solution: Synthesis, Characterization and Perspectives of Application in Boron Neutron Capture Therapy

    Directory of Open Access Journals (Sweden)

    Alexander N. Zelenetskii

    2018-02-01

    Full Text Available In this report, we propose a new polyborate fragment synthesis strategy along the whole chain of the polysaccharide hyaluronic acid (HA to produce boron neutron capture therapy (BNCT compounds. Under high pressure and deformatory solid-state conditions, polymolecular system formation takes place due to association of phase-specific transition components into a more or less distinct microscopic organization. Fourier transform infrared (FTIR spectroscopy shows that HA and polyborates form a network of cyclic polychelate complexes. HA acts as a multidentate ligand using carboxylic and hydroxyl proton donor groups to link oxygen atoms in B–O–B bonds and borate-anions B–O(−: O–H···O, O–H···(−O. With free electron pairs in heteroatoms –O(:···B, –N(:···B, HA can act simultaneously as an electron donor. Nuclear magnetic resonance (NMR with 13C and 1H reveals a preserved complex interaction after both solubilizing and attenuating the HA-polyborate system. Stability of the product in water, low cost, ease of synthesis and scalability of manufacturing indicate that HA-polyborate complexes might have advantages over current chemotherapeutic approaches in creating therapeutic agents for BNCT.

  16. Erbium(III) in aqueous solution: an ab initio molecular dynamics study.

    Science.gov (United States)

    Canaval, Lorenz R; Sakwarathorn, Theerathad; Rode, Bernd M; Messner, Christoph B; Lutz, Oliver M D; Bonn, Günther K

    2013-12-05

    Structural and dynamical properties of the erbium(III) ion in water have been obtained by means of ab initio quantum mechanical charge field molecular dynamics (QMCF-MD) simulations for the ground state and an excited state. The quality of the simulations has been monitored by recording UV/vis and Raman spectra of dilute solutions of ErCl3 and Er(NO3)3 in water and by comparison with EXAFS data from literature. Slight deviations between these data can be mainly attributed to relativistic effects, which are not sufficiently considered by the methodological framework. In both simulations, a mixture of coordination numbers eight and nine and a ligand exchange on the picosecond range are observed. The strength of the Er-ligand bond is considerably lower than that of trivalent transition metal ions but higher than that for La(III) and Ce(III) in aqueous solution. The main difference between ground state and excited state is the ligand exchange rate of the first shell. The second hydration shell is stable in both cases but with significantly different properties.

  17. -Pincer Ligand Family through Ligand Post-Modification

    KAUST Repository

    Huang, Mei-Hui; Hu, Jinsong; Huang, Kuo-Wei

    2017-01-01

    A series of air-stable nickel complexes containing triazine-based PN3P-pincer ligands were synthesized and fully characterized. Complex 3 contains a de-aromatized central triazine ring from the deprotonation of one of the N–H arms. With a post-modification strategy, the Me-PN3P*NiCl complex (3) could be converted into a new class of diimine–traizine PN3P-pincer nickel complexes.

  18. -Pincer Ligand Family through Ligand Post-Modification

    KAUST Repository

    Huang, Mei-Hui

    2017-10-02

    A series of air-stable nickel complexes containing triazine-based PN3P-pincer ligands were synthesized and fully characterized. Complex 3 contains a de-aromatized central triazine ring from the deprotonation of one of the N–H arms. With a post-modification strategy, the Me-PN3P*NiCl complex (3) could be converted into a new class of diimine–traizine PN3P-pincer nickel complexes.

  19. Aqueous Solution Chemistry of Plutonium

    Energy Technology Data Exchange (ETDEWEB)

    Clark, David L. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2014-01-28

    Things I have learned working with plutonium: Chemistry of plutonium is complex; Redox equilibria make Pu solution chemistry particularly challenging in the absence of complexing ligands; Understanding this behavior is key to successful Pu chemistry experiments; There is no suitable chemical analog for plutonium.

  20. Engineering solutions to the long-term stabilization and isolation of uranium mill tailings in the United States

    International Nuclear Information System (INIS)

    Sanders, D.R.; Lommler, J.C.

    1995-01-01

    Engineering solutions to the safe and environmentally protective disposal and isolation of uranium mill tailings in the US include many factors. Cover design, materials selection, civil engineering, erosive forces, and cost effectiveness are only a few of those factors described in this paper. The systems approach to the engineering solutions employed in the US is described, with emphasis on the standards prescribed for the Uranium Mill Tailings Remedial Action Project. Stabilization and isolation of the tailings from humans and the environment are the primary goals of the US uranium mill tailings control standards. The performance of cover designs with respect to water infiltration, radon exhalation, geotechnical stability, erosion protection, human and animal intrusion prevention, and longevity are addressed. The need for and frequency of surveillance efforts to ensure continued disposal system performance are also assessed

  1. A grand unified model for liganded gold clusters

    Science.gov (United States)

    Xu, Wen Wu; Zhu, Beien; Zeng, Xiao Cheng; Gao, Yi

    2016-12-01

    A grand unified model (GUM) is developed to achieve fundamental understanding of rich structures of all 71 liganded gold clusters reported to date. Inspired by the quark model by which composite particles (for example, protons and neutrons) are formed by combining three quarks (or flavours), here gold atoms are assigned three `flavours' (namely, bottom, middle and top) to represent three possible valence states. The `composite particles' in GUM are categorized into two groups: variants of triangular elementary block Au3(2e) and tetrahedral elementary block Au4(2e), all satisfying the duet rule (2e) of the valence shell, akin to the octet rule in general chemistry. The elementary blocks, when packed together, form the cores of liganded gold clusters. With the GUM, structures of 71 liganded gold clusters and their growth mechanism can be deciphered altogether. Although GUM is a predictive heuristic and may not be necessarily reflective of the actual electronic structure, several highly stable liganded gold clusters are predicted, thereby offering GUM-guided synthesis of liganded gold clusters by design.

