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Sample records for complex formation constants

  1. Analysis of the association constants for charge-transfer complex formation

    NASA Astrophysics Data System (ADS)

    McKim, William D.; Ray, Jayanta; Arnold, Bradley R.

    2013-02-01

    The phenomenon of charge transfer (CT) complex formation has been of interest for more than 50 years and has led to the development of numerous applications. Even with the prolonged interest in these complexes the interactions responsible for complex formation have yet to be fully characterized and remain an area of sustained relevance. This report outlines the measurement of the association constants for CT complex formation of a series of methylated benzene donors with tetracyanoethylene, pyromellitic dianhydride, 2,3-dichloro-5,6-dicyano-p-benzoquinone, and 1,2,4,5-tetracyanobenzene acceptors in 1,2-dichloroethane solvent. The evaluation of the position of the CT absorption maximum and the magnitudes of the association constants within a theoretical model is described. The influence of solvent polarity on the magnitudes of the association constants was also discussed. These studies show that non-bonding interactions are important in most complexes while ion-pair interactions play a significant role in a select few of the complexes studied.

  2. Formation constants of neodymium acetate complexes at elevated temperatures by laser-induced photoacoustic spectroscopy

    SciTech Connect

    Wruck, D.A.; Kadkhodayan, B.; Palmer, C.E.A.; Silva, R.J.

    1995-12-01

    Chemical thermodynamic data on the formation of solution complexes by radionuclides as a function of temperature are needed for performance assessment studies of proposed radioactive waste repositories. Optical absorption spectroscopy is a preferred method for the measurement of complexation constants in aqueous solutions. Because many of radionuclides of interest, e.g., actinides, must be studied at very low solution concentrations, a system of high sensitivity is required. Therefore, a photoacoustic spectrometer has been developed for high sensitivity optical absorption measurements of aqueous solutions at elevated temperatures. The light source is a Nd: YAG-pumped dye laser system. The photoacoustic signal generated in the sample solution is detected with a piezoelectric transducer coupled to the thermostatted sample cell. The spectrometer has been tested by applying it to the determination of the formation constants of Nd(III) acetate complexes. The formation constants are reported for the temperature range 20 to 70{degrees}C; and are compared to measurements by spectrophotometry and calorimetry.

  3. Studies on chalcone derivatives: complex formation, thermal behavior, stability constant and antioxidant activity.

    PubMed

    El-Sayed, Yusif S; Gaber, M

    2015-02-25

    The chalcone 3-[4'-dimethylaminophenyl]-1-(2-pyridyl) prop-2-en-1-one (DMAPP) and 3-(4'-diethylaminophenyl)-1-(2-pyridinyl) prop-2-en-1-one abbreviated as DEAPP have been synthesized and characterized with IR, (1)H NMR, (13)C NMR spectroscopic techniques as described previously (El-Daly et al., 2008; Gaber et al., 2009; El-Sayed, 2013). By using UV visible spectroscopy method the mole fraction ratio for copper with DMAPP and DEAPP complexes were determined and it was found to be 1:1. The stability constants of this complex have been determined by Job's method. The stability constant (Kf) of copper with DMAPP and DEAPP complexes in universal buffer pH=3.2 was determined to be 9.9×10(4) and 5.2×10(4) respectively. The effect of Cu(II) ion on the emission spectrum of the free chalcone is also assigned. Adherence to Beer's law and Ringbom optimum concentration ranges are determined. The thermal decomposition of the metal complexes is studied by TGA technique. The kinetic parameters like activation energy, pre-exponential factor and entropy of activation are estimated. The structure of complexes was energetically optimized through molecular mechanics applying MM(+) force field coupled with molecular dynamics simulation. The bond lengths and bond angles have been calculated to confirm the geometry of the ligands and their Cu(II) complexes. The mode of interaction of the chalcone to copper nanoparticles was studied. The apparent association constants of the colloidal copper nanoparticles:chalcone complexes in solution were evaluated using the spectral method and compared with the formation constant of the Cu(II) chalcone complexes. Antioxidant activity of these chalcones was evaluated by using 1,1'-diphenyl-2-picrylhydrazyl (DPPH) radicals scavenging method, which showed that the antioxidant activity of DMAPP has higher value than the DEAPP. Semi-empirical study results showed that DMAPP have higher dipole moment than DEAPP. PMID:25238180

  4. Studies on chalcone derivatives: Complex formation, thermal behavior, stability constant and antioxidant activity

    NASA Astrophysics Data System (ADS)

    El-Sayed, Yusif S.; Gaber, M.

    2015-02-01

    The chalcone 3-[4‧-dimethylaminophenyl]-1-(2-pyridyl) prop-2-en-1-one (DMAPP) and 3-(4‧-diethylaminophenyl)-1-(2-pyridinyl) prop-2-en-1-one abbreviated as DEAPP have been synthesized and characterized with IR, 1H NMR, 13C NMR spectroscopic techniques as described previously (El-Daly et al., 2008; Gaber et al., 2009; El-Sayed, 2013). By using UV visible spectroscopy method the mole fraction ratio for copper with DMAPP and DEAPP complexes were determined and it was found to be 1:1. The stability constants of this complex have been determined by Job's method. The stability constant (Kf) of copper with DMAPP and DEAPP complexes in universal buffer pH = 3.2 was determined to be 9.9 × 104 and 5.2 × 104 respectively. The effect of Cu(II) ion on the emission spectrum of the free chalcone is also assigned. Adherence to Beer's law and Ringbom optimum concentration ranges are determined. The thermal decomposition of the metal complexes is studied by TGA technique. The kinetic parameters like activation energy, pre-exponential factor and entropy of activation are estimated. The structure of complexes was energetically optimized through molecular mechanics applying MM+ force field coupled with molecular dynamics simulation. The bond lengths and bond angles have been calculated to confirm the geometry of the ligands and their Cu(II) complexes. The mode of interaction of the chalcone to copper nanoparticles was studied. The apparent association constants of the colloidal copper nanoparticles:chalcone complexes in solution were evaluated using the spectral method and compared with the formation constant of the Cu(II) chalcone complexes. Antioxidant activity of these chalcones was evaluated by using 1,1‧-diphenyl-2-picrylhydrazyl (DPPHrad) radicals scavenging method, which showed that the antioxidant activity of DMAPP has higher value than the DEAPP. Semi-empirical study results showed that DMAPP have higher dipole moment than DEAPP [1].

  5. Formation constants of copper(i) complexes with cysteine, penicillamine and glutathione: implications for copper speciation in the human eye.

    PubMed

    Knigsberger, Lan-Chi; Knigsberger, Erich; Hefter, Glenn; May, Peter M

    2015-12-21

    Protonation constants for the biologically-important thioamino acids cysteine (CSH), penicillamine (PSH) and glutathione (GSH), and the formation constants of their complexes with Cu(i), have been measured at 25 C and an ionic strength of 1.00 mol dm(-3) (Na)Cl using glass electrode potentiometry. The first successful characterisation of binary Cu(i)-CSH and Cu(i)-GSH species over the whole pH range was achieved in this study by the addition of a second thioamino acid, which prevented the precipitation that normally occurs. Appropriate combinations of binary and ternary (mixed ligand) titration data were used to optimise the speciation models and formation constants for the binary species. The results obtained differ significantly from literature data with respect to the detection and quantification of protonated and polynuclear complexes. The present results are thought to be more reliable because of the exceptionally wide pH and concentration ranges employed, the excellent reproducibility of the data, the close agreement between the calculated and observed formation functions, and the low standard deviations and absence of numerical correlation in the constants. The present formation constants were incorporated into a large Cu speciation model which was used to predict, for the first time, metal-ligand equilibria in the biofluids of the human eye. This simulation provided an explanation for the precipitation of metallic copper in lens and cornea, which is known to occur as a consequence of Wilson's disease. PMID:26505238

  6. Dynamic titration: determination of dissociation constants for noncovalent complexes in multiplexed format using HPLC-ESI-MS.

    PubMed

    Fryck, Petr; Schug, Kevin A

    2008-03-01

    With recent growth in fields such as life sciences and supramolecular chemistry, there has been an ever increasing need for high-throughput methods that would permit determination of binding affinities for noncovalent complexes of various host-guest systems. These are traditionally measured by titration experiments where concentration-dependent signals of species participating in solution-based binding equilibria are monitored by methods such as UV-vis spectrophotometry, calorimetry, or nuclear magnetic resonance spectrometry. Here we present a new titration technique that unifies and allows chromatographic separation of guests with determination of dissociation constants by electrospray mass spectrometry in a multiplexed format. A theoretical model has been derived that describes the complex formation for the guests eluted from a chromatographic column when hosts are admixed postcolumn. The model takes possible competition equilibria into account; i.e., it can deal with unresolved peaks of guests with the possible addition of multiple hosts in one experiment. This on-line workflow makes determination of binding affinities for large libraries of compounds possible. The potential of the method is demonstrated on the determination of dissociation constants for complexes of beta- and gamma-cyclodextrins with nonsteroidal antiinflammatory drugs ibuprofen, naproxen, and flurbiprofen. PMID:18237190

  7. Determination of formation constants and structural characterization of cyclodextrin inclusion complexes with two phenolic isomers: carvacrol and thymol

    PubMed Central

    Kfoury, Miriana; Landy, David; Ruellan, Steven; Auezova, Lizette; Greige-Gerges, Hélène

    2016-01-01

    Summary Carvacrol and thymol have been widely studied for their ability to control food spoilage and to extend shelf-life of food products due to their antimicrobial and antioxidant activities. However, they suffer from poor aqueous solubility and pronounced flavoring ability that limit their application in food systems. These drawbacks could be surpassed by encapsulation in cyclodextrins (CDs). Applications of their inclusion complexes with CDs were reported without investigating the inclusion phenomenon in deep. In this study, inclusion complexes were characterized in terms of formation constants (K f), complexation efficiency (CE), CD:guest molar ratio and increase in bulk formulation by using an UV–visible competitive method, phase solubility studies as well as 1H and DOSY 1H NMR titration experiments. For the first time, a new algorithmic treatment that combines the chemical shifts and diffusion coefficients variations for all guest protons was applied to calculate K f. The position of the hydroxy group in carvacrol and thymol did not affect the stoichiometry of the inclusion complexes but led to a different binding stability with CDs. 2D ROESY NMR experiments were also performed to prove the encapsulation and illustrate the stable 3D conformation of the inclusion complexes. The structural investigation was accomplished with molecular modeling studies. Finally, the radical scavenging activity of carvacrol and thymol was evaluated by the ABTS radical scavenging assay. An improvement of this activity was observed upon encapsulation. Taken together, these results evidence that the encapsulation in CDs could be valuable for applications of carvacrol and thymol in food. PMID:26877806

  8. Formation constants and composition of Ga3+ and In3+ complexes with iminodisuccinic acid in aqueous solutions according to potentiometric data

    NASA Astrophysics Data System (ADS)

    Tolkacheva, L. N.; Nikol'skii, V. M.

    2013-09-01

    The complexation of Ga3+ and In3+ with iminodisuccinic acid (H4L) at 25C in 0.1, 0.4, 0.6, and 0.8 M KNO3 supporting solutions was studied by potentiometry and mathematical modeling. The thermodynamic constants of formation of neutral, protonated, and hydroxo complexes were calculated by extrapolating the concentration constants to the zero ionic strength using an equation with one individual parameter.

  9. Stability constants for the formation of lead chloride complexes as a function of temperature and ionic strength

    PubMed Central

    Luo, Yanxin; Millero, Frank J.

    2015-01-01

    The stability constants for the formation of lead (Pb2+) with chloride Pb2+=nCl??PbCln2?n?n(n=1,2,3) have been determined using a spectrophotometric method in NaClO4 solutions as a function of ionic strength (06 m) and temperature (1545 C). The results have been fitted to the equations: log?1?=log?1+0.21I?8.61I0.5?(1+1.2I0.5)+1927.40[I0.5?(1+1.2I0.5)]?Tlog?2?=log?2+0.32I?4.67I0.5(1+1.2I0.5)+594.54[I0.5?(1+1.2I0.5)]?Tlog?3?=log?3+0.40I?2.68I0.5(1+1.2I0.5)?43.98[I0.5?(1+1.2I0.5)]?T with standard errors of 0.05, 0.04 and 0.06, respectively. The thermodynamic values of log ?1, log?2 and log?3 at 25.0 C and the enthalpies of formation of PbCl+, PbCl20 and PbCl3? are in good agreement with literature values. We have combined our results with the earlier work of Seward (1984) to yield thermodynamic constants that are valid from 15 to 300 C: log?1=44.82+0.031T?21.21logTlog?2=61.42+0.046T?29.51logTlog?3=107.97+0.071T?51.46logT with standard errors of 0.05, 0.08 and 0.10, respectively.

  10. Stability constants of aluminium fluoride complexes.

    PubMed

    Agarwal, R P; Moreno, E C

    1971-09-01

    Pointwise titrations of aluminium nitrate solutions with sodium fluoride were made at ionic strengths of 0.5, 0.2, 0.1 and 0.05M and at temperatures of 25 degrees and 37 degrees . The total Al(3+) concentration was kept constant at 5 x 10(-4)M and the total F(-) concentration covered the range 5-20 x 10(-4)M with a minimum of 20 points per titration. It is shown that only mononuclear complexes were present with these solution compositions. Determinations of H(+) and F(-) in solution were made by the use of quinhydrone and lanthanum fluoride electrodes, respectively. Formation constants were calculated by three different procedures. Best results were obtained by a non-linear generalized least-squares method that (a) permits calculation of the formation constants with the simultaneous presence of all the complexes being taken into account, (b) does not require segregation of data according to the values of the formation function (n), and (c) yields standard errors that reflect the errors in all the experimental measurements. Values for the formation constants at infinite dilution were obtained by a linear least-squares adjustment of the values obtained for the four finite ionic strengths. The formation constants thus obtained for the reaction AlF(n-1) + F <==> AlF(n) (charges omitted) at 25 degrees have logarithmic values of 6.69 +/- 0.02, 5.35 +/- 0.03, 3.68 +/- 0.01 and 2.75 +/- 0.04 for n = 1, 2, 3 and 4, respectively. The corresponding values at 37 degrees are 6.68 +/- 0.10,5.34 +/- 0.02,3.94 +/- 0.04, and 3.29 +/- 0.05. PMID:18960958

  11. Formation constants of copper(II) complexes with tripeptides containing Glu, Gly, and His: potentiometric measurements and modeling by generalized multiplicative analysis of variance.