  2. Reactivity of halide and pseudohalide ligands

    International Nuclear Information System (INIS)

    Kukushkin, Yu.N.

    1987-01-01

    Reactivity of halide and pseudohalide (cyanide, azide, thiocyanate, cyanate) ligands tending to form bridge bonds in transition metal (Re, Mo, W) complexes is considered. Complexes where transition metal salts are ligands of other, complex-forming ion, are described. Transformation of innerspheric pseudohalide ligands is an important way of directed synthesis of these metal coordination compounds

  3. Phase Behaviour and Miscibility Studies of Collagen/Silk Fibroin Macromolecular System in Dilute Solutions and Solid State.

    Science.gov (United States)

    Ghaeli, Ima; de Moraes, Mariana A; Beppu, Marisa M; Lewandowska, Katarzyna; Sionkowska, Alina; Ferreira-da-Silva, Frederico; Ferraz, Maria P; Monteiro, Fernando J

    2017-08-18

    Miscibility is an important issue in biopolymer blends for analysis of the behavior of polymer pairs through the detection of phase separation and improvement of the mechanical and physical properties of the blend. This study presents the formulation of a stable and one-phase mixture of collagen and regenerated silk fibroin (RSF), with the highest miscibility ratio between these two macromolecules, through inducing electrostatic interactions, using salt ions. For this aim, a ternary phase diagram was experimentally built for the mixtures, based on observations of phase behavior of blend solutions with various ratios. The miscibility behavior of the blend solutions in the miscible zones of the phase diagram was confirmed quantitatively by viscosimetric measurements. Assessing the effects of biopolymer mixing ratio and salt ions, before and after dialysis of blend solutions, revealed the importance of ion-specific interactions in the formation of coacervate-based materials containing collagen and RSF blends that can be used in pharmaceutical, drug delivery, and biomedical applications. Moreover, the conformational change of silk fibroin from random coil to beta sheet, in solution and in the final solid films, was detected by circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR), respectively. Scanning electron microscopy (SEM) exhibited alterations of surface morphology for the biocomposite films with different ratios. Surface contact angle measurement illustrated different hydrophobic properties for the blended film surfaces. Differential scanning calorimetry (DSC) showed that the formation of the beta sheet structure of silk fibroin enhances the thermal stability of the final blend films. Therefore, the novel method presented in this study resulted in the formation of biocomposite films whose physico-chemical properties can be tuned by silk fibroin conformational changes by applying different component mixing ratios.

  4. Exact solution of the relativistic Coulomb problem for two-particle bound states in the quasipotential approach

    International Nuclear Information System (INIS)

    Kapshay, V.N.; Skachkov, N.B.

    1979-01-01

    A composite system of two relativistic particles is studied on the basis of the Kadyshevsky quasipotential equation, in which the ''Coulomb'' potential is taken in the form of a propagator of the massless-scalar-particle exchange. The obtained exact solutions to this equation are shown to be a geometrical generalization of nonrelativistic Coulomb wave functions in the sense of change of the Euclidean geometry of momentum space to the Lobachevsky geometry

  5. Applications of alternating direction methods to the solution of the heat conduction equation, with source, and in transient state

    International Nuclear Information System (INIS)

    Oliveira Barroso, A.C. de; Alvim, A.C.M.; Gebrin, A.N.; Santos, R.S. dos

    1981-01-01

    Various types and variants of alternating direction methods. (ADM), were applied to the solution of the time-dependent heat conduction equation, with source, in regions with axial simmetry. Among the basic ADM's, the alternating direction explicit was the one which performed better. An exponential transformation coupled to the ADE seems to be the variant with greater potential, especially if used with a variable time step scheme. (Author) [pt

  6. Renewable Energy Prices in State-Level Feed-in Tariffs: Federal Law Constraints and Possible Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Hempling, S.; Elefant, C.; Cory, K.; Porter, K.

    2010-01-01

    State legislatures and state utility commissions trying to attract renewable energy projects are considering feed-in tariffs, which obligate retail utilities to purchase electricity from renewable producers under standard arrangements specifying prices, terms, and conditions. The use of feed-in tariffs simplifies the purchase process, provides revenue certainty to generators, and reduces the cost of financing generating projects. However, some argue that federal law--including the Public Utility Regulatory Policies Act of 1978 (PURPA) and the Federal Power Act of 1935 (FPA)--constrain state-level feed-in tariffs. This report seeks to reduce the legal uncertainties for states contemplating feed-in tariffs by explaining the constraints imposed by federal statutes. It describes the federal constraints, identifies transaction categories that are free of those constraints, and offers ways for state and federal policymakers to interpret or modify existing law to remove or reduce these constraints. This report proposes ways to revise these federal statutes. It creates a broad working definition of a state-level feed-in tariff. Given this definition, this report concludes there are paths to non-preempted, state-level feed-in tariffs under current federal law.

  7. Experience in safety review of design solutions of the state-of-the-art WWER-type NPPs

    International Nuclear Information System (INIS)

    Khamaza, A.A.

    2015-01-01

    The experience of the Federal Budget Institution of the Scientific and Technical Center for Nuclear and Radiation Safety in the field of expertise of the safety rationales for nuclear power plants with WWER-type reactors of new projects is disclosed. In determining the priority, in addition to the necessary time and financial resources, it also took into account the extent to which these activities significantly affect the completeness of the implementation of levels of defense in depth related to the management of beyond-design-basis accidents, including severe ones. And also, what impact does this or that measure have on reducing the likelihood of the onset of severe radiation effects. When examining the safety justification for new design solutions (including for nuclear power plants with a reactor type WWER), it is advisable to adhere to the following approach: during the examination it is necessary to study the experience in the country and the world related to the proposed new design solutions; It is preferable to take advantage of the differential approach to assessing various aspects related to nuclear and radiation safety. The result of the examination of the justification for new design solutions may be recommendations on the development of existing regulatory documents or development of the Regulatory Authority [ru

  8. Application of COMSOL in the solution of the neutron diffusion equations for fast nuclear reactors in stationary state

    International Nuclear Information System (INIS)

    Silva A, L.; Del Valle G, E.

    2012-10-01

    This work shows an application of the program COMSOL Multi physics Ver. 4.2a in the solution of the neutron diffusion equations for several energy groups in nuclear reactors whose core is formed by assemblies of hexagonal transversal cut as is the cas of fast reactors. A reference problem of 4 energy groups is described of which takes the cross sections which are processed by means of a program that prepares the definition of the constants utilized in COMSOL for the generic partial differential equations that this uses. The considered solution domain is the sixth part of the core which is applied frontier conditions of reflection and incoming flux zero. The discretization mesh is elaborated in automatic way by COMSOL and the solution method is one of finite elements of Lagrange grade two. The reference problem is known as the Knk with and without control rod which led to propose the calculation of the effective multiplication factor in function of the control rod fraction from a value 0 (completely inserted control rod) until the value 1 (completely extracted control rod). Besides this the reactivity was determined as well as the change of this in function of control rod fraction. The neutrons scalar flux for each energy group with and without control rod is proportioned. The reported results show a behavior similar to the one reported in other works but using the discreet ordinates S 2 approximation. (Author)

  9. Surface ligands affect photoinduced modulation of the quantum dots optical performance

    Science.gov (United States)

    Krivenkov, Victor A.; Samokhvalov, Pavel S.; Linkov, Pavel A.; Solovyeva, Daria O.; Kotkovskii, Gennadii E.; Chistyakov, Alexander A.; Nabiev, Igor

    2014-05-01

    Changes of optical properties of the solutions of CdSe/ZnS quantum dots (QDs) covered with the trioctylphosphine oxide (TOPO) ligands under the pulsed ultraviolet (UV) laser irradiation are observed. The fluorescence quantum yield (QY) of QDs decreases by more than an order of magnitude when the radiation dose approaches 2 × 10-15 J per particle. This process is accompanied by a blue shift of both fluorescence and the first excitonic absorption peaks. The fluorescence quenching becomes less pronounced when the overall TOPO content in the solution is increased. When ТОРО ligands are replaced with n-hexadecylamine (HDA), QY and spectral properties are not changed at the same irradiation conditions. We assume that the above changes of the optical properties are associated with photooxidation of TOPO ligands by excited QD. Such process is less probable for the HDA ligand due to its different energy structure.

  10. Exploring a United States Maize Cellulose Biofuel Scenario Using an Integrated Energy and Agricultural Markets Solution Approach

    Science.gov (United States)

    Biofuel feedstock production in the United States (US) is an emergent environmental nutrient management issue, whose exploration can benefit from a multi-scale and multimedia systems modeling approach that explicitly addresses diverging stakeholder interests. In the present anal...

  11. 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.

  12. Numerical Solutions of One Reduced Bethe-Salpeter Equation for the Coulombic Bound States Composed of Virtual Constituents

    Science.gov (United States)

    Chen, Jiao-Kai

    2018-04-01

    We present one reduction of the Bethe-Salpeter equation for the bound states composed of two off-mass-shell constituents. Both the relativistic effects and the virtuality effects can be considered in the obtained spinless virtuality distribution equation. The eigenvalues of the spinless virtuality distribution equation are perturbatively calculated and the bound states e+e-, μ+μ-, τ+τ-, μ+e-, and τ+e- are discussed.

  13. Rich Ground State Chemical Ordering in Nanoparticles: Exact Solution of a Model for Ag-Au Clusters

    DEFF Research Database (Denmark)

    Larsen, Peter Mahler; Jacobsen, Karsten Wedel; Schiøtz, Jakob

    2018-01-01

    We show that nanoparticles can have very rich ground state chemical order. This is illustrated by determining the chemical ordering of Ag-Au 309-atom Mackay icosahedral nanoparticles. The energy of the nanoparticles is described using a cluster expansion model, and a Mixed Integer Programming (MIP......) approach is used to find the exact ground state configurations for all stoichiometries. The chemical ordering varies widely between the different stoichiometries, and display a rich zoo of structures with non-trivial ordering....