    PubMed

    Khoury, Rima Raffoul; Sutton, Gordon J; Ebrahimi, Diako; Hibbert, D Brynn

    2014-02-01

    We report a systematic study of the effects of types and positions of amino acid residues of tripeptides on the formation constants logβ, acid dissociation constants pKa, and the copper coordination modes of the copper(II) complexes with 27 tripeptides formed from the amino acids glutamic acid, glycine, and histidine. logβ values were calculated from pH titrations with l mmol L(-1):1 mmol L(-1) solutions of the metal and ligand and previously reported ligand pKa values. Generalized multiplicative analysis of variance (GEMANOVA) was used to model the logβ values of the saturated, most protonated, monoprotonated, logβ(CuL) - logβ(HL), and pKa of the amide group. The resulting model of the saturated copper species has a two-term model describing an interaction between the central and the C-terminal residues plus a smaller, main effect of the N-terminal residue. The model supports the conclusion that two copper coordination modes exist depending on the absence or presence of His at the central position, giving species in which copper is coordinated via two or three fused chelate rings, respectively. The GEMANOVA model for pKamide, which is the same as that for the saturated complex, showed that Gly-Gly-His has the lowest pKamide values among the 27 tripeptides. Visible spectroscopy indicated the formation of metal-ligand dimers for tripeptides His-His-Gly and His-His-Glu, but not for His-His-His, and the formation of multiple ligand bis compexes CuL2 and Cu(HL)2 for tripeptides (Glu/Gly)-His-(Glu/Gly) and His-(Glu/Gly)-(Glu/Gly), respectively. PMID:24432726

  12. How the cosmological constant affects gravastar formation

    SciTech Connect

    Chan, R.; Silva, M.F.A. da; Rocha, P. E-mail: mfasnic@gmail.com

    2009-12-01

    Here we generalized a previous model of gravastar consisted of an internal de Sitter spacetime, a dynamical infinitely thin shell with an equation of state, but now we consider an external de Sitter-Schwarzschild spacetime. We have shown explicitly that the final output can be a black hole, a ''bounded excursion'' stable gravastar, a stable gravastar, or a de Sitter spacetime, depending on the total mass of the system, the cosmological constants, the equation of state of the thin shell and the initial position of the dynamical shell. We have found that the exterior cosmological constant imposes a limit to the gravastar formation, i.e., the exterior cosmological constant must be smaller than the interior cosmological constant. Besides, we have also shown that, in the particular case where the Schwarzschild mass vanishes, no stable gravastar can be formed, but we still have formation of black hole.

  13. Bacterial formate hydrogenlyase complex

    PubMed Central

    McDowall, Jennifer S.; Murphy, Bonnie J.; Haumann, Michael; Palmer, Tracy; Armstrong, Fraser A.; Sargent, Frank

    2014-01-01

    Under anaerobic conditions, Escherichia coli can carry out a mixed-acid fermentation that ultimately produces molecular hydrogen. The enzyme directly responsible for hydrogen production is the membrane-bound formate hydrogenlyase (FHL) complex, which links formate oxidation to proton reduction and has evolutionary links to Complex I, the NADH:quinone oxidoreductase. Although the genetics, maturation, and some biochemistry of FHL are understood, the protein complex has never been isolated in an intact form to allow biochemical analysis. In this work, genetic tools are reported that allow the facile isolation of FHL in a single chromatographic step. The core complex is shown to comprise HycE (a [NiFe] hydrogenase component termed Hyd-3), FdhF (the molybdenum-dependent formate dehydrogenase-H), and three iron-sulfur proteins: HycB, HycF, and HycG. A proportion of this core complex remains associated with HycC and HycD, which are polytopic integral membrane proteins believed to anchor the core complex to the cytoplasmic side of the membrane. As isolated, the FHL complex retains formate hydrogenlyase activity in vitro. Protein film electrochemistry experiments on Hyd-3 demonstrate that it has a unique ability among [NiFe] hydrogenases to catalyze production of H2 even at high partial pressures of H2. Understanding and harnessing the activity of the FHL complex is critical to advancing future biohydrogen research efforts. PMID:25157147

  14. Thiocyanato Chromium (III) Complexes: Separation by Paper Electrophoresis and Estimate of Stability Constants

    ERIC Educational Resources Information Center

    Larsen, Erik; Eriksen, J.

    1975-01-01

    Describes an experiment wherein the student can demonstrate the existence of all the thiocyanato chromium complexes, estimate the stepwise formation constants, demonstrate the robustness of chromium III complexes, and show the principles of paper electrophoresis. (GS)

  15. Hydrolysis and formation constants at 25/sup 0/C

    SciTech Connect

    Phillips, S.L.

    1982-05-01

    A database consisting of hydrolysis and formation constants for about 20 metals associated with the disposal of nuclear waste is given. Complexing ligands for the various ionic species of these metals include OH, F, Cl, SO/sub 4/, PO/sub 4/ and CO/sub 3/. Table 1 consists of tabulated calculated and experimental values of log K/sub xy/, mainly at 25/sup 0/C and various ionic strengths together with references to the origin of the data. Table 2 consists of a column of recommended stability constants at 25/sup 0/C and zero ionic strength tabulated in the column headed log K/sub xy/(0); other columns contain coefficients for an extended Debye-Huckel equation to permit calculations of stability constants up to 3 ionic strength, and up to 0.7 ionic strength using the Davies equation. Selected stability constants calculated with these coefficients for various ionic strengths agree to an average of +- 2% when compared with published experimental and calculated values.

  16. Complex format synchronization and decommutation

    NASA Astrophysics Data System (ADS)

    Thom, Gary A.

    Some complex telemetry formats currently used for data transmission by airborn data acquisition systems are reviewed. The formats discussed include asynchronous embedded formats, tagged data formats, IRIG 106 Chapter 8 formats, multiplexed formats, and adaptive formats. The need for designing decommutation systems characterized by extended life or capable of supporting multiple applications that are flexible enough to adapt to new formats is emphasized. It is suggested that existing complex formats be used as a guide in designing new systems with flexibility for future applications.

  17. Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory

    DOE PAGESBeta

    Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S.

    2015-04-02

    The ability to predict the equilibrium constants for the formation of 1:1 uranyl:ligand complexes (log K1 values) provides the essential foundation for the rational design of ligands with enhanced uranyl affinity and selectivity. We also use density functional theory (B3LYP) and the IEFPCM continuum solvation model to compute aqueous stability constants for UO22+ complexes with 18 donor ligands. Theoretical calculations permit reasonably good estimates of relative binding strengths, while the absolute log K1 values are significantly overestimated. Accurate predictions of the absolute log K1 values (root mean square deviation from experiment 1 values ranging from 0more »to 16.8) can be obtained by fitting the experimental data for two groups of mono and divalent negative oxygen donor ligands. The utility of correlations is demonstrated for amidoxime and imide dioxime ligands, providing a useful means of screening for new ligands with strong chelate capability to uranyl.« less

  18. Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory

    SciTech Connect

    Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S.

    2015-04-02

    The ability to predict the equilibrium constants for the formation of 1:1 uranyl:ligand complexes (log K1 values) provides the essential foundation for the rational design of ligands with enhanced uranyl affinity and selectivity. We also use density functional theory (B3LYP) and the IEFPCM continuum solvation model to compute aqueous stability constants for UO22+ complexes with 18 donor ligands. Theoretical calculations permit reasonably good estimates of relative binding strengths, while the absolute log K1 values are significantly overestimated. Accurate predictions of the absolute log K1 values (root mean square deviation from experiment < 1.0 for log K1 values ranging from 0 to 16.8) can be obtained by fitting the experimental data for two groups of mono and divalent negative oxygen donor ligands. The utility of correlations is demonstrated for amidoxime and imide dioxime ligands, providing a useful means of screening for new ligands with strong chelate capability to uranyl.

  19. Variation of stability constants of thorium citrate complexes and of thorium hydrolysis constants with ionic strength

    SciTech Connect

    Choppin, G.R.; Erten, H.N.; Xia, Y.X.

    1995-09-01

    Citrate is among the organic anions that are expected to be present in the wastes planned for deposition in the Waste Isolation Pilot Plant repository. In this study, a solvent extraction method has been used to measure the stability constants of Thorium(IV)[Th(IV)] with citrate anions in aqueous solutions with (a) NaClO{sub 4} and (b) NaCl as the background electrolytes. The ionic strengths were varied up to 5 m (NaCl) and 14 m (NaClO{sub 4}). The data from the NaClO{sub 4} solutions at varying pH values were used to calculate the hydrolysis constants for formation of Th(OH){sup 3+} at the different ionic strengths.

  20. Stability constants of europium complexes with a nitrogen heterocycle substituted methane-1,1-diphosphonic acid

    SciTech Connect

    Jensen, M.P.; Rickert, P.G.; Schmidt, M.A.; Nash, K.L.

    1996-06-01

    Even in moderately acidic solutions ([H{sup +}] > 0.01 M), N-piperidinomethane-1,1-diphosphonic acid (H{sub 4}PMDPA) is a strong complexant of trivalent lanthanide ions that shows enhanced complex solubility over previously studied 1,1-diphosphonic acids. The protonation constants of PMDPA in 2.0 M H/NaClO{sub 4} were determined by potentiometric and NMR titrations, and the stability constants for formation of complexes with Eu{sup 3+} were determined by solvent extraction. Difference in protonation equilibria induced by addition of the nitrogen heterocycle results in an increase in the complexation strength of PMDPA. In solutions containing 0.1 M H{sup +} and ligand concentrations greater than 0.02 M, PMDPA is the most effective 1,1-diphosphonic acid for europium complexation studied thus far.

  1. Stability constants of nickel(II)-nicotinamide complexes in aqueous-ethanol solutions

    NASA Astrophysics Data System (ADS)

    Gamov, G. A.; Dushina, S. V.; Sharnin, V. A.

    2014-05-01

    The change in stability of 1: 1 and 1: 2 nicotinamide nickel(II) complexes in an aqueous ethanol with ethanol contents of 0 to 0.85 molar fractions is studied via potentiometry at 298.2 0.1 K and a ionic strength of 0.25 (NaClO4). The constant of complex formation for the first step increases at concentrations of organic solvent lower than 0.5 molar fractions and decreases at a higher content of ethanol. The weakening of the solvation of the donor center in nicotinamide corresponds to the observed change in the stability of the complex. A linear interrelation between the change in the coordination equilibrium constant and the difference between the effect of solvent composition on the solvation of the complex ions and complexing agent is revealed.

  2. Spectrophotometric Determination of Iron(III)-Glycine Formation Constant in Aqueous Medium Using Competitive Ligand Binding

    ERIC Educational Resources Information Center

    Prasad, Rajendra; Prasad, Surendra

    2009-01-01

    The formation constant of iron(III) complex with glycine (Gly) ligand in aqueous acidic medium (0.2 M HNO[subscript 3], I = 0.2 M at 28 plus or minus 1 degree C) was determined spectrophotometrically in which a competing color reaction between Fe(III) and SCN[superscript -] was used as an indicator reaction. Under the specified conditions Fe(III)

  3. Spectrophotometric Determination of Iron(III)-Glycine Formation Constant in Aqueous Medium Using Competitive Ligand Binding

    ERIC Educational Resources Information Center

    Prasad, Rajendra; Prasad, Surendra

    2009-01-01

    The formation constant of iron(III) complex with glycine (Gly) ligand in aqueous acidic medium (0.2 M HNO[subscript 3], I = 0.2 M at 28 plus or minus 1 degree C) was determined spectrophotometrically in which a competing color reaction between Fe(III) and SCN[superscript -] was used as an indicator reaction. Under the specified conditions Fe(III)…

  4. Taurocholate and taurodeoxycholate: gel formation and protonation constants.

    PubMed

    Antonilli, Marco; Bottari, Emilio; Festa, Maria Rosa

    2007-01-01

    Taurocholate (TC) and taurodeoxycholate (TDC) in aqueous solutions, in the presence of sodium and hydrogen ions can give micellar products, even differently protonated. This phenomenon is investigated in this paper to explain whether the assumption of hydrogen ions is to attribute to the micellar aggregates, or to the protonation of taurocholate and taurodeoxycholate, respectively. In the course of this research, often the formation of gel occurred immediately after the mixture of the reagents (sodium, hydrogen ions and anions of bile acids) or after some time, depending on the concentrations of the reagents. No author mentions this evidence, but experiments carried out in the presence of gel are not reproducible because the investigated solutions cannot be considered in real equilibrium. The protonation study was performed by means of electromotive force measurements of a galvanic cell involving a glass electrode, at 25 degrees C and 1.00 mol dm(-3) NaCl, as ionic medium. The obtained protonation constants had the following values: log k1 = 0.07+/- 0.02 for TC and log k'1 = 1.60 +/- 0.03 for TDC. PMID:17822262

  5. Damage formation associated with bending under a constant moment

    NASA Astrophysics Data System (ADS)

    Manaker, David M.; Turcotte, Donald L.; Kellogg, Louise H.

    2007-04-01

    Deformation within the Earth's lithosphere is largely controlled by the rheology of the rock. Fracture and faulting are characterized by elastic rheologies with brittle mechanisms, while folding and flow are characterized by plastic and/or viscous rheologies due to ductile mechanisms. However, it has been recognized that deformation that resembles ductile behavior can be produced within the confines of the brittle lithosphere. Specific examples are folds that form in the shallow crust, steep hinges at subduction zones that are accompanied by seismicity, and large-scale deformation at plate boundaries. In these cases, the brittle lithosphere behaves elastically with fracture and faulting yet produces ductile behavior. In this paper, we attempt to simulate such ductile behavior in elastic materials using continuum damage mechanics. Engineers utilize damage mechanics to model the continuum deformation of brittle materials. We utilize a modified form of damage mechanics that represents a reduction in frictional strength of preexisting fractures and faults. We use this empirical approach to simulate the bending of the lithosphere under the application of a constant moment. We use numerical simulations to obtain elastostatic solutions for plate bending and where the longitudinal stress at a particular node exceeds a yield stress, we apply damage to reduce Young's modulus at the node. Damage is calculated at each time step by a power-law relationship of the ratio of the yield stress to the longitudinal stress and the yield strain to the longitudinal strain. This results in the relaxation of the material due to increasing damage. To test our method, we apply our damage rheology to an infinite plate deforming under a constant bending moment. We simulate a wide range of behaviors from slow relaxation to instantaneous failure, over timescales that span six orders of magnitude. Using this method, stress relaxation produces elastic-perfectly plastic behavior in cases where failure does not occur. For cases of failure, we observe a rapid increase in damage leading to failure, analogous to the acceleration of microcrack formation and acoustic emissions prior to failure. The changes in the rate of damage accumulation in failure cases are similar to the changes in b-values of acoustic emissions observed in triaxial compression tests of fractured rock and b-value changes prior to some large earthquakes. Thus continuum damage mechanics can simulate the phenomenon of ductile behavior due to brittle mechanisms as well as observations of laboratory experiments and seismicity.