  14. Ligand-regulated peptide aptamers.

    Science.gov (United States)

    Miller, Russell A

    2009-01-01

    The peptide aptamer approach employs high-throughput selection to identify members of a randomized peptide library displayed from a scaffold protein by virtue of their interaction with a target molecule. Extending this approach, we have developed a peptide aptamer scaffold protein that can impart small-molecule control over the aptamer-target interaction. This ligand-regulated peptide (LiRP) scaffold, consisting of the protein domains FKBP12, FRB, and GST, binds to the cell-permeable small-molecule rapamycin and the binding of this molecule can prevent the interaction of the randomizable linker region connecting FKBP12 with FRB. Here we present a detailed protocol for the creation of a peptide aptamer plasmid library, selection of peptide aptamers using the LiRP scaffold in a yeast two-hybrid system, and the screening of those peptide aptamers for a ligand-regulated interaction.

  15. Ligand binding by PDZ domains

    DEFF Research Database (Denmark)

    Chi, Celestine N.; Bach, Anders; Strømgaard, Kristian

    2012-01-01

    , for example, are particularly rich in these domains. The general function of PDZ domains is to bring proteins together within the appropriate cellular compartment, thereby facilitating scaffolding, signaling, and trafficking events. The many functions of PDZ domains under normal physiological as well...... as pathological conditions have been reviewed recently. In this review, we focus on the molecular details of how PDZ domains bind their protein ligands and their potential as drug targets in this context....

  16. Bitopic Ligands and Metastable Binding Sites

    DEFF Research Database (Denmark)

    Fronik, Philipp; Gaiser, Birgit I; Sejer Pedersen, Daniel

    2017-01-01

    of orthosteric binding sites. Bitopic ligands have been employed to address the selectivity problem by combining (linking) an orthosteric ligand with an allosteric modulator, theoretically leading to high-affinity subtype selective ligands. However, it remains a challenge to identify suitable allosteric binding...... that have been reported to date, this type of bitopic ligands would be composed of two identical pharmacophores. Herein, we outline the concept of bitopic ligands, review metastable binding sites, and discuss their potential as a new source of allosteric binding sites....

  17. Radioiodinated ligands for dopamine receptors

    International Nuclear Information System (INIS)

    Kung, H.F.

    1994-01-01

    The dopamine receptor system is important for normal brain function; it is also the apparent action site for various neuroleptic drugs for the treatment of schizophrenia and other metal disorders. In the past few years radioiodinated ligands for single photon emission tomography (SPECT) have been successfully developed and tested in humans: [ 123 I]TISCH for D1 dopamine receptors; [ 123 I]IBZM, epidepride, IBF and FIDA2, four iodobenzamide derivatives, for D2/D3 dopamine receptors. In addition, [ 123 I]β-CIT (RTI-55) and IPT, cocaine derivatives, for the dopamine reuptake site are potentially useful for diagnosis of loss of dopamine neurons. The first iodinated ligand, (R)trans-7-OH-PIPAT, for D3 dopamine receptors, was synthesized and characterized with cloned cell lines (Spodoptera frugiperda, Sf9) expressing the D2 and D3 dopamine receptors and with rat basal forebrain membrane preparations. Most of the known iodobenzamides displayed similar potency in binding to both D2 and D3 dopamine receptors expressed in the cell lines. Initial studies appear to suggest that by fine tuning the structures it may be possible to develop agents specific for D2 and D3 dopamine receptors. It is important to investigate D2/D3 selectivity for this series of potent ligands

  18. Solution of non-steady-state substrate concentration in the action of biosensor response at mixed enzyme kinetics

    Science.gov (United States)

    Senthamarai, R.; Jana Ranjani, R.

    2018-04-01

    In this paper, a mathematical model of an amperometric biosensor at mixed enzyme kinetics and diffusion limitation in the case of substrate inhibition has been developed. The model is based on time dependent reaction diffusion equation containing a non -linear term related to non -Michaelis - Menten kinetics of the enzymatic reaction. Solution for the concentration of the substrate has been derived for all values of parameters using the homotopy perturbation method. All the approximate analytic expressions of substrate concentration are compared with simulation results using Scilab/Matlab program. Finally, we have given a satisfactory agreement between them.

  19. Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces.

    Science.gov (United States)

    Arai, Yuji; Fuller, C C

    2012-01-01

    Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na(2)SO(4) solutions to simulate the major chemical composition of U-contaminated groundwater (i.e., [SO(4)(2-)] ~13 mM L(-1)) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO(2)-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (carbonato U(VI) ternary surface species became more important. At 2% pCO(2), there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO(2) fluctuates between 1 and 2 pCO(2)%. Copyright © 2011 Elsevier Inc. All rights reserved.

  20. Atom states and interatomic interactions in complex perovskite-like oxides. 4. Spin state of nickel(2) atoms in LaCa0.5Sr0.5NixAl1-xO4 solid solutions

    International Nuclear Information System (INIS)

    Chezhina, N.V.; Kuznetsova, I.V.

    1995-01-01

    Solid solutions of LaCa 0.5 Sr 0.5 Ni x Al 1-x O 4 (0≤x≤0.10) have been synthesized and their magnetic susceptibility in the temperature range of 77-400 K has been studied. The change in the basic state of nickel atoms in case of partial substitution of calcium for strontium atoms has been studied. The change in the basic state of nickel atoms in case of partial substitution of calcium for strontium atoms has been studied, as well as the way it affects exchange interaction in a complex oxide. It is shown that the substitution results in increase of the degree of paramagnetic atoms aggregation in solid solution. 9 refs., 2 figs., 1 tab

  1. Trapping of palindromic ligands within native transthyretin prevents amyloid formation

    Science.gov (United States)

    Kolstoe, Simon E.; Mangione, Palma P.; Bellotti, Vittorio; Taylor, Graham W.; Tennent, Glenys A.; Deroo, Stéphanie; Morrison, Angus J.; Cobb, Alexander J. A.; Coyne, Anthony; McCammon, Margaret G.; Warner, Timothy D.; Mitchell, Jane; Gill, Raj; Smith, Martin D.; Ley, Steven V.; Robinson, Carol V.; Wood, Stephen P.; Pepys, Mark B.

    2010-01-01

    Transthyretin (TTR) amyloidosis is a fatal disease for which new therapeutic approaches are urgently needed. We have designed two palindromic ligands, 2,2'-(4,4'-(heptane-1,7-diylbis(oxy))bis(3,5-dichloro-4,1-phenylene)) bis(azanediyl)dibenzoic acid (mds84) and 2,2'-(4,4'-(undecane-1,11-diylbis(oxy))bis(3,5-dichloro-4,1-phenylene)) bis(azanediyl)dibenzoic acid (4ajm15), that are rapidly bound by native wild-type TTR in whole serum and even more avidly by amyloidogenic TTR variants. One to one stoichiometry, demonstrable in solution and by MS, was confirmed by X-ray crystallographic analysis showing simultaneous occupation of both T4 binding sites in each tetrameric TTR molecule by the pair of ligand head groups. Ligand binding by native TTR was irreversible under physiological conditions, and it stabilized the tetrameric assembly and inhibited amyloidogenic aggregation more potently than other known ligands. These superstabilizers are orally bioavailable and exhibit low inhibitory activity against cyclooxygenase (COX). They offer a promising platform for development of drugs to treat and prevent TTR amyloidosis. PMID:21059958

  2. The Colloidal Stabilization of Quantum Dots: Towards Manufacturable, Efficient Solution-Processed Solar Cells

    Science.gov (United States)

    Rollny, Lisa

    Understanding colloidal stabilization can influence the design of optoelectronic devices and enable improvements to their performance and stability. For photovoltaics, important characteristics of the active layer material are high conductivity along with a minimum of recombination centers. In order to capitalize on the benefits of solution-processed materials, it is important to minimize the number of processing steps: ideally, to achieve a low-cost solution, materials would be deposited using a single process step compatible with roll-to-roll manufacturing. Prior to this work, the highest-performing colloidal quantum dots (CQD) solar cells have relied on several deposition steps that are repeated in a layer-by-layer (LBL) fashion. The purpose of these process steps has been to remove the long insulating ligands used in synthesis and replace them with short ligands that allow electrical conduction. The large number of steps combined, typically implemented via spin coating, leads to inefficient materials utilization and fails to show a path to a manufacturable solution. In this work, the first CQD solar cells were designed, built, and characterized combining state-of-art performance with scalable manufacture. Firstly, I report the first automated CQD synthesis to result in CQDs that form high-performance CQD solar cells. I analyze the CQD synthesis and by separating it into two phases---nucleation and growth phase---my insights are used to create higher-quality CQDs exhibiting enhanced monodispersity. I then proceed to develop a CQD ink: a CQD solution ready for direct deposition to form a semiconducting film exhibiting low trap state density. In early trials the CQD ink showed only limited power conversion efficiencies of 2%. I designed a new ink strategy, which I term cleavable hemiketal ligands. This novel two-component ligand strategy enables the combination of colloidal stabilization (via this longer two-component ligand) and cleavability (enabling excellent

  3. Numerical solution of the state-delayed optimal control problems by a fast and accurate finite difference θ-method

    Science.gov (United States)

    Hajipour, Mojtaba; Jajarmi, Amin

    2018-02-01

    Using the Pontryagin's maximum principle for a time-delayed optimal control problem results in a system of coupled two-point boundary-value problems (BVPs) involving both time-advance and time-delay arguments. The analytical solution of this advance-delay two-point BVP is extremely difficult, if not impossible. This paper provides a discrete general form of the numerical solution for the derived advance-delay system by applying a finite difference θ-method. This method is also implemented for the infinite-time horizon time-delayed optimal control problems by using a piecewise version of the θ-method. A matrix formulation and the error analysis of the suggested technique are provided. The new scheme is accurate, fast and very effective for the optimal control of linear and nonlinear time-delay systems. Various types of finite- and infinite-time horizon problems are included to demonstrate the accuracy, validity and applicability of the new technique.

  4. Solubilities of gases in ionic liquids using a corresponding-states approach to Kirkwood-Buff solution theory

    DEFF Research Database (Denmark)

    Ellegaard, Martin Dela; Abildskov, Jens; O’Connell, John P.

    2011-01-01

    The solubilities of gases in ionic liquids and compressed liquid densities have been successfully described over a wide range of conditions using a reformulated corresponding-states formulation for direct correlation function integrals. In addition, comparisons with experimental data show reliabl...... prediction of ionic liquid characteristic properties from simple rules.......The solubilities of gases in ionic liquids and compressed liquid densities have been successfully described over a wide range of conditions using a reformulated corresponding-states formulation for direct correlation function integrals. In addition, comparisons with experimental data show reliable...