  6. Pattern Formation and Complexity Emergence

    NASA Astrophysics Data System (ADS)

    Berezin, Alexander A.

    2001-03-01

    Success of nonlinear modelling of pattern formation and self-organization encourages speculations on informational and number theoretical foundations of complexity emergence. Pythagorean "unreasonable effectiveness of integers" in natural processes is perhaps extrapolatable even to universal emergence "out-of-nothing" (Leibniz, Wheeler). Because rational numbers (R = M/N) are everywhere dense on real axis, any digital string (hence any "book" from "Library of Babel" of J.L.Borges) is "recorded" infinitely many times in arbitrary many rationals. Furthermore, within any arbitrary small interval there are infinitely many Rs for which (either or both) integers (Ms and Ns) "carry" any given string of any given length. Because any iterational process (such as generation of fractal features of Mandelbrot Set) is arbitrary closely approximatable with rational numbers, the infinite pattern of integers expresses itself in generation of complexity of the world, as well as in emergence of the world itself. This "tunnelling" from Platonic World ("Platonia" of J.Barbour) to a real (physical) world is modern recast of Leibniz's motto ("for deriving all from nothing there suffices a single principle").

  7. Stoichiometry and Formation Constant Determination by Linear Sweep Voltammetry.

    ERIC Educational Resources Information Center

    Schultz, Franklin A.

    1979-01-01

    In this paper an experiment is described in which the equilibrium constants necessary for determining the composition and distribution of lead (II)-oxalate species may be measured by linear sweep voltammetry. (Author/BB)

  8. Laboratory measurement of the complex dielectric constant of soils

    NASA Technical Reports Server (NTRS)

    Wiebe, M. L.

    1971-01-01

    The dielectric constant of a material is an extremely important parameter when considering passive radiometric remote sensing applications. This is because the emitted energy measured by a microwave radiometer is dependent on the dielectric constant of the surface being scanned. Two techniques of measuring dielectric constants are described. The first method involves a dielectric located in air. The second method uses basically the same theoretical approach, but the dielectric under consideration is located inside a section of waveguide.

  9. Pattern Formation in Complex Fluids

    NASA Astrophysics Data System (ADS)

    Shelley, Michael

    2000-03-01

    Classical fluid instabilities -- such as the Saffman-Taylor instability in a Hele-Shaw cell -- are dramatically modified by using complex fluids. For example, polymeric liquids driven in a Hele-Shaw cell yield "dendritic" patterns with an apparent directional anisotropy. The dynamics of complex liquids can also lead to new instabilities and patterns, such as space-filling patterns formed by successive bucklings of growing "elastica" seen in the phase transition of a liquid crystalline material. Understanding such problems requires an interplay between physical modeling, mathematical analysis, and sophisticated nonlinear simulation. For the first problem, I will discuss a non-Newtonian version of Darcy's law for Hele-Shaw flow. This yields a free-boundary problem for the pattern formation, and requires the solution of a nonlinear elliptic equation in a time-dependent domain. This is pushing the development of adaptive grid methods that represent the geometry accurately and efficiently. Our simulations yield insight into how shear-thinning, as is evinced by polymeric liquids, can produce patterns reminiscent of experiment, with "dendritic fingers", side-branching, and reduced tip-splitting. In the second problem, a long filament in a smectic-A phase grows within an isotropic fluid. The splay deformation of the material gives this filament an elastic response. The macroscopic model describes the dynamics of a growing, elastic filament immersed in a Stokesian fluid. The model marries filament elasticity and tensile forces with a numerically tractable nonlocal slender-body theory. Analysis shows that growth of the filament, despite fluid drag, produces a buckling instability. When coupled to a nonlocal hydrodynamic self-interaction, our fully nonlinear simulations show that such instabilities iterate along the filament, and give "space-filling" patterns.

  10. Surface tension method for determining binding constants for cyclodextrin inclusion complexes of ionic surfactants

    SciTech Connect

    Dharmawardana, U.R.; Christian, S.D.; Tucker, E.E.; Taylor, R.W.; Scamehorn, J.F. )

    1993-09-01

    A new method has been developed for determining binding constants of complexes of cyclodextrins with surface-active compounds, including water-soluble ionic surfactants. The technique requires measuring the change in surface tension caused by addition of a cyclodextrin (CD) to aqueous solutions of the surfactant; the experimental results lead directly to inferred values of the thermodynamic activity of the surfactant. Surface tension results are reported for three different surfactants sodium dodecyl sulfate (SDS), cetylpyridinium chloride (CPC), and cetyltrimethylammonium bromide (CTAB) in the presence and in the absence of added [beta]-CD. Data for CPC have been obtained at surfactant concentrations below and above the critical micelle concentration. Correlations between surface tension and surfactant activity are expressed by the Szyszkowski equation, which subsumes the Langmuir adsorption model and the Gibbs equation. It is observed that the surface tension increases monotonically as [beta]-cyclodextrin is added to ionic surfactant solutions. At concentrations of CD well in excess of the surfactant concentration, the surface tension approaches that of pure water, indicating that neither the surfactant-CD complexes nor CD itself are surface active. Binding constants are inferred from a model that incorporates the parameters of the Szyszkowski equation and mass action constants relating to the formation of micelles from monomers of the surfactant and the counterion. Evidence is given that two molecules of CD can complex the C-16 hydrocarbon chain of the cetyl surfactants. 30 refs., 5 figs., 1 tab.

  11. Stability constants of Ni(II)- and Cu(II)-N-heterocycle complexes according to spectrophotometric data

    NASA Astrophysics Data System (ADS)

    Badhe, Samata; Tekade, Pradip; Bajaj, Sonal; Thakare, Shrikant

    2015-12-01

    The interaction of Ni(II) and Cu(II) with ethyl 4-(4-hydroxyphenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine- 5-carboxylate [Ligand 1], 4-(1H-benzimidazol-2-yl)phenol [Ligand 2], and 2-(3-phenylamino- 4,5-dihydro-1,2-oxazol-5-yl)phenol [Ligand 3] have been studied by spectrophotometric technique at 0.01 M ionic strength and 28°C in 70% dioxane—water mixture. The data obtained were used to estimate the stability constant of these ligands. Spectrophotometric investigation of Ni(II) and Cu(II) complexes with these ligands shows 1: 1 complex formation. The formation of complexes has been studied by Job's variation method. The values of conditional stability constants of Cu(II) complexes are greater than the corresponding Ni(II) complexes. The greater value of stability constant of Cu(II) complexes may be due to the fact of more stable nature of Cu(II). The value of stability constant of Cu(II)—Ligand 2 complex is greater than that of Cu(II)-Ligand 1 and Cu(II)-Ligand 3. The same of Ni(II)-Ligand 3 complex is greater than that of Ni(II)-Ligand 1 and Ni(II)-Ligand 2.

  12. The potentiometric determination of stability constants for zinc acetate complexes in aqueous solutions to 295C

    NASA Astrophysics Data System (ADS)

    Glordano, Thomas H.; Drummond, S. E.

    1991-09-01

    A potentiometric method was used to determine the formation quotients of zinc acetate complexes in aqueous solutions from 50 to 295C at ionic strengths of 0.03,0.3, and 1.0 m. The potentiometric titrations were carried out in an externally heated, Teflon-lined concentration cell fitted with hydrogen electrodes. Formal sodium acetate concentrations of the experimental solutions ranged from 0.001 to 0. 1 m with acetic acid to sodium acetate ratios ranging from 30 to 300. Sodium trifluoromethanesulfonate (F3CSO3Na) was used as a supporting electrolyte. Stoichiometries and formation quotients for the complexes ZnCH3COO+, Zn(CH3COO)2, and Zn(CH3COO)-3 were derived from the titration data by regression analysis. Stability constants at infinite dilution (Kn) and other relevant thermodynamic quantities were calculated for these three complexes. Logarithms for the formation constants of the general reaction Zn2+ + nCH3COO- = Zn(CH3COO)n2-n are n = 1-(1.9 0.2, 50C), (2.3 0.1, 100C), (2.8 0.1, 150C), (3.5 0.1, 200C), (4.3 0.2, 250C), (5.3 0.3, 300C); n = 2-(3.4 0.1, 50C), (4.0 0.1, 100C), (4.83 0.09, 150C), (5.9 0.1, 200C), (7.1 0.1, 250C), (8.7 0.2, 300C); n = 3-(4.1 0.3, 50C), (4.7 0.3, 100C), (5.5 0.3, 150C), (6.6 0.3, 200C), (7.9 0.3, 250C), (9.4 0.3, 300C). Calculations of zinc speciation in acetate-chloride solutions show that zinc acetate complexes should have an importance similar to zinc chloride complexes in high acetate waters where chloride to acetate molal ratios are less than about 10.

  13. Complex formation in the system zirconium-diantipyrylpropylmethane-acidic dye

    SciTech Connect

    Shtokalo, M.I.; Kostenko, E.E.

    1985-05-01

    Previously, the authors used a metal indicator method to examine the formation of complexes of zirconium with diantipyrylpropylmethane (DAPM) and have shown that two complexes, Zr (DAPM)/sup 4 +/ and Zr (DAPM) /sup 4 +//sub 2/ are formed in 0.1 and 1.0 M HC1, with stability constants of 5.10.10/sup 10/ and 3.80.10/sup 14/ respectively. Now the authors combine this complex with the acidic dye 2-(4-sulfonphenylazo)-1.8-dihydroxynaphthalene-3.6-disulfonic acid (SPADNS). The optimal conditions have been found for the formation of the heteroligand complex. It is shown that Zr (IV) ions are involved in coordination, giving the compound (Zr (DAPM) (HR) 2)/sup 2 -/. A method has been developed for the photometric determination of (0.202.0).10/sup -5/ M solutions of zirconium, and this has been used for the analysis of process water from the Rovensk nuclear power station.

  14. Microchip-ESI-MS determination of dissociation constant of the lysozyme-NAG(3) complex.

    PubMed

    Svobodov, Jaroslava; Mathur, Sonal; Muck, Alexander; Letzel, Thomas; Svatos, Ales

    2010-08-01

    An on-line microfluidic system for determination of dissociation constants of enzyme/substrate weak interactions by nanoESI-MS is introduced. The microchip was designed to permit the enzyme and the substrate to mix by molecular diffusion in a pressure-driven laminar flow. Introduction of reagent solutions into the chip was an optimized combination of a micropump and an autosampler to enable automation of the measurements. The system performance was tested for monitoring of non-covalent interactions of hen egg white lysozyme with N-acetyl glucosamine oligomers. Dissociation constant (K(D)) of the hen egg white lysozyme-N-acetyl glucosamine oligomer complex was determined by non-linear regression analysis, and the range of K(D) values (39+/-6 x 10(-6) and 19.6+/-8 x 10(-6) M for manual and automated infusions, respectively) confirms the previously reported values. Such miniaturization of a continuous-flow enzyme assay system to a microfluidic format can maximize the capabilities of mass spectrometric detection, reduce the sample size and analysis time required, as well as the associated costs for on-line enzymatic kinetic studies. PMID:20665926

  15. Class pi glutathione S-transferase: Meisenheimer complex formation.

    PubMed

    Bico, P; Chen, C Y; Jones, M; Erhardt, J; Dirr, H

    1994-08-01

    The enzyme-catalysed formation of the dead-end Meisenheimer complex, 1-(S-glutathionyl)-2,4,6-trinitrocyclohexadienate, between glutathione and 1,3,5-trinitrobenzene by two class pi glutathione S-transferases was studied under equilibrium conditions. The apparent formation constant of the complex at pH6.5, is 1.21 x 10(3) M-1 and 1.47 x 10(3) M-1 for isoenzyme pGSTP1-1 from porcine lung and hGSTP1-1 the human recombinant orthologue, respectively. These values are about 40- to 50-times larger than that determined for the nonenzymatic reaction in solution. Competitive inhibitors in the form of glutathione analogues that bind the G-site (glutathione sulphonate) or both the G-site and the H-site (S-hexylglutathione) regions of the active site markedly diminish complex formation. Comparison of kinetic data for glutathione S-transferase isoenzymes from the pi and mu gene classes suggests that the catalytic efficiencies for nucleophilic aromatic substitution reactions correspond with the ability of the enzyme's active site to stabilise the Meisenheimer complex. Formation of the red-coloured complex in orthorhombic crystals of pGSTP1-1 demonstrated that the crystallized protein retains its catalytically functional conformation in the crystal lattice. PMID:7987257

  16. Correlation between stabilities of uranyl ion complexes with various monocarboxylic acids and Hammett-Taft substituent constants

    SciTech Connect

    Poluektov, N.S.; Perfil'ev, V.A.; Meshkova, S.B.; Mishchenko, V.T.

    1987-01-01

    A correlation has been observed between the stabilities of uranyl ion complexes (1:1 composition) and the substituent inductive constants in formic and acetic acid derivatives. For substituents which are not directly involved in couples formation the parameters of the Hammett-Taft equation log K/sub 1/ = A + B have the following values: A = 1.311, B = -2.360. For substituents which form a coordination bond with the uranyl ion, A = 7.0077 and B = - 17.321. In the case of complexes formed between the uranyl ion and salicylic acid and its derivatives, there is a correlation between complex stability and sigma/sub m/ and sigma/sub p/ substituent constants for the meta- and para-positions, respectively (A = 12.72, B = -4.41).

  17. Star Formation Across the W3 Complex

    NASA Astrophysics Data System (ADS)

    Román-Zúñiga, Carlos G.; Ybarra, Jason E.; Megías, Guillermo D.; Tapia, Mauricio; Lada, Elizabeth A.; Alves, Joáo F.

    2015-09-01

    We present a multi-wavelength analysis of the history of star formation in the W3 complex. Using deep, near-infrared ground-based images combined with images obtained with Spitzer and Chandra observatories, we identified and classified young embedded sources. We identified the principal clusters in the complex and determined their structure and extension. We constructed extinction-limited samples for five principal clusters and constructed K-band luminosity functions that we compare with those of artificial clusters with varying ages. This analysis provided mean ages and possible age spreads for the clusters. We found that IC 1795, the centermost cluster of the complex, still hosts a large fraction of young sources with circumstellar disks. This indicates that star formation was active in IC 1795 as recently as 2 Myr ago, simultaneous to the star-forming activity in the flanking embedded clusters, W3-Main and W3(OH). A comparison with carbon monoxide emission maps indicates strong velocity gradients in the gas clumps hosting W3-Main and W3(OH) and shows small receding clumps of gas at IC 1795, suggestive of rapid gas removal (faster than the T Tauri timescale) in the cluster-forming regions. We discuss one possible scenario for the progression of cluster formation in the W3 complex. We propose that early processes of gas collapse in the main structure of the complex could have defined the progression of cluster formation across the complex with relatively small age differences from one group to another. However, triggering effects could act as catalysts for enhanced efficiency of formation at a local level, in agreement with previous studies.