  5. Remediation of lead-contaminated soil with non-toxic biodegradable natural ligands extracted from soybean.

    Science.gov (United States)

    Lee, Yong-Woo; Kim, Chulsung

    2012-01-01

    Bench-scale soil washing studies were performed to evaluate the potential application of non-toxic, biodegradable extracted soybean-complexing ligands for the remediation of lead-contaminated soils. Results showed that, with extracted soybean-complexing ligands, lead solubility extensively increased when pH of the solution was higher than 6, and approximately 10% (500 mg/kg) of lead was removed from a rifle range soil. Two potential primary factors controlling the effectiveness of lead extraction from lead-contaminated soils with natural ligands are adsorption of extracted aqueous lead ions onto the ground soybean and the pH of the extraction solution. More complexing ligands were extracted from the ground soybean as the reaction pH increased. As a result, significantly higher lead extraction efficiency was observed under basic environments. In addition, less adsorption onto soybean was observed when the pH of the solution was higher than 7. Among two available Lewis base functional groups in the extracted soybean-complexing ligands such as carboxylate and the alpha-amino functional groups, the non-protonated alpha-amino functional groups may play an important role for the dissolution of lead from lead-contaminated soil through the formation of soluble lead--ligand complexes.

  6. Moessbauer studies of iron(III)-(indole-3-alkanoic acids) systems in frozen aqueous solutions

    International Nuclear Information System (INIS)

    Kovacs, K.; Kuzmann, E.; Homonnay, Z.; Szilagyi, P.A.; Vertes, A.; Kamnev, A.A.; Sharma, V.K.

    2005-01-01

    Moessbauer investigations of iron(III) salts in aqueous solutions in the presence of indole-3-alkanoic acid ligands are described. The measurements showed two parallel reactions between the ligands and ferric ions: a complex formation and a redox process. The oxidation process takes place in the ligands, and a part of Fe 3+ is reduced to Fe 2+ . (author)

  7. Study of actinide paramagnetism in solution

    International Nuclear Information System (INIS)

    Autillo, Matthieu

    2015-01-01

    The physiochemical properties of actinide (An) solutions are still difficult to explain, particularly the behavioral differences between An(III) and Ln(III). The study of actinide paramagnetic behavior may be a 'simple' method to analyze the electronic properties of actinide elements and to obtain information on the ligand-actinide interaction. The objective of this PhD thesis is to understand the paramagnetic properties of these elements by magnetic susceptibility measurements and chemical shift studies. Studies on actinide electronic properties at various oxidation states in solution were carried out by magnetic susceptibility measurements in solution according to the Evans method. Unlike Ln(III) elements, there is no specific theory describing the magnetic properties of these ions in solution. To obtain accurate data, the influence of experimental measurement technique and radioactivity of these elements was analyzed. Then, to describe the electronic structure of their low energy states, the experimental results were complemented with quantum chemical calculations from which the influence of the ligand field was studied. Finally, these interpretations were applied to better understand the variations in the magnetic properties of actinide cations in chloride and nitrate media. Information about ligand-actinide interactions may be determined from an NMR chemical shift study of actinide complexes. Indeed, modifications induced by a paramagnetic complex can be separated into two components. The first component, a Fermi contact contribution (δ_c) is related to the degree of covalency in coordination bonds with the actinide ions and the second, a dipolar contribution (δ_p_c) is related to the structure of the complex. The paramagnetic induced shift can be used only if we can isolate these two terms. To achieve this study on actinide elements, we chose to work with the complexes of dipicolinic acid (DPA). Firstly, to characterize the geometrical parameters, a

  8. Health Care Crossroads: What's the Right Solution? Putting Consumer-Driven Ideas to Work at Louisiana State University

    Science.gov (United States)

    Benedict, Forest; Guinn, Shayla

    2006-01-01

    Idling at the crossroads and faced with ever-increasing health care costs, the Louisiana State University System chose the road less traveled and instituted a consumer-driven benefits plan. In this article, the authors provide an overview of the consumer-driven programs LSU has adopted and how these programs have helped curb costs and improve the…

  9. Renewable Energy Prices in State-Level Feed-in Tariffs. Federal Law Constraints and Possible Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Hempling, Scott [National Regulatory Research Inst., Silver Spring, MD (United States); Elefant, Carolyn [Law Offices of Carolyn Elefant, Washington, DC (United States); Cory, Karlynn [National Renewable Energy Lab. (NREL), Golden, CO (United States); Porter, Kevin [Exeter Associates, Inc., Golden, CO (United States)

    2010-01-01

    This report details how state feed-in tariff (FIT) programs can be legally implemented and how they can comply with federal requirements. The report describes the federal constraints on FIT programs and identifies legal methods that are free of those constrains.

  10. A solution thermodynamics definition of the fiber saturation point and the derivation of a wood-water phase (state) diagram

    Science.gov (United States)

    Samuel L. Zelinka; Samuel V. Glass; Joseph E. Jakes; Donald S. Stone

    2016-01-01

    The fiber saturation point (FSP) is an important concept in wood– moisture relations that differentiates between the states of water in wood and has been discussed in the literature for over 100 years. Despite its importance and extensive study, the exact theoretical definition of the FSP and the operational definition (the correct way to measure the FSP) are still...

  11. Enhancing the Performance of CdSe/CdS Dot-in-Rod Light-Emitting Diodes via Surface Ligand Modification.

    Science.gov (United States)

    Rastogi, Prachi; Palazon, Francisco; Prato, Mirko; Di Stasio, Francesco; Krahne, Roman

    2018-02-14

    The surface ligands on colloidal nanocrystals (NCs) play an important role in the performance of NC-based optoelectronic devices such as photovoltaic cells, photodetectors, and light-emitting diodes (LEDs). On one hand, the NC emission depends critically on the passivation of the surface to minimize trap states that can provide nonradiative recombination channels. On the other hand, the electrical properties of NC films are dominated by the ligands that constitute the barriers for charge transport from one NC to its neighbor. Therefore, surface modifications via ligand exchange have been employed to improve the conductance of NC films. However, in LEDs, such surface modifications are more critical because of their possible detrimental effects on the emission properties. In this work, we study the role of surface ligand modifications on the optical and electrical properties of CdSe/CdS dot-in-rods (DiRs) in films and investigate their performance in all-solution-processed LEDs. The DiR films maintain high photoluminescence quantum yield, around 40-50%, and their electroluminescence in the LED preserves the excellent color purity of the photoluminescence. In the LEDs, the ligand exchange boosted the luminance, reaching a fourfold increase from 2200 cd/m 2 for native surfactants to 8500 cd/m 2 for the exchanged aminoethanethiol (AET) ligands. Moreover, the efficiency roll-off, operational stability, and shelf life are significantly improved, and the external quantum efficiency is modestly increased from 5.1 to 5.4%. We relate these improvements to the increased conductivity of the emissive layer and to the better charge balance of the electrically injected carriers. In this respect, we performed ultraviolet photoelectron spectroscopy (UPS) to obtain a deeper insight into the band alignment of the LED structure. The UPS data confirm similar flat-band offsets of the emitting layer to the electron- and hole-transport layers in the case of AET ligands, which translates to

  12. Ligand binding and crystal structures of the substrate-binding domain of the ABC transporter OpuA.

    Directory of Open Access Journals (Sweden)

    Justina C Wolters

    2010-04-01

    Full Text Available The ABC transporter OpuA from Lactococcus lactis transports glycine betaine upon activation by threshold values of ionic strength. In this study, the ligand binding characteristics of purified OpuA in a detergent-solubilized state and of its substrate-binding domain produced as soluble protein (OpuAC was characterized.The binding of glycine betaine to purified OpuA and OpuAC (K(D = 4-6 microM did not show any salt dependence or cooperative effects, in contrast to the transport activity. OpuAC is highly specific for glycine betaine and the related proline betaine. Other compatible solutes like proline and carnitine bound with affinities that were 3 to 4 orders of magnitude lower. The low affinity substrates were not noticeably transported by membrane-reconstituted OpuA. OpuAC was crystallized in an open (1.9 A and closed-liganded (2.3 A conformation. The binding pocket is formed by three tryptophans (Trp-prism coordinating the quaternary ammonium group of glycine betaine in the closed-liganded structure. Even though the binding site of OpuAC is identical to that of its B. subtilis homolog, the affinity for glycine betaine is 4-fold higher.Ionic strength did not affect substrate binding to OpuA, indicating that regulation of transport is not at the level of substrate binding, but rather at the level of translocation. The overlap between the crystal structures of OpuAC from L.lactis and B.subtilis, comprising the classical Trp-prism, show that the differences observed in the binding affinities originate from outside of the ligand binding site.

  13. A feasibility study of unconventional planar ligand spacers in chalcogenide nanocrystals.

    Science.gov (United States)

    Lukose, Binit; Clancy, Paulette

    2016-05-18

    The solar cell efficiency of chalcogenide nanocrystals (quantum dots) has been limited in the past by the insulation between neighboring quantum dots caused by intervening, often long-chain, aliphatic ligands. We have conducted a computationally based feasibility study to investigate the use of ultra-thin, planar, charge-conducting ligands as an alternative to traditional long passive ligands. Not only might these radically unconventional ligands decrease the mean distance between adjacent quantum dots, but, since they are charge-conducting, they have the potential to actively enhance charge migration. Our ab initio studies compare the binding energies, electronic energy gaps, and absorption characteristics for both conventional and unconventional ligands, such as phthalocyanines, porphyrins and coronene. This comparison identified these unconventional ligands with the exception of titanyl phthalocyanine, that bind to themselves more strongly than to the surface of the quantum dot, which is likely to be less desirable for enhancing charge transport. The distribution of finite energy levels of the bound system is sensitive to the ligand's binding site and the levels correspond to delocalized states. We also observed a trap state localized on a single Pb atom when a sulfur-containing phenyldithiocarbamate (PTC) ligand is attached to a slightly off-stoichiometric dot in a manner that the sulfur of the ligand completes stoichiometry of the bound system. Hence, this is indicative of the source of trap state when thio-based ligands are bound to chalcogenide nanocrystals. We also predict that titanyl phthalocyanine in a mix with chalcogenide dots of diameter ∼1.5 Å can form a donor-acceptor system.

  14. A new paradigm for core design aimed at the sustainability of nuclear energy: The solution of the extended equilibrium state

    International Nuclear Information System (INIS)

    Artioli, Carlo; Grasso, Giacomo; Petrovich, Carlo

    2010-01-01

    The future expansion of nuclear energy, a technology identified as one of the main candidates for reducing the world's dependence on fossil fuels, requires a thorough analysis of the sustainability of this energy source for long-term supply. Generation-IV nuclear systems could represent a turning point for energy production by minimizing the environmental footprint of the fuel cycle. A new paradigm is thus required for reactor design, focusing, at the core design level, on both the closure of the fuel cycle and the effective utilization of natural resources. Within this framework, the so-called 'adiabatic core' concept represents a particularly interesting solution. It is based on the idea of ensuring by design a condition of equilibrium in the fuel cycle (i.e., an equilibrium 'fuel vector'), foreseeing nuclear power systems able to maintain a constant total amount of both plutonium and minor actinides (TRU), consuming only uranium (either natural or depleted), while discharging to the environment only fission products and reprocessing losses. Under such a hypothesis, all actinides can be continuously recycled in the same system, reducing both the waste volume and its long-term radiotoxicity, as well as utilizing effectively uranium resources. Two mathematical approaches have been devised to find the 'extended' equilibrium solution for the fuel vector. These methods are compared, validated with the codes MCNPX and FISPACT and applied to the European lead-cooled fast reactor ELSY, confirming the potential of this approach (e.g., a reduction by two orders of magnitude of the TRU mass in the final waste in comparison with the fuel cycle of Light Water Reactors operated in a once-through scenario).