  18. STABILITY CONSTANTS OF NP(V) COMPLEXES WITH FLOURIDE AND SULFATE AT VARIABLE TEMPERATURES

    SciTech Connect

    Y. Xia; J.I. Friese; D.A. Moore; L. Rao

    2005-07-11

    A solvent extraction method was used to determine the stability constants of Np(V) complexes with fluoride and sulfate in 1.0 M NaClO{sub 4} from 25 C to 60 C. The distribution ratio of Np(V) between the organic and aqueous phases was found to decrease as the concentrations of fluoride and sulfate were increased. Stability constants of the 1:1 Np(V)-fluoride complexes and the 1:1 Np(V)-sulfate and 1:2 Np(V)-sulfate complexes, dominant in the aqueous phase under the experimental conditions, were calculated from the effect of [F{sup -}] and [SO{sub 4}{sup 2-}] on the distribution ratio. The enthalpy and entropy of complexation were calculated from the stability constants at different temperatures by using the Van't Hoff equation.

  19. Measuring Dissociation Rate Constants of Protein Complexes through Subunit Exchange: Experimental Design and Theoretical Modeling

    SciTech Connect

    Pan, Chongle

    2011-01-01

    Protein complexes are generally dynamic macromolecules that constantly disintegrate into, and simultaneously are assembled from, free subunits. Dissociation rate constants, koff, provide important structure and function information on protein complexes. However, because all existing methods for measuring koff require high-quality purification and specific modifications of protein complexes, dissociation kinetics has only been studied for a small set of model complexes. Here we propose a new method, called Metabolically-labeled Affinity-tagged Subunit Exchange (MASE) to measure koff using metabolic labeling, affinity purification and mass spectrometry. MASE is based on a subunit exchange process between an unlabeled affinity-tagged variant and a metabolically-labeled untagged variant of a complex. In this study, the subunit exchange process was modeled theoretically for a heterodimeric complex. The results showed that koff determines, and hence can be estimated from, the observed rate of subunit exchange. Future study will be needed to experimentally validate the new method.

  20. A Simple Method for the Consecutive Determination of Protonation Constants through Evaluation of Formation Curves

    ERIC Educational Resources Information Center

    Hurek, Jozef; Nackiewicz, Joanna

    2013-01-01

    A simple method is presented for the consecutive determination of protonation constants of polyprotic acids based on their formation curves. The procedure is based on generally known equations that describe dissociation equilibria. It has been demonstrated through simulation that the values obtained through the proposed method are sufficiently

  1. Quantum mechanical capture/phase space theory calculation of the rate constants for the complex-forming CH + H{sub 2} reaction.

    SciTech Connect

    Saracibar, A.; Goldfield, E. M.; Gray, S. K.; Chemical Sciences and Engineering Division; Wayne State Univ.; Univ. del Pais Vasco

    2008-11-01

    Six-dimensional wave packet calculations on an accurate potential energy surface are used to obtain the quantum mechanical capture (QM C) probabilities for CH + H{sub 2} corresponding to a variety of total angular momenta and internal reactant states. Rate constant calculations are made feasible by employing a Monte Carlo based sampling procedure. The QM C probabilities alone are also used to estimate the high pressure CH + H{sub 2} rate constants corresponding to stabilization or CH{sub 3} formation. The rate constants for CH + H{sub 2} {yields} CH{sub 2} + H reaction in the low pressure limit are obtained by combining the QM C probabilities with a phase space theory (PST) approximation for product formation from the complex. Our results are compared with the experimental results of Brownsword et al. (J. Chem. Phys. 1997, 106, 7662), as well as with purely classical PST calculations. The QM C probabilities are shown to be highly dependent on the initial rotational states of the reactants corresponding to orientational restrictions on complex formation. Consistent with this, our QM C high pressure rate constants for CH{sub 3} formation are lower than the purely classical PST rate constants. These QM C rate constants also are in reasonable accord with experiment. A similar but somewhat more subtle picture emerges regarding the QM C/PST rate constants for CH{sub 2} + H formation.

  2. Determination of stability constants for complexes from catalytic linear scan voltammetric currents

    NASA Astrophysics Data System (ADS)

    Muiz Alvarez, J. L.; Garca Calzn, J. A.; Lpez Fonseca, J. M.

    1998-05-01

    A linear scan voltammetric method for determining stability constants for complexes formed in the bulk solution between metal ions and ligands that catalyse their reduction is proposed. The method is based on the pure limiting kinetic current produced in the electrocatalytic process, which is recorded following preconcentration of ligands by convective transport on a hanging mercury drop electrode until surface excesses reach the values for adsorption equilibrium with the bulk solution. The stability constant for the Ni(o-phenylenediamine)2+ complex provided by the proposed method is reasonably consistent with reported values obtained from catalytic dc polarographic currents. Une mthode voltammtrique balayage linaire de potentiel a t dveloppe pour la dtermination des constants de stabilit des complexes des ions mtalliques avec des ligands capables de catalyser leur rduction. La mthode utilise le courant limite cintique produite par la raction lectrocatalytique. Cette courante est enregistre aprs une priode de prconcentration du ligand la surface de l'lectrode de goutte pendante de mercure jusqu' la concentration superficiale atteint la valeur correspondante l'quilibre d'adsorption avec la solution. La valeur de la constant de stabilit mesure avec cette mthode pour le complexe Ni(o-phnylndiamine) est d'accord avec les valeurs obtenues de la courant catalytique en polarographie de courant continu.

  3. DISSOCIATION OF ARSENITE-PEPTIDE COMPLEXES: TRIPHASIC NATURE, RATE CONSTANTS, HALF LIVES AND BIOLOGICAL IMPORTANCE

    EPA Science Inventory

    We determined the number and the dissociation rate constants of different complexes formed from arsenite and two peptides containing either one (RV AVGNDYASGYHYGV for peptide 20) or three cysteines (LE AWQGK VEGTEHLYSMK K for peptide 10) via radioactive 73As labeled arsenite and ...

  4. Complex formation between uranyl and various thiosemicarbazide derivatives

    SciTech Connect

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

    1987-01-01

    Complex formation between hexavalent uranium and salicylaldehyde thiosemicarbazone (H/sub 2/L), salicylaldehyde S-methyl-isothiosemicarbazone (H/sub 2/Q), S-methyl-N/sub 1/,N/sub 4/-bis(salicylidene)isothiosemicarbazide(H/sub 2/Z), and thiosemicarbazidodiacetic acid (H/sub 2/R) has been studied spectrophotometrically in solution. Stability constants for complexes having the composition UO/sub 2/A have been calculated. Solid uranyl derivatives having the composition UO/sub 2/L x 2H/sub 2/O, UO/sub 2/Q x 2H/sub 2/O, UO/sub 2/Z x 2H/sub 2/O, and UO/sub 2/R x 2H/sub 2/O have been obtained. These derivatives were isolated and their IR spectroscopic behavior and thermal properties were investigated.

  5. Determination of the complex dielectric constant of an epithelial cell monolayer in the terahertz region

    NASA Astrophysics Data System (ADS)

    Shiraga, K.; Ogawa, Y.; Suzuki, T.; Kondo, N.; Irisawa, A.; Imamura, M.

    2013-02-01

    We present a method to determine the complex dielectric constant of a cell monolayer using terahertz time-domain attenuated total reflection spectroscopy combined with a two-interface model. The imaginary part of the dielectric constant of the cell monolayer shows a lower absorption of slow relaxation mode than that of the liquid medium. This result allows us to estimate the intracellular water dynamics on a picosecond time scale, and the existence of weakly hydrated water molecules inside the cell monolayer was indicated. This method will provide a perspective to investigate the intracellular water dynamics in detail.

  6. Stability constants important to the understanding of plutonium in environmental waters, hydroxy and carbonate complexation of PuO{sub 2}{sup +}

    SciTech Connect

    Bennett, D A

    1990-04-20

    The formation constants for the reactions PuO{sub 2}{sup +} + H{sub 2}O = PuO{sub 2}(OH) + H{sup +} and PuO{sub 2}{sup +} + CO{sub 3}{sup 2} = PuO{sub 2}(CO{sub 3}){sup {minus}} were determined in aqueous sodium perchlorate solutions by laser-induced photoacoustic spectroscopy. The molar absorptivity of the PuO{sub 2}{sup +} band at 569 nm decreased with increasing hydroxide concentration. Similarly, spectral changes occurred between 540 and 580 nm as the carbonate concentration was increased. The absorption data were analyzed by the non-linear least-squares program SQUAD to yield complexation constants. Using the specific ion interaction theory, both complexation constants were extrapolated to zero ionic strength. These thermodynamic complexation constants were combined with the oxidation-reduction potentials of Pu to obtain Eh versus pH diagrams. 120 refs., 35 figs., 12 tabs.

  7. Factors affecting the threading of axle molecules through macrocycles: Binding constants for semirotaxane formation

    PubMed Central

    Clifford, Thomas; Abushamleh, Ahmad; Busch, Daryle H.

    2002-01-01

    The threading of more or less linear axle molecules through macrocyclic molecules, a fundamental process relating to the formation of interlocked molecular structures, has been investigated through the study in acetone of the equilibrium constants for the formation of pseudorotaxanes by NMR methods. The 30 new axle molecules have in common a secondary ammonium group, present as the thiocyanate salt, and an anthracen-9-ylmethyl group, but are rendered unique by the second amine substituent. All rotaxanes involve the well known polyether macrocycle, benzo[24]crown-8. The constants for the binding of axles having linear groups ranging from 2 to 18 carbon atoms show little variation in binding constant but are divided into two groups by their equilibration rates. Those with less than five methylene groups react rapidly on the NMR timescale, whereas those having more than five methylene groups are slow. Branching inhibits binding, but the effect decreases as the branch is moved away from the amine. Phenyl groups weaken binding when close to the amine but strengthen binding when more remote. Some functional groups decrease pseudorotaxane stability (alcohol functions), whereas others increase binding (carboxylic acid groups). PMID:11959934

  8. Vortex formation in a complex plasma

    NASA Astrophysics Data System (ADS)

    Ishihara, Osamu

    Complex plasma experiments in ground-based laboratories as well as in microgravity conditions have shown the formation of vortex structures in various conditions (e.g., 1,2,3,4). The vortex structures formed in a complex plasma are visible by naked eyes with the help of irradiating laser and the individual dust particles in the structure give us the opportunity to study detailed physics of the commonly observed natural phenomena known such as tornadoes, typhoons, hurricanes and dust devils. Based on the Navier-Stokes equation with proper complex plasma conditions we analyze as much as possible in a universal way the vortex structure and clarifies the role of the controlling parameters like flow velocity and external magnetic field. 1. G. E. Morfill,H. M. Thomas, U. Konopka,H. Rothermel, M. Zuzic, A. Ivlev, and J. Goree, Phys,. Rev. Lett. 83, 1598 (1999). 2. E. Nebbat and R. Annou, Phys. Plasmas 17, 093702 (2010). 3. Y. Saitou and O. Ishihara, Phys. Rev. Lett. 111, 185003 (2013). 4. V. N. Tsytovich and N. G. Gusein-zade, Plasma Phys. Rep. 39, 515 (2013).

  9. Quasi-optical measurement of complex dielectric constant at 300 GHz

    NASA Astrophysics Data System (ADS)

    Stöckel, Bernd

    1993-10-01

    A two beam interferometer in the Martin-Puplett configuration is used to determine the complex dielectric constant at 300 GHz of teflon, TPX-plastics, SPECTRALON and paraffin waxes with melting temperatures of 48° C and 72° C, respectively. The design of the quasi-optical system leads to a constant beam diameter at the power detector independent of path delay and frequency. The power detector signal is recorded not only along one period but over about 50 periods. A spectrum estimation routine allows to determine more exactly amplitude and phase angle of the signal. A basic problem is noticed: imperfect detector and source match cause harmonic distortion of the power detector signal. The effects on processing the loss tangent and the invalidation are shown. Finally loss tangent and dielectric constant are determined indirectly by optimizing an equivalent microwave circuit using a commercial available microwave design system to take multiple reflections and losses in consideration.

  10. Simplified Representation of Partial and Total Rate Constants of Complex-Forming Bimolecular Reactions.

    PubMed

    Troe, J

    2015-12-17

    The temperature and pressure dependence of partial and total rate constants of complex-forming bimolecular reactions are investigated with the goal to obtain simplified and compact rate constant expressions suitable for data compilations. The transition of the reactions from low pressure chemical activation to high pressure association character is analyzed. The two processes are modeled separately first by solving master equations, leading to "inverse" and "normal" falloff curves, respectively, and allowing for a compact representation of the separated rate constants. It is shown that broadening factors of the two falloff curves are different, and those of chemical activation often approaching unity. Coupling of the two separate processes then is modeled in a simplified manner. Finally, thermal redissociation of the adducts formed by association is accounted for. PMID:26334454

  11. Temperature dependency of the equilibrium constant for the formation of carbamate from diethanolamine

    SciTech Connect

    Aroua, M.K.; Amor, A.B.; Haji-Sulaiman, M.Z.

    1997-07-01

    Aqueous alkanolamine solutions are frequently used to remove acidic components such as H{sub 2}S and CO{sub 2} from process gas streams. The equilibrium constant for the formation of diethanolamine carbamate was determined experimentally at (303, 313, 323, and 331) K for ionic strengths up to 1.8 mol/dm{sup 3}, the inert electrolyte being NaClO{sub 4}. A linear relationship was found to hole between log K and I{sup 0.5}. The thermodynamical constant has been determined and expressed by the equation log K{sub 1} = {minus}5.12 + 1.781 {times} 10{sup 3} K/T.

  12. Stability Constants of Technetium (IV) Oxalate Complexes as a Function of Ionic Strength

    SciTech Connect

    Xia, Yuanxian; Hess, Nancy J.; Felmy, Andrew R.

    2006-03-01

    Solvent extraction methods were used to determine the stability constants of Tc(IV) with oxalate anions in NaCl solutions ranging in concentration from 0.5 M to 2.0 M. All experiments were conducted in an atmosphere-controlled chamber under Ar atmosphere (< 1.0ppm O2). A reducing agent (hydrazine) was used during extractions to maintain technetium in the tetravalent oxidation state. Independent tests confirmed that the oxidation state of technetium did not change during extractions. The distribution ratio of Tc(IV) between the organic and aqueous phases was found to decrease as the concentration of oxalic acid increased. At the oxalic acid concentrations used in these experiments, the complexes TcO(Ox) and TcO(Ox)22- were found to be the dominant aqueous species. Based on these data, the thermodynamic stability constants of Tc(IV) with oxalate complexes were calculated by the Specific Ion Interaction Theory (SIT).