  15. (p,V{sub m},T,x) measurements for aqueous LiNO{sub 3} solutions[Density; Concentration; Electrolyte solutions; Equation of state; Lithium nitrate; Saturated density; Saturated pressure; Temperature; Water

    Energy Technology Data Exchange (ETDEWEB)

    Abdulagatov, I.M. E-mail: ilmutdin@boulder.nist.govmangur@datacom.ru; Azizov, N.D. E-mail: Nazim_Azizov@yahoo.com

    2004-01-01

    (p,V{sub m},T,x) properties of four aqueous LiNO{sub 3} solutions (0.181, 0.526, 0.963, and 1.728) mol {center_dot} kg{sup -1} H{sub 2}O were measured in the liquid phase with a constant-volume piezometer immersed in a precision liquid thermostat. Measurements were made for 10 isotherms between (298 and 573) K. The range of pressure was from (2 to 40) MPa. The total uncertainty of density, pressure, temperature, and concentration measurements were estimated to be less than 0.06 %, 0.05 %, 10 mK, and 0.014 %, respectively. The values of saturated density were determined by extrapolating experimental (p,{rho}) data to the vapor-pressure at fixed temperature and composition using an interpolating equation. A polynomial type of equation of state for specific volume was obtained as a function of temperature, pressure, and composition by a least-squares method from the experimental data. The average absolute deviation (AAD) between measured and calculated values from this polynomial equation for density was 0.02 %. Measured values of solution density were compared with values calculated from Pitzer's ion-interaction equation. The agreement is within (0.2 to 0.4) % depending of concentration range.

  16. Gravity-driven pH adjustment for site-specific protein pKa measurement by solution-state NMR

    Science.gov (United States)

    Li, Wei

    2017-12-01

    To automate pH adjustment in site-specific protein pKa measurement by solution-state NMR, I present a funnel with two caps for the standard 5 mm NMR tube. The novelty of this simple-to-build and inexpensive apparatus is that it allows automatic gravity-driven pH adjustment within the magnet, and consequently results in a fully automated NMR-monitored pH titration without any hardware modification on the NMR spectrometer.

  17. The state-of-the-art of the LTA{sub N} method in the solution of the transport equation in a slab

    Energy Technology Data Exchange (ETDEWEB)

    Vieira Cardona, A. [Faculty of Mathematics, PUCRS, Porto-Alegre (Brazil); Panta Pazos, R. [Nulcear Engineering Department, UFRGS, Porto-Alegre (Brazil); Tullio de Vilhena, M. [Institute of Mathematics, UFRGS, Porto-Alegre (Brazil)

    2004-07-01

    In this work we report the state-of-the-art of the LTA{sub N} method, reporting the derivation of the LTA{sub N} homogeneous and particular solution in a slab for large N (N < 650), as well its accelerated version, which reduces drastically the computational time. We also sketch the mathematical background for the error bound estimate and convergence analysis of the LTA{sub N} method. We show that the LTA{sub N} method, consequently the Laplace transform technique, is a quite general approach to solve a wide class of transport problems in a slab mainly the ones requiring an arbitrary source and large N.

  18. Solution and solid-state studies on the halide binding affinity of perfluorophenyl-armed uranyl-salophen receptors enhanced by anion-π interactions

    Energy Technology Data Exchange (ETDEWEB)

    Leoni, Luca; Mele, Andrea; Giannicchi, Ilaria; Mihan, Francesco Yafteh; Dalla Cort, Antonella [Dipartimento di Chimica and IMC-CNR, Universita di Roma La Sapienza (Italy); Puttreddy, Rakesh; Jurcek, Ondrej; Rissanen, Kari [University of Jyvaeskylae, Department of Chemistry, Nanoscience Center (Finland)

    2016-12-23

    The enhancement of the binding between halide anions and a Lewis acidic uranyl-salophen receptor has been achieved by the introduction of pendant electron-deficient arene units into the receptor skeleton. The association and the occurrence of the elusive anion-π interaction with halide anions (as tetrabutylammonium salts) have been demonstrated in solution and in the solid state, providing unambiguous evidence on the interplay of the concerted interactions responsible for the anion binding. (copyright 2016 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. State-dependent electron delocalization dynamics at the solute-solvent interface: soft-x-ray absorption spectroscopy and ab initio calculations.

    Science.gov (United States)

    Bokarev, Sergey I; Dantz, Marcus; Suljoti, Edlira; Kühn, Oliver; Aziz, Emad F

    2013-08-23

    Nonradiative decay channels in the L-edge fluorescence yield spectra from transition-metal-aqueous solutions give rise to spectral distortions with respect to x-ray transmission spectra. Their origin is unraveled here using partial and inverse partial fluorescence yields on the microjet combined with multireference ab initio electronic structure calculations. Comparing Fe2+, Fe3+, and Co2+ systems we demonstrate and quantify unequivocally the state-dependent electron delocalization within the manifold of d orbitals as one origin of this observation.

  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...