  13. Association constants and heats of formation of heteroassociates of anions of sulphophthaleine dyes

    NASA Astrophysics Data System (ADS)

    Shapovalov, S. A.

    2010-11-01

    The tendency of anions of sulphophthaleine dyes to heteroassociation was studied in aqueous solutions of phenol red, bromophenol blue, bromocresol green, bromocresol purple, and bromothymol blue. It was spectrophotometrically determined that single-(Han-) and double-charged anions (An2-) of sul-phophthaleines can form stable heteroassociates of composition Ct+ HAn- and (Ct+)2 An2- with cations (Ct+) of polymethine dyes, pinacyanol, and quinaldine red. The values of enthalpy formation of ions of dyes and heteroassociates were calculated using semi-empirical methods, then correlated with experimentally determined values of equilibrium association constants.

  14. QSPR prediction of the stability constants of gadolinium(III) complexes for magnetic resonance imaging.

    PubMed

    Dioury, Fabienne; Duprat, Arthur; Dreyfus, Gérard; Ferroud, Clotilde; Cossy, Janine

    2014-10-27

    Gadolinium(III) complexes constitute the largest class of compounds used as contrast agents for Magnetic Resonance Imaging (MRI). A quantitative structure-property relationship (QSPR) machine-learning based method is applied to predict the thermodynamic stability constants of these complexes (log KGdL), a property commonly associated with the toxicity of such organometallic pharmaceuticals. In this approach, the log KGdL value of each complex is predicted by a graph machine, a combination of parametrized functions that encodes the 2D structure of the ligand. The efficiency of the predictive model is estimated on an independent test set; in addition, the method is shown to be effective (i) for estimating the stability constants of uncharacterized, newly synthesized polyamino-polycarboxylic compounds and (ii) for providing independent log KGdL estimations for complexants for which conflicting or questionable experimental data were reported. The exhaustive database of log KGdL values for 158 complexants, reported for potential application as contrast agents for MRI and used in the present study, is available in the Supporting Information (122 primary literature sources). PMID:25181704

  15. Negative ion formation by Rydberg electron transfer: Isotope-dependent rate constants

    SciTech Connect

    Carman, H.S. Jr.; Klots, C.E.; Compton, R.N.

    1991-01-01

    The formation of negative ions during collisions of rubidium atoms in selected ns and nd Rydberg states with carbon disulfide molecules has been studied for a range of effective principal quantum numbers (10 {le} n* {le} 25). For a narrow range of n* near n* = 17, rate constants for CS{sub 2}{sup {minus}} formation are found to depend upon the isotopic composition of the molecule, producing a negative ion isotope ratio (mass 78 to mass 76, amu) up to 10.5 times larger than the natural abundance ratio of CS{sub 2} isotopes in the reagent. The isotope ratio is found to depend strongly upon the initial quantum state of the Rydberg atom and perhaps upon the collision energy and CS{sub 2} temperature. 32 refs., 5 figs., 1 tab.

  16. Stability Constants for Sulfate Complexation of Yttrium and the Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Schijf, J.; Byrne, R. H.

    2002-12-01

    In natural waters, yttrium and the rare earth elements (YREE) are mostly complexed with inorganic anions such as carbonate and chloride. YREE complexation with sulfate is minor (<5%) in seawater and generally negligible in fresh waters, yet it can be quite important in situations where oxidation of pyrite leads to high dissolved sulfate concentrations. The development of a consensus pattern of stability constants for YREE monosulfato-complexes has a quite convoluted history. It is based on a 1974 'compilation' that was derived from a much older, somewhat questionable, dataset, by adding interpolations and omitting a few elements. During subsequent transcriptions, some errors were introduced and the omitted data were interpolated rather than replaced with the original values. All this has resulted in a consensus pattern that is essentially flat, without any structure or fractionation between light and heavy REE. It is widely quoted and has been used to argue that sulfate complexation does not cause YREE fractionation. Conversely, flat YREE patterns in natural waters have been taken as evidence for substantial complexation of the YREE with sulfate. We have taken a new approach to measuring the stability constants of all YREE monosulfato-complexes with the greatest possible precision. Stability constants were determined by comparing the solubility of barium sulfate in YREE chloride solutions and in an ammonium chloride reference solution, all at the ionic strength of seawater. The reference solution and solutions of individual YREE chlorides were equilibrated with a small amount of high purity barium sulfate at t = 25C for at least one week. The equilibrated solutions were then filtered and analyzed for concentrations of YREE and Ba (ICP-MS), chloride and sulfate (ion chromatography), and pH (glass electrode). A simple model was used to determine the stability constants from these measurements. Averaged results from four experiments, two with and two without added sulfate, have standard deviations of 0.03 log units or less. Within this precision, the pattern of stability constants is not flat, as has been assumed, but has a very distinct shape. The pattern is nearly flat from La to Gd, possibly with a slight maximum at Eu. From Gd to Lu it shows a gradual and almost linear decrease, with the stability constant of Lu being more than 0.2 log units below that of La. The stability constant of Y is close to that of Er. Our pattern is in broad agreement with several careful earlier studies that have been largely ignored in the recent literature. Comparison with the substantial body of existing work also indicates that our stability constants are well within the published range for individual YREE. This revised pattern may have significant consequences for the interpretation of YREE patterns in high-sulfate environments such as runoff from mine tailings and certain groundwaters.

  17. Estimating the acidity of transition metal hydride and dihydrogen complexes by adding ligand acidity constants.

    PubMed

    Morris, Robert H

    2014-02-01

    A simple equation (pKa(THF) = ?AL + Ccharge + Cnd + Cd6) can be used to obtain an estimate of the pKa of diamagnetic transition metal hydride and dihydrogen complexes in tetrahydrofuran, and, by use of conversion equations, in other solvents. It involves adding acidity constants AL for each of the ligands in the 5-, 6-, 7-, or 8-coordinate conjugate base complex of the hydride or dihydrogen complex along with a correction for the charge (Ccharge = -15, 0 or 30 for x = +1, 0 or -1 charge, respectively) and the periodic row of the transition metal (Cnd = 0 for 3d or 4d metal, 2 for 5d metal) as well as a correction for d(6) octahedral acids (Cd6 = 6 for d(6) metal ion in the acid, 0 for others) that are not dihydrogen complexes. Constants AL are provided for 13 commonly occurring ligand types; of these, nine neutral ligands are correlated with Lever's electrochemical ligand parameters EL. This method gives good estimates of the over 170 literature pKa values that range from less than zero to 50 with a standard deviation of 3 pKa units for complexes of the metals chromium to nickel, molybdenum, ruthenium to palladium, and tungsten to platinum in the periodic table. This approach allows a quick assessment of the acidity of hydride complexes found in nature (e.g., hydrogenases) and in industry (e.g., catalysis and hydrogen energy applications). The pKa values calculated for acids that have bulky or large bite angle chelating ligands deviate the most from this correlation. The method also provides an estimate of the base strength of the deprotonated form of the complex. PMID:24410025

  18. Three stages of bubble formation on submerged orifice under constant gas flow rate

    NASA Astrophysics Data System (ADS)

    Yu, Xianxian; Wang, Yiwei; Huang, Chenguang; Du, Tezhuan

    2015-12-01

    Bubble formation is involved in many engineering applications. It is important to understand the dynamics of bubble formation. This work reports experimental and numerical results of bubble formation on submerged orifice under constant gas flow rate. Compressible large eddy simulation combined volume of fluid (VOF) was adopted in simulation and results was validated by experiment. Bubble formation is divided into three stages in this paper, expansion stage, elongation stage and pinch-off stage. In expansion stage, The bubble grows radially due to the incoming gas flux, but the bubble base remains attached to the orifice. But as gas injected, the spherical bubble will go into the elongation stage when the downward resultant force is lager than upward resultant force. And when bubble neck's length is bigger than ?2Ro the bubble will go into pinch-off stage. Cylindrical Rayleigh-Plesset equation can be used to describe the pinch-off stage. Uncertain parameter r in it is given reference value in this paper.

  19. Analysis of association constant for ground state dye-electron acceptor complex of photoinitiator systems and the association constant effect on the kinetics of visible-light-induced polymerizations

    PubMed Central

    Kim, Dongkwan; Scranton, Alec B.; Stansbury, Jeffrey W.

    2009-01-01

    We investigated the formation of ground state donor/acceptor complexes between xanthene dyes (rose Bengal (RB) and fluorescein (FL)) and a diphenyl iodonium salt (DPI) which is dissolved in 2-hydroxyethyl methacrylate (HEMA) monomer. To characterize the association constant of the complex, we have suggested a new analysis model based upon the Benesi-Hildebrand model. Because the assumption of the original Benesi-Hildebrand model is that the absorption bands are due only to the presence of the complex and that the absorption by the free component is negligible; the model cannot be applied to our systems, which is a dye-based initiator system. For each dye, the molar absorptivity of the ground state complex was evaluated as a function of wavelength and this analysis confirmed the validity of the modified Benesi-Hildebrand model. In addition, we observed the RB/DPI photoinitiator system failed to produce a perceptible polymerization rate but the FL/DPI photoinitiator system provided very high rates of polymerization. Based upon the association constant for these complexes, we concluded that the observed kinetic differences arise from the different association constant values of the ground state dye-acceptor complex, resulting in back electron transfer reaction. PMID:20161099

  20. Constant Electric and Magnetic Fields Effect on the Structuring and Thermomechanical and Thermophysical Properties of Nanocomposites Formed from Pectin-Cu(2+)-Polyethyleneimine Interpolyelectrolyte-Metal Complexes.

    PubMed

    Demchenko, V; Shtompel', V; Riabov, S; Lysenkov, E

    2015-12-01

    Applying wide-angle X-ray scattering method, thermomechanical analysis, and differential scanning calorimetry, the structural organization and properties of nanocomposites formed by chemical reduction of ?u(2+) cations in the interpolyelectrolyte-metal complex (pectin-Cu(2+)-polyethyleneimine) under the influence of a constant magnetic and electric fields have been studied. It has been found that the chemical reduction of Cu(2+) cations in the interpolyelectrolyte-metal complex bulk under constant electric and magnetic fields leads to formation of nanocomposite consisting of interpolyelectrolyte complex, including pectin-polyethyleneimine and nanoparticles of the metal Cu phase, whereas nanocomposite with Cu/Cu2O nanoparticles is formed in original state (without any field). It was observed that, under constant field, nanocomposites obtained have higher structural glass-transition temperatures and thermal stability. PMID:26659610

  1. Constant Electric and Magnetic Fields Effect on the Structuring and Thermomechanical and Thermophysical Properties of Nanocomposites Formed from Pectin-Cu2+-Polyethyleneimine Interpolyelectrolyte-Metal Complexes

    NASA Astrophysics Data System (ADS)

    Demchenko, V.; Shtompel', V.; Riabov, S.; Lysenkov, E.

    2015-12-01

    Applying wide-angle X-ray scattering method, thermomechanical analysis, and differential scanning calorimetry, the structural organization and properties of nanocomposites formed by chemical reduction of Cu2+ cations in the interpolyelectrolyte-metal complex (pectin-Cu2+-polyethyleneimine) under the influence of a constant magnetic and electric fields have been studied. It has been found that the chemical reduction of Cu2+ cations in the interpolyelectrolyte-metal complex bulk under constant electric and magnetic fields leads to formation of nanocomposite consisting of interpolyelectrolyte complex, including pectin-polyethyleneimine and nanoparticles of the metal Cu phase, whereas nanocomposite with Cu/Cu2O nanoparticles is formed in original state (without any field). It was observed that, under constant field, nanocomposites obtained have higher structural glass-transition temperatures and thermal stability.

  2. Cyclodextrins in pharmaceutical formulations II: solubilization, binding constant, and complexation efficiency.

    PubMed

    Jambhekar, Sunil S; Breen, Philip

    2016-02-01

    Cyclodextrins are cyclic oligosaccharides that have been recognized as pharmaceutical adjuvants for the past 20 years. The molecular structure of these glucose derivatives, which approximates a truncated cone, bucket, or torus, generates a hydrophilic exterior surface and a nonpolar interior cavity. Cyclodextrins can interact with appropriately sized drug molecules to yield an inclusion complex. These noncovalent inclusion complexes offer a variety of advantages over noncomplexed forms of a drug. Cyclodextrins are carbohydrates that are primarily used to enhance the aqueous solubility, physical chemical stability, and bioavailability of drugs. Their other applications include preventing drug-drug interactions, converting liquid drugs into microcrystalline powders, minimizing gastrointestinal and ocular irritation, and reducing or eliminating unpleasant taste and smell. Here, we focus on the solubilization of drugs by complexation, and discuss the determination and significance of binding constants for cyclodextrin complexes, and the determination of complexation efficiency and factors that influence it. We also make some general observations on cyclodextrin complexation and the use of cyclodextrins in solid, as well as parenteral, dosage forms. PMID:26687191

  3. Stability Constants of Mixed Ligand Complexes of Nickel(II) with Adenine and Some Amino Acids

    PubMed Central

    Türkel, Naciye

    2015-01-01

    Nickel is one of the essential trace elements found in biological systems. It is mostly found in nickel-based enzymes as an essential cofactor. It forms coordination complexes with amino acids within enzymes. Nickel is also present in nucleic acids, though its function in DNA or RNA is still not clearly understood. In this study, complex formation tendencies of Ni(II) with adenine and certain L-amino acids such as aspartic acid, glutamic acid, asparagine, leucine, phenylalanine, and tryptophan were investigated in an aqueous medium. Potentiometric equilibrium measurements showed that both binary and ternary complexes of Ni(II) form with adenine and the above-mentioned L-amino acids. Ternary complexes of Ni(II)-adenine-L-amino acids are formed by stepwise mechanisms. Relative stabilities of the ternary complexes are compared with those of the corresponding binary complexes in terms of Δlog10⁡K, log10⁡X, and % RS values. It was shown that the most stable ternary complex is Ni(II):Ade:L-Asn while the weakest one is Ni(II):Ade:L-Phe in aqueous solution used in this research. In addition, results of this research clearly show that various binary and ternary type Ni(II) complexes are formed in different concentrations as a function of pH in aqueous solution. PMID:26843852

  4. Efficient Algorithm Using a Broadband Approach to Determine the Complex Constants of Piezoelectric Ceramics

    NASA Astrophysics Data System (ADS)

    Buiochi, F.; Kiyono, C. Y.; Perz, N.; Adamowski, J. C.; Silva, E. C. N.

    A new systematic and efficient algorithm to obtain the ten complex constants of piezoelectric materials belonging to the 6 mm symmetry class was developed. A finite element method routine was implemented in Matlab using eight-node axisymmetric elements. The algorithm raises the electrical conductance and resistance curves and calculates the quadratic difference between the experimental and numerical curves. Finally, to minimize the difference, an optimization algorithm based on the "Method of Moving Asymptotes" (MMA) is used. The algorithm is able to adjust the curves over a wide frequency range obtaining the real and imaginary parts of the material properties simultaneously.

  5. Variation of lattice constant and cluster formation in GaAsBi

    SciTech Connect

    Puustinen, J.; Schramm, A.; Guina, M.; Wu, M.; Luna, E.; Laukkanen, P.; Laitinen, M.; Sajavaara, T.

    2013-12-28

    We investigate the structural properties of GaAsBi layers grown by molecular beam epitaxy on GaAs at substrate temperatures between 220315 C. Irrespective of the growth temperature, the structures exhibited similar Bi compositions, and good overall crystal quality as deduced from X-Ray diffraction measurements. After thermal annealing at temperatures as low as 500 C, the GaAsBi layers grown at the lowest temperatures exhibited a significant reduction of the lattice constant. The lattice variation was significantly larger for Bi-containing samples than for Bi-free low-temperature GaAs samples grown as a reference. Rutherford backscattering spectrometry gave no evidence of Bi diffusing out of the layer during annealing. However, dark-field and Z-contrast transmission electron microscopy analyses revealed the formation of GaAsBi clusters with a Bi content higher than in the surrounding matrix, as well as the presence of metallic As clusters. The apparent reduction of the lattice constant can be explained by a two-fold process: the diffusion of the excess As incorporated within As{sub Ga} antisites to As clusters, and the reduction of the Bi content in the GaAs matrix due to diffusion of Bi to GaAsBi clusters. Diffusion of both As and Bi are believed to be assisted by the native point defects, which are present in the low-temperature as-grown material.

  6. Ion pair formation in water. association constants of bolaform, bisquaternary ammonium, electrolytes by chemical trapping.

    PubMed

    Geng, Yan; Romsted, Laurence S

    2005-12-15

    The first and second association constants, K1 and K2, for ion pair formation in aqueous 0.02-3.5 M solutions of bis(trimethyl)-alpha,omega-alkanediammonium halides with variable spacer lengths, 1-n-1 2X (n = 2-4, X = Cl, Br) and bolaform salts and for tetramethylammonium halides (TMAX, X = Cl, Br), K(TMAX), were determined by the chemical trapping method. Values for K(TMAX) are small, K(TMABr) = 0.83 M(-1) and K(TMACl) = 0.29 M(-1), in agreement with literature values. For the bolaform salts, K1 depends on spacer length and counterion type, ranges from 0.4 to 17 M(-1), is 2-10 times larger than K2, is larger for Br- than Cl-, and decreases by a factor of approximately 3 for Cl- and approximately 10 for Br- as n increases from 2 to 4. K2, for the formation of bolaform dihalide pair, is essentially the same as that for ion pair formation in TMAX solutions, i.e., K2 approximately K(TMAX). Values of K1 and K(TMABr) obtained from changes in 79Br line widths are in good agreement with those obtained by chemical trapping. The results are consistent with a thermodynamic model in which the ion association depends on the balance of the ion specific hydration free energies of cations and anions and their ion specific and hydration interactions in ion pairs. Spacer length dependent ion pairing by bolaform electrolytes, which are analogues of the headgroups and counterions of gemini amphiphiles, suggests a new model for the spacer length dependent sphere-to-rod transitions of gemini micelles. Neutral, but polar, headgroup-counterion pairs have a lower demand for hydration that free headgroups and counterions, and headgroup-counterion pair formation releases interfacial water into the bulk aqueous phase, permitting tighter amphiphile packing in rodlike micelles. PMID:16375341

  7. Models for ionic contribution to the complex dielectric constant of nematic liquid crystals

    NASA Astrophysics Data System (ADS)

    Alexe-Ionescu, A. L.; Barbero, G.; Lelidis, I.

    2009-12-01

    We analyze the models that account the ionic contribution to the complex dielectric constant of a nematic liquid crystal. We compare the predictions of the model of [Sawada , Mol. Cryst. Liq. Cryst. Sci. Technol., Sect. A 318, 225 (1998)] based on the assumption that the electric field in the liquid coincides with the applied one, with the model of Macdonald where the electric field in the sample is determined in self-consistent manner by solving the equation of Poisson. We show that the model of Sawada , widely used to determine the bulk density of ions and their diffusion coefficient in liquid crystal cells, predicts a thickness dependence of the real and imaginary parts of the dielectric constant different from that predicted by the model of Macdonald. On the contrary, the predictions of the two models coincide for what concerns the frequency dependencies of the two components of the dielectric constant. By considering a typical case, we show that the numerical values of the ionic properties derived by means of the model of Sawada may differ even more than 1 order of magnitude by those predicted by the model of Macdonald. A rescaling procedure allowing to evaluate the bulk density of ions and the ionic diffusion coefficient determined by means of the model of Sawada in agreement with the one of Macdonald is proposed.

  8. Solubility of schoepite: comparison and selection of complexation constants for U(VI).

    PubMed

    Jang, Je-Hun; Dempsey, Brian A; Burgos, William D

    2006-08-01

    Solubility of UO(3) x nH(2)O and sorption of U(VI) onto ferric (hydr)oxides were measured at pH 5.9, 6.8, and 7.8 at 10(-3.5)atm CO(2) using reaction times up to 48 days. Precipitation was fastest in the presence of hydrous ferric oxide and slower with hematite or without an initial solid phase. Solubility after 48 days was statistically similar for low to intermediate initial supersaturation conditions and increased for the highest initial supersaturation. Schoepite was identified for low-to-intermediate initial conditions of supersaturation and was not found for the highest initial supersaturation. Predicted concentrations of monomeric and polymeric species differed considerably with the different suites of complexation constants, resulting in significant differences in predicted oxidation-reduction potential and mobility of U(VI) in groundwater. Solubilities for low to intermediate initial supersaturation were best represented using complexation constants from Langmuir, D. [1978. Uranium solution-mineral equilibria at low temperatures with applications to sedimentary ore deposits. Geochim. Cosmochim. Acta 42, 547-569] and log*K(sp)=5.39 for schoepite, while solubilities for very high initial supersaturation were consistent with amorphous UO(3) x nH(2)O. PMID:16780919

  9. The Complexity of Integrable Hamiltonian Systems on a Prescribed Three-Dimensional Constant-Energy Submanifold

    NASA Astrophysics Data System (ADS)

    T'en Zung, Nguen

    1993-02-01

    This paper is devoted to a description of \\mathcal{Q}-regions, i.e., domains in the molecular table of Fomenko that are filled with integrable systems with constant energy surfaces \\mathcal{Q} that occur most frequently in physics. Namely, the \\mathcal{Q}-regions for \\mathcal{Q}=S^3, \\mathbf{R}P^3, S^1\\otimes S^2, T^3, and \\char93 ^l S^1\\otimes S^2 are computed explicitly. The \\mathcal{Q}-regions for an arbitrary three-dimensional constant energy submanifold \\mathcal{Q} are determined up to a finite number of points. These results make it possible to predict the topological properties of integrable Hamiltonian systems as yet not discovered in physics. The concepts of the order of torsion of integrable Hamiltonian systems and of a minimal system are also introduced, and the connection between these concepts and the concepts of complexity of systems and complexity of three-manifolds due to Matveev is indicated.

  10. On the Formation of "Hypercoordinated" Uranyl Complexes

    SciTech Connect

    Schoendorff, George E.; De Jong, Wibe A.; van Stipdonk, Michael J.; Gibson, John K.; Rios, Daniel; Gordon, Mark S.; Windus, Theresa L.

    2011-09-05

    Recent gas phase experimental studies suggest the presence of hypercoordinated uranyl complexes. Coordination of acetone (Ace) to uranyl to form hypercoordinated species is examined using density functional theory (DFT) with a range of functionals and second order perturbation theory (MP2). Complexes with up to eight acetones were studied. It is shown that no more than six acetones can bind directly to uranium and that the observed uranyl complexes are not hypercoordinated.

  11. Complex unconstrained three-dimensional hand movement and constant equi-affine speed.

    PubMed

    Maoz, Uri; Berthoz, Alain; Flash, Tamar

    2009-02-01

    One long-established simplifying principle behind the large repertoire and high versatility of human hand movements is the two-thirds power law-an empirical law stating a relationship between local geometry and kinematics of human hand trajectories during planar curved movements. It was further generalized not only to various types of human movements, but also to motion perception and prediction, although it was unsuccessful in explaining unconstrained three-dimensional (3D) movements. Recently, movement obeying the power law was proved to be equivalent to moving with constant planar equi-affine speed. Generalizing such motion to 3D space-i.e., to movement at constant spatial equi-affine speed-predicts the emergence of a new power law, whose utility for describing spatial scribbling movements we have previously demonstrated. In this empirical investigation of the new power law, subjects repetitively traced six different 3D geometrical shapes with their hand. We show that the 3D power law explains the data consistently better than both the two-thirds power law and an additional power law that was previously suggested for spatial hand movements. We also found small yet systematic modifications of the power-law's exponents across the various shapes, which further scrutiny suggested to be correlated with global geometric factors of the traced shape. Nevertheless, averaging over all subjects and shapes, the power-law exponents are generally in accordance with constant spatial equi-affine speed. Taken together, our findings provide evidence for the potential role of non-Euclidean geometry in motion planning and control. Moreover, these results seem to imply a relationship between geometry and kinematics that is more complex than the simple local one stipulated by the two-thirds power law and similar models. PMID:19073811

  12. Measurements of the complex dielectric constant of sand and dust particles at 11 GHz

    NASA Astrophysics Data System (ADS)

    Al-Rizzo, Hussain M.; Al-Hafid, Hafid T.

    1988-03-01

    Measurements are reported of the refractive index (Delta-n) and loss tangent (tan delta) of dust particles in a laboratory-simulated model of dust storms, carried out at 11 GHz utilizing a confocal microwave open-cavity resonator. Four samples were used namely, sandy, silty, clayey silt, and clayey, for concentrations varying from 10-4 to 4 x 10-3 g/cu cm. The particle-size distribution (PSD) of each sample was measured by seiving along with the hydrometer technique. Dielectric-constant measurements were also conducted at bulk concentrations using the standing-wave technique for the dry samples and as a function of volumetric moisture content for up to 0.5 cu cm/cu cm. The complex dielectric constant of the dust particle material was evaluated by two approaches. In one the data for permittivities obtained over the whole range of measured concentrations were extrapolated to the particle densities of the samples. In the other a mixing formula was utilized for the determination of epsilon(s) from permittivities measured at bulk concentrations.

  13. Polarographic determination of lead hydroxide formation constants at low ionic strength

    USGS Publications Warehouse

    Lind, Carol J.

    1978-01-01

    Values of formation constants for lead hydroxide at 25 ??C were calculated from normal pulse polarographic measurements of 10-6 M lead in 0.01 M sodium perchlorate. The low concentrations simulate those found in many freshwaters, permitting direct application of the values when considering distributions of lead species. The precise evaluation of species distribution in waters at other ionic strengths requires activity coefficient corrections. As opposed to much of the previously published work done at high ionic strength, the values reported here were obtained at low ionic strength, permitting use of smaller and better defined activity coefficient corrections. These values were further confirmed by differential-pulse polarography and differential-pulse anodic stripping voltammetry data. The logs of the values for ??1??? ??2???, and ??3??? were calculated to be 6.59, 10.80, and 13.63, respectively. When corrected to zero ionic strength these values were calculated to be 6.77, 11.07, and 13.89, respectively.

  14. The shock-induced star formation sequence resulting from a constant spiral pattern speed

    SciTech Connect

    Martnez-Garca, Eric E.; Puerari, Ivnio E-mail: puerari@inaoep.mx

    2014-08-01

    We utilize a suite of multiwavelength data of nine nearby spirals to analyze the shock-induced star formation sequence that may result from a constant spiral pattern speed. The sequence involves tracers as the H I, CO 24 ?m, and FUV, where the spiral arms were analyzed with Fourier techniques in order to obtain their azimuthal phases as a function of radius. It was found that only two of the objects, NGC 628 and NGC 5194, present coherent phases resembling the theoretical expectations, as indicated by the phase shifts of CO- 24 ?m. The evidence is more clear for NGC 5194 and moderate for NGC 628. It was also found that the phase shifts are different for the two spiral arms. With the exception on NGC 3627, a two-dimensional Fourier analysis showed that the rest of the objects do not exhibit bi-symmetric spiral structures of stellar mass, i.e., grand-design spirals. A phase order inversion indicates a corotation radius of ?89'' for NGC 628 and ?202'' for NGC 5194. For these two objects, the CO-H? phase shifts corroborate the CO-24 ?m azimuthal offsets. Also for NGC 5194, the CO-70 ?m, CO-140 ?m, and CO-250 ?m phase shifts indicate a corotation region.

  15. Spectrophotometric quantification of the thermodynamic constants of the complexes formed by dopamine and Cu(II) in aqueous media

    NASA Astrophysics Data System (ADS)

    Verastegui-Omaña, B.; Palomar-Pardavé, M.; Rojas-Hernández, A.; Corona Avendaño, S.; Romero-Romo, M.; Ramírez-Silva, M. T.

    2015-05-01

    The thermodynamic constants of the complex Cu(II)-dopamine in aqueous solution were evaluated from spectrophotometric data using the software SQUAD. It was found that there exist Cu(II):DA complexes with 1:1 and 1:2 stoichiometries and that their predominance depends on both the solution pH and the [Cu(II)]/[DA] ratio. Moreover, it is shown that the solubility of Cu(OH)2(s) increases drastically when these complexes are thermodynamically stable.

  16. Direct electronic probing of biological complexes formation

    NASA Astrophysics Data System (ADS)

    Macchia, Eleonora; Magliulo, Maria; Manoli, Kyriaki; Giordano, Francesco; Palazzo, Gerardo; Torsi, Luisa

    2014-10-01

    Functional bio-interlayer organic field - effect transistors (FBI-OFET), embedding streptavidin, avidin and neutravidin as bio-recognition element, have been studied to probe the electronic properties of protein complexes. The threshold voltage control has been achieved modifying the SiO2 gate diaelectric surface by means of the deposition of an interlayer of bio-recognition elements. A threshold voltage shift with respect to the unmodified dielectric surface toward more negative potential values has been found for the three different proteins, in agreement with their isoelectric points. The relative responses in terms of source - drain current, mobility and threshold voltage upon exposure to biotin of the FBI-OFET devices have been compared for the three bio-recognition elements.

  17. Formation of a Bridging Phosphinidene Thorium Complex.

    PubMed

    Behrle, Andrew C; Castro, Ludovic; Maron, Laurent; Walensky, Justin R

    2015-12-01

    The synthesis and structural determination of the first thorium phosphinidene complex are reported. The reaction of 2 equiv of (C5Me5)2Th(CH3)2 with H2P(2,4,6-(i)Pr3C6H2) at 95 C produces [(C5Me5)2Th]2(?2-P[(2,6-CH2CHCH3)2-4-(i)PrC6H2] as well as 4 equiv of methane, 2 equiv from deprotonation of the phosphine and 2 equiv from C-H bond activation of one methyl group of each of the isopropyl groups at the 2- and 6-positions. Transition state calculations indicate that the steps in the mechanism are P-H, C-H, C-H, and then P-H bond activation to form the phosphinidene. PMID:26575219

  18. Universal reaction mechanism of boronic acids with diols in aqueous solution: kinetics and the basic concept of a conditional formation constant.

    PubMed

    Furikado, Yuki; Nagahata, Tomomi; Okamoto, Takuya; Sugaya, Tomoaki; Iwatsuki, Satoshi; Inamo, Masahiko; Takagi, Hideo D; Odani, Akira; Ishihara, Koji

    2014-10-01

    To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants (Ka(BL)) of boronic acid diol esters (HBLs) were determined based on the well-established concept of conditional formation constants of metal complexes. The pKa values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4-difluorophenylboronic acid and chromotropic acid, 3-nitrophenylboronic acid and alizarin red?S, and phenylboronic acid and alizarin red?S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a)?the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b)?the determined pKa values of HBLs. The use of the conditional formation constant, K', based on the main reaction: RB(OH)2 + H2L (K1)? RB(L)(OH)(-) + H3O(+) instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B') with uncomplexed diol species (L') to form boronic acid diol complex species (esters, BL') in aqueous solution at pH?5-11: B' + L' (K')? BL'. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution. PMID:25169423

  19. Dynamics of Lane Formation in Driven Binary Complex Plasmas

    SciTech Connect

    Suetterlin, K. R.; Ivlev, A. V.; Raeth, C.; Thomas, H. M.; Rubin-Zuzic, M.; Morfill, G. E.; Wysocki, A.; Loewen, H.; Goedheer, W. J.; Fortov, V. E.; Lipaev, A. M.; Molotkov, V. I.; Petrov, O. F.

    2009-02-27

    The dynamical onset of lane formation is studied in experiments with binary complex plasmas under microgravity conditions. Small microparticles are driven and penetrate into a cloud of big particles, revealing a strong tendency towards lane formation. The observed time-resolved lane-formation process is in good agreement with computer simulations of a binary Yukawa model with Langevin dynamics. The laning is quantified in terms of the anisotropic scaling index, leading to a universal order parameter for driven systems.

  20. Complex formation of metal ions with xylenol orange

    SciTech Connect

    Tikhonov, V.N.

    1987-01-20

    The complex formation of metals with xylenol orange, purified by gel filtration on Molselekt G-10, was studied. The spectrophotometric characteristics of the complexes formed were refined. The chemistry of the reaction with xylenol orange was studied. A method was developed for the determination of aluminum in copper alloys.

  1. Depassivation of aged Fe 0 by divalent cations: correlation between contaminant degradation and surface complexation constants.

    PubMed

    Liu, Tongxu; Li, Xiaomin; Waite, T David

    2014-12-16

    The dechlorination of trichloroethylene (TCE) by aged Fe(0) in the presence of a series of divalent cations was investigated with the result that while no significant degradation of TCE was observed in Milli-Q water or in solutions of Ba(2+), Sr(2+), or Ca(2+), very effective TCE removal was observed in solutions containing Mg(2+), Mn(2+), Co(2+), Fe(2+), Ni(2+), Zn(2+), Cu(2+), or Pb(2+). The rate constants of TCE removal in the presence of particular cations were positively correlated to the log K representing the affinity of the cations for hydrous ferric oxide (HFO) surface sites though the treatments with Co(2+) and Ni(2+) were found to provide particularly strong enhancement in TCE degradation rate. The extent of Fe(II) release to solution also increased with increase in log K, while the solution pH from both experimental measurement and thermodynamic calculation decreased with increasing log K. While the peak areas of Fe and O XPS spectra of the passivated ZVI in the presence of Ba(2+), Sr(2+), and Ca(2+) were very close to those in Milli-Q water, very significant increases in surface Fe and O (and OH) were observed in solutions of Mg(2+), Mn(2+), Co(2+), Fe(2+), Ni(2+), Zn(2+), Cu(2+) and Pb(2+), revealing that the surface oxide layer dissolution is consistent with the recovery of aged Fe(0) with respect to TCE degradation. The depassivation process is proposed to involve (i) surface complexation of cations on surface coatings of aged Fe(0), (ii) dissolution of the hydrated surface as a consequence of magnetite exposure, and (iii) transport of electrons from underlying Fe(0) via magnetite to TCE, resulting in TCE dechlorination and, for some cations (Co(2+), Ni(2+), Cu(2+), and Pb(2+)), reduction to their zero or +1 valence state (with potential for these reduced metals to enhance TCE degradation). PMID:25383907

  2. Complex molecule formation around massive young stellar objects.

    PubMed

    Oberg, Karin I; Fayolle, Edith C; Reiter, John B; Cyganowski, Claudia

    2014-01-01

    Interstellar complex organic molecules were first identified in the hot inner regions of massive young stellar objects (MYSOs), but have more recently been found in many colder sources, indicating that complex molecules can form at a range of temperatures. However, individually these observations provide limited constraints on how complex molecules form, and whether the same formation pathways dominate in cold, warm and hot environments. To address these questions, we use spatially resolved observations from the Submillimeter Array of three MYSOs together with mostly unresolved literature data to explore how molecular ratios depend on environmental parameters, especially temperature. Towards the three MYSOs, we find multiple complex organic emission peaks characterized by different molecular compositions and temperatures. In particular, CH3CCH and CH3CN seem to always trace a lukewarm (T = 60 K) and a hot (T > 100 K) complex chemistry, respectively. These spatial trends are consistent with abundance-temperature correlations of four representative complex organics--CH3CCH, CH3CN, CH3OCH3 and CH3CHO--in a large sample of complex molecule hosts mined from the literature. Together, these results indicate a general chemical evolution with temperature, i.e. that new complex molecule formation pathways are activated as a MYSO heats up. This is qualitatively consistent with model predictions. Furthermore, these results suggest that ratios of complex molecules may be developed into a powerful probe of the evolutionary stage of a MYSO, and may provide information about its formation history. PMID:25302375

  3. Complex molecule formation around massive young stellar objects

    NASA Astrophysics Data System (ADS)

    berg, Karin I.; Fayolle, Edith C.; Reiter, John B.; Cyganowski, Claudia

    2014-02-01

    Interstellar complex organic molecules were first identified in the hot inner regions of massive young stellar objects (MYSOs), but have more recently been found in many colder sources, indicating that complex molecules can form at a range of temperatures. However, individually these observations provide limited constraints on how complex molecules form, and whether the same formation pathways dominate in cold, warm and hot environments. To address these questions, we use spatially resolved observations from the Submillimeter Array of three MYSOs together with mostly unresolved literature data to explore how molecular ratios depend on environmental parameters, especially temperature. Towards the three MYSOs, we find multiple complex organic emission peaks characterized by different molecular compositions and temperatures. In particular, CH3CCH and CH3CN seem to always trace a lukewarm (T ? 60 K) and a hot (T > 100 K) complex chemistry, respectively. These spatial trends are consistent with abundance-temperature correlations of four representative complex organics - CH3CCH, CH3CN, CH3OCH3 and CH3CHO - in a large sample of complex molecule hosts mined from the literature. Together, these results indicate a general chemical evolution with temperature, i.e. that new complex molecule formation pathways are activated as a MYSO heats up. This is qualitatively consistent with model predictions. Furthermore, these results suggest that ratios of complex molecules may be developed into a powerful probe of the evolutionary stage of a MYSO, and may provide information about its formation history.

  4. Particle formation during oxidation catalysis with Cp* iridium complexes.

    PubMed

    Hintermair, Ulrich; Hashmi, Sara M; Elimelech, Menachem; Crabtree, Robert H

    2012-06-13

    Real-time monitoring of light scattering and UV-vis profiles of four different Cp*Ir(III) precursors under various conditions give insight into nanoparticle formation during oxidation catalysis with NaIO(4) as primary oxidant. Complexes bearing chelate ligands such as 2,2'-bipyridine, 2-phenylpyridine, or 2-(2'-pyridyl)-2-propanolate were found to be highly resistant toward particle formation, and oxidation catalysis with these compounds is thus believed to be molecular in nature under our conditions. Even with the less stable hydroxo/aqua complex [Cp*(2)Ir(2)(?-OH)(3)]OH, nanoparticle formation strongly depended on the exact conditions and elapsed time. Test experiments on the isolated particles and comparison of UV-vis data with light scattering profiles revealed that the formation of a deep purple-blue color (~580 nm) is not indicative of particle formation during oxidation catalysis with molecular iridium precursors as suggested previously. PMID:22594951

  5. /sup 15/N chemical shifts and /sup 13/C-/sup 15/N coupling constants of cyanide complexes

    SciTech Connect

    Sano, M.; Yoshikawa, Y.; Yamatera, H.

    1982-06-01

    The /sup 13/C NMR spectra of cyanide complexes have been reported by Hirota et al. and Pesek et al. However, no reports have been found concerning /sup 15/N resonances and C-N nuclear-spin coupling constants, J/sub C-N/, for cyano complexes. The data for J/sub C-N/ and /sup 15/N and /sup 13/C resonances may be useful in interpreting the NMR spetra of cyano complexes. In this paper, we present the results of the /sup 13/C and /sup 15/N spectra for 13 cyano complexes.

  6. The thermodynamic characteristics of the formation of Al3+ ion complexes with iminodisuccinic acid in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Tolkacheva, L. N.; Nikol'Skii, V. M.

    2012-03-01

    Complex formation between Al3+ and iminodisuccinic acid (H4L) was studied at 25C against the background of 0.1, 0.4, 0.6, and 0.8 N solutions of KNO3 by potentiometry and mathematical modeling. The extrapolation of concentration constants to zero ionic strength was used to calculate the thermodynamic constants of the formation of the AlL-, AlHL, and AlOHL2- complexes using an equation with one individual parameter (log?0 = 16.48 0.08, 8.93 0.14, and 22.88 0.08, respectively).

  7. Estimation of the initial equilibrium constants in the formation of tetragonal lysozyme nuclei

    NASA Technical Reports Server (NTRS)

    Pusey, Marc L.

    1991-01-01

    Results are presented from a study of the equilibria, kinetic rates, and the aggregation pathway which leads from a lysozyme monomer crystal to a tetragonal crystal, using dialyzed and recrystallized commercial hen eggwhite lysozyme. Relative light scattering intensity measurements were used to estimate the initial equilibrium constants for undersaturated lysozyme solutions in the tetragonal regime. The K1 value was estimated to be (1-3) x 10 exp 4 L/mol. Estimates of subsequent equilibrium constants depend on the crystal aggregation model chosen or determined. Experimental data suggest that tetragonal lysozyme crystal grows by addition of aggregates preformed in the bulk solution, rather than by monomer addition.

  8. Estimation of apparent binding constant of complexes of selected acyclic nucleoside phosphonates with ?-cyclodextrin by affinity capillary electrophoresis.

    PubMed

    olnov, Veronika; Mikyskov, Hana; Kaiser, Martin Maxmilin; Janeba, Zlatko; Hol, Antonn; Kai?ka, Vclav

    2016-01-01

    Affinity capillary electrophoresis (ACE) has been applied to estimation of apparent binding constant of complexes of (R,S)-enantiomers of selected acyclic nucleoside phosphonates (ANPs) with chiral selector ?-cyclodextrin (?CD) in aqueous alkaline medium. The noncovalent interactions of five pairs of (R,S)-enantiomers of ANPs-based antiviral drugs and their derivatives with ?CD were investigated in the background electrolyte (BGE) composed of 35 or 50 mM sodium tetraborate, pH 10.0, and containing variable concentration (0-25 mM) of ?CD. The apparent binding constants of the complexes of (R,S)-enantiomers of ANPs with ?CD were estimated from the dependence of effective electrophoretic mobilities of (R,S)-enantiomers of ANPs (measured simultaneously by ACE at constant reference temperature 25C inside the capillary) on the concentration of ?CD in the BGE using different nonlinear and linear calculation methodologies. Nonlinear regression analysis provided more precise and accurate values of the binding constants and a higher correlation coefficient as compared to the regression analysis of the three linearized plots of the effective mobility dependence on ?CD concentration in the BGE. The complexes of (R,S)-enantiomers of ANPs with ?CD have been found to be relatively weak - their apparent binding constants determined by the nonlinear regression analysis were in the range 13.3-46.4 L/mol whereas the values from the linearized plots spanned the interval 12.3-55.2 L/mol. PMID:26426398

  9. A two force-constant model for complexes B?M-X (B is a Lewis base and MX is any diatomic molecule): Intermolecular stretching force constants from centrifugal distortion constants D or ?J.

    PubMed

    Bittner, Dror M; Walker, Nicholas R; Legon, Anthony C

    2016-02-21

    A two force-constant model is proposed for complexes of the type B?MX, in which B is a simple Lewis base of at least C2v symmetry and MX is any diatomic molecule lying along a Cn axis (n ? 2) of B. The model assumes a rigid subunit B and that force constants beyond quadratic are negligible. It leads to expressions that allow, in principle, the determination of three quadratic force constants F11, F12, and F22 associated with the r(B?M) = r2 and r(M-X) = r1 internal coordinates from the equilibrium centrifugal distortion constants DJ (e) or ?J (e), the equilibrium principal axis coordinates a1 and a2, and equilibrium principal moments of inertia. The model can be applied generally to complexes containing different types of intermolecular bond. For example, the intermolecular bond of B?MX can be a hydrogen bond if MX is a hydrogen halide, a halogen-bond if MX is a dihalogen molecule, or a stronger, coinage-metal bond if MX is a coinage metal halide. The equations were tested for BrCN, for which accurate equilibrium spectroscopic constants and a complete force field are available. In practice, equilibrium values of DJ (e) or ?J (e) for B?MX are not available and zero-point quantities must be used instead. The effect of doing so has been tested for BrCN. The zero-point centrifugal distortion constants DJ (0) or ?J (0) for all B?MX investigated so far are of insufficient accuracy to allow F11 and F22 to be determined simultaneously, even under the assumption F12 = 0 which is shown to be reasonable for BrCN. The calculation of F22 at a series of fixed values of F11 reveals, however, that in cases for which F11 is sufficiently larger than F22, a good approximation to F22 is obtained. Plots of F22 versus F11 have been provided for Kr?CuCl, Xe?CuCl, OC?CuCl, and C2H2?AgCl as examples. Even in cases where F22 ? F11 (e.g., OC?CuCl), such plots will yield either F22 or F11 if the other becomes available. PMID:26896987

  10. A two force-constant model for complexes B⋯M-X (B is a Lewis base and MX is any diatomic molecule): Intermolecular stretching force constants from centrifugal distortion constants DJ or ΔJ

    NASA Astrophysics Data System (ADS)

    Bittner, Dror M.; Walker, Nicholas R.; Legon, Anthony C.

    2016-02-01

    A two force-constant model is proposed for complexes of the type B⋯MX, in which B is a simple Lewis base of at least C2v symmetry and MX is any diatomic molecule lying along a Cn axis (n ≥ 2) of B. The model assumes a rigid subunit B and that force constants beyond quadratic are negligible. It leads to expressions that allow, in principle, the determination of three quadratic force constants F11, F12, and F22 associated with the r(B⋯M) = r2 and r(M-X) = r1 internal coordinates from the equilibrium centrifugal distortion constants DJ e or ΔJ e , the equilibrium principal axis coordinates a1 and a2, and equilibrium principal moments of inertia. The model can be applied generally to complexes containing different types of intermolecular bond. For example, the intermolecular bond of B⋯MX can be a hydrogen bond if MX is a hydrogen halide, a halogen-bond if MX is a dihalogen molecule, or a stronger, coinage-metal bond if MX is a coinage metal halide. The equations were tested for BrCN, for which accurate equilibrium spectroscopic constants and a complete force field are available. In practice, equilibrium values of DJ e or ΔJ e for B⋯MX are not available and zero-point quantities must be used instead. The effect of doing so has been tested for BrCN. The zero-point centrifugal distortion constants DJ 0 or ΔJ 0 for all B⋯MX investigated so far are of insufficient accuracy to allow F11 and F22 to be determined simultaneously, even under the assumption F12 = 0 which is shown to be reasonable for BrCN. The calculation of F22 at a series of fixed values of F11 reveals, however, that in cases for which F11 is sufficiently larger than F22, a good approximation to F22 is obtained. Plots of F22 versus F11 have been provided for Kr⋯CuCl, Xe⋯CuCl, OC⋯CuCl, and C2H2⋯AgCl as examples. Even in cases where F22 ˜ F11 (e.g., OC⋯CuCl), such plots will yield either F22 or F11 if the other becomes available.

  11. Complexation of Al(III) with gluconate in alkaline to hyperalkaline solutions: formation, stability and structure.

    PubMed

    Pallagi, Attila; Tasi, gost Gyula; Peintler, Gbor; Forgo, Pter; Plink, Istvn; Sipos, Pl

    2013-10-01

    Contrary to suggestions in the literature, it has been proven that Al(III) forms a 1?:?1 complex with gluconate (hereafter Gluc(-)) in strongly alkaline (pH > 12) aqueous solutions. The complex formation was proven via(27)Al and (1)H NMR, freezing-point depression, polarimetric measurements as well as potentiometric and conductometric titrations. This complexation is a pH independent process, i.e., a condensation reaction takes place. The stability constant of the complex formed was derived from (1)H NMR and polarimetric measurements, and was found to be log K = 2.4 0.4. In the complex formed, Al(III) has a tetrahedral geometry, and the Al(OH)4(-) is most probably statistically distributed between the alcoholate groups of the Gluc(-). PMID:23897548

  12. Activation of immobilized plasminogen by tissue activator. Multimolecular complex formation

    SciTech Connect

    Silverstein, R.L.; Nachman, R.L.; Leung, L.L.; Harpel, P.C.

    1985-08-25

    Ternary complex formation of tissue plasminogen activator (TPA) and plasminogen (Plg) with thrombospondin (TSP) or histidine-rich glycoprotein (HRGP) has been demonstrated using an enzyme-linked immunosorbent assay, an affinity bead assay, and a rocket immunoelectrophoresis assay. The formation of these complexes was specific, concentration dependent, saturable, lysine binding site-dependent, and inhibitable by fluid phase plasminogen. Apparent Kd values were approximately 12-36 nM for the interaction of TPA with TSP-Plg complexes and 15-31 nM with HRGP-Plg complexes. At saturation the relative molar stoichiometry of Plg:TPA was 3:1 within the TSP-containing complexes and 1:1 within HRGP-containing complexes. The activation of Plg to plasmin by TPA on TSP- and HRGP-coated surfaces was studied using a synthetic fluorometric plasmin substrate (D-Val-Leu-Lys-7-amino-4-trifluoromethyl coumarin). Kinetic analysis demonstrated a marked increase in the affinity of TPA for plasminogen in the presence of surface-associated TSP or HRGP. Complex formation of locally released tissue plasminogen activator with Plg immobilized on TSP or HRGP surfaces may thus play an important role in effecting proteolytic events in nonfibrin-containing microenvironments.

  13. Mechanisms Underlying Methamphetamine-Induced Dopamine Transporter Complex Formation

    PubMed Central

    Hadlock, Gregory C.; Baucum, Anthony J.; King, Jill L.; Horner, Kristen A.; Cook, Glen A.; Gibb, James W.; Wilkins, Diana G.; Hanson, Glen R.; Fleckenstein, Annette E.

    2009-01-01

    Repeated, high-dose methamphetamine (METH) administrations cause persistent dopaminergic deficits in rodents, nonhuman primates, and humans. In rats, this treatment also causes the formation of high-molecular mass (greater than approximately 120 kDa) dopamine transporter (DAT)-associated complexes, the loss of DAT monomer immunoreactivity, and a decrease in DAT function, as assessed in striatal synaptosomes prepared 24 h after METH treatment. The present study extends these findings by demonstrating the regional selectivity of DAT complex formation and monomer loss because these changes in DAT immunoreactivity were not observed in the nucleus accumbens. Furthermore, DAT complex formation was not a consequence limited to METH treatment because it was also caused by intrastriatal administration of 6-hydroxydopamine. Pretreatment with the D2 receptor antagonist, eticlopride [S-(-)-3-chloro-5-ethyl-N-[(1-ethyl-2-pyrrolidinyl)methyl]-6-hydroxy-2-methoxybenzamide hydrochloride], but not the D1 receptor antagonist, SCH23390 [R(+)-7-chloro-8-hydroxy-3-methyl-1-phenyl-2,3,4,5-tetrahydro-1H-3-benzazepine hydrochloride], attenuated METH-induced DAT complex formation. Eticlopride pretreatment also attenuated METH-induced DAT monomer loss and decreases in DAT function; however, the attenuation was much less pronounced than the effect on DAT complex formation. Finally, results also revealed a negative correlation between METH-induced DAT complex formation and DAT activity. Taken together, these data further elucidate the underlying mechanisms and the functional consequences of repeated administrations of METH on the DAT protein. Furthermore, these data suggest a multifaceted role for D2 receptors in mediating METH-induced alterations of the DAT and its function. PMID:19141713

  14. Effect of acidity on the equilibria of formation of mixed Co2+ complexes with heparin and arginine in aqueous solutions at 37C

    NASA Astrophysics Data System (ADS)

    Feofanova, M. A.; Frantseva, Yu. V.; Semenov, A. N.; Baranova, N. V.; Zhuravlev, E. V.

    2014-02-01

    Results from studying interactions in the heparin-Co2+ ion-arginine system are presented. The constants of formation of mixed Co2+ complexes with heparin and arginine in aqueous solutions in a broad pH range at 37C are determined potentiometrically. The chemical equilibria in the system are simulated and the stoichiometry of formation of the complex forms is determined.

  15. Flexible Acyclic Polyol-Chloride Anion Complexes and Their Characterization by Photoelectron Spectroscopy and Variable Temperature Binding Constant Determinations.

    PubMed

    Shokri, Alireza; Wang, Xue-Bin; Wang, Yanping; O'Doherty, George A; Kass, Steven R

    2016-03-17

    Flexible acyclic alcohols with one to five hydroxyl groups were bound to a chloride anion and these complexes were interrogated by negative ion photoelectron spectroscopy and companion density functional theory computations. The resulting vertical detachment energies are reproduced on average to 0.10 eV by M06-2X/aug-cc-pVTZ predictions and range from 4.45-5.96 eV. These values are 0.84-2.35 eV larger than the adiabatic detachment energy of Cl(-) as a result of the larger hydrogen bond networks in the bigger polyols. Adiabatic detachment energies of the alcohol-Cl(-) clusters are more difficult to determine both experimentally and computationally. This is due to the large geometry changes that occur upon photodetachment and the large bond dissociation energy of H-Cl which enables the resulting chlorine atom to abstract a hydrogen from any of the methylene (CH2) or methine (CH) positions. Both ionic and nonionic hydrogen bonds (i.e., OH···Cl(-) and OH···OH···Cl(-)) form in the larger polyols complexes and are found to be energetically comparable. Subtle structural differences, consequently can lead to the formation of different types of hydrogen bonds, and maximizing the ionic ones is not always preferred. Solution equilibrium binding constants between the alcohols and tetrabutylammonium chloride (TBACl) in acetonitrile at -24.2, +22.0, and +53.6 °C were also determined. The free energies of association are nearly identical for all of the substrates (i.e., ΔG° = -2.8 ± 0.7 kcal mol(-1)). Compensating enthalpy and entropy values reveal, contrary to expectation and the intrinsic gas-phase preferences, that the bigger systems with more hydroxyl groups are entropically favored and enthalpically disfavored relative to the smaller species. This suggests that more solvent molecules are released upon binding TBACl to alcohols with more hydroxyl groups and is consistent with the measured negative heat capacities. These quantities increase with molecular complexity of the substrate, however, contrary to common interpretation of these values. PMID:26909527

  16. 31P{1H}NMR and carbonyl force constants of unsymmetrical bidentate phosphine complexes of group (VI) metal carbonyls

    NASA Astrophysics Data System (ADS)

    Jesu Raj, Joe Gerald; Pathak, Devendra Deo; Kapoor, Pramesh N.

    2015-05-01

    In our present work we report synthesis of an unsymmetrical diphos ligand, 1-diphenylphosphino-2-di-m-tolylphosphinoethane and its coordinate complexes with group (VI) metal carbonyls such as Cr(CO)6 Mo(CO)6 and W(CO)6. The synthesized ligand and its complexes have been completely characterized by elemental analyses, FTIR, 1HNMR, 31P{1H}NMR and FAB mass spectrometry methods. Special emphasis has been given to calculations of carbonyl force constants. Based on the spectroscopic evidences it has been confirmed that these metal carbonyl complexes with the ditertiary phosphine ligand showed cis geometry in their molecular structure.

  17. Spectrophotometric quantification of the thermodynamic constants of the complexes formed by dopamine and Cu(II) in aqueous media.

    PubMed

    Verastegui-Omaa, B; Palomar-Pardav, M; Rojas-Hernndez, A; Corona Avendao, S; Romero-Romo, M; Ramrez-Silva, M T

    2015-05-15

    The thermodynamic constants of the complex Cu(II)-dopamine in aqueous solution were evaluated from spectrophotometric data using the software SQUAD. It was found that there exist Cu(II):DA complexes with 1:1 and 1:2 stoichiometries and that their predominance depends on both the solution pH and the [Cu(II)]/[DA] ratio. Moreover, it is shown that the solubility of Cu(OH)2(s) increases drastically when these complexes are thermodynamically stable. PMID:25727295

  18. Measurement of the complex dielectric constant of lossy fibers and rods at microwave frequencies

    NASA Astrophysics Data System (ADS)

    Lind, Arthur C.; Wenger, Terry R.

    1987-05-01

    Three related waveguide devices are described for measuring the dielectric constants of fibers and rods. In each device the sample is located one-quarter guide wavelength from the shorted end of the waveguide. A slot in the side or end of the guide permits easy insertion and removal of a fiber sample without having to thread it through holes in the waveguide. The dielectric constant along the length of the fibers can be measured as they are rapidly pulled through the device. The technique allows accurate measurement of samples having a wide range of diameters and dielectric constants. Measurements of carbon, nickel alloy, and alumina samples are described, and the experimental sources of error are analyzed.

  19. A tethering complex dimer catalyzes trans-SNARE complex formation in intracellular membrane fusion

    PubMed Central

    Kulkarni, Aditya; Alpadi, Kannan; Namjoshi, Sarita; Peters, Christopher

    2012-01-01

    SNARE complexes mediate membrane fusion in the endomembrane system. They consist of coiled-coil bundles of four helices designated as Qa, Qb, Qc and R. A critical intermediate in the fusion pathway is the trans-SNARE complex generated by the assembly of SNAREs residing in opposing membranes. Mechanistic details of trans-SNARE complex formation and topology in a physiological system remain largely unresolved. Our studies on native yeast vacuoles revealed that SNAREs alone are insufficient to form trans-SNARE complexes and that additional factors, potentially tethering complexes and Rab GTPases, are required for the process. Here we report a novel finding that a HOPS tethering complex dimer catalyzes Rab GTPase-dependent formation of a topologically preferred QbQcR-Qa trans-SNARE complex. PMID:22754631

  20. Quantitative assessment of complex formation of nuclear-receptor accessory proteins.

    PubMed Central

    Graumann, K; Jungbauer, A

    2000-01-01

    Like other nuclear receptors, steroid hormone receptors form large protein hetero-complexes in their inactive, ligand-friendly state. Several heat-shock proteins, immunophilins and others have been identified as members of these highly dynamic complexes. The interaction kinetics and dynamics of hsp90, hsp70, p60 (Hop), FKBP52, FKBP51, p48 (Hip) and p23 have been assessed by a biosensor approach measuring the complex formation in real time. A core chaperone complex has been reconstituted from p60, hsp90 and hsp70. p60 forms a molecular bridge between hsp90 and hsp70 with an affinity in the range of 10(5) M(-1). Dynamics of hsp90-p60 complex formation is modulated by ATP through changes in the co-operativity of interaction. At low protein concentrations ATP stabilizes the complex. Binding of p23 to hsp90 did not change the affinity of the hsp90-p60 complex and the stabilizing effect of ATP. Saturation of the p48-hsp70 interaction could not be achieved, suggesting multiple binding sites. A picture of the protein complex, including stoichiometric coefficients, co-operativity of interaction and equilibrium-binding constants, has been formed. PMID:10642522

  1. Sub-THz complex dielectric constants of smectite clay thin samples with Na+/Ca++ ions

    NASA Astrophysics Data System (ADS)

    Rahman, Rezwanur; McCarty, Douglas K.; Prasad, Manika

    2015-09-01

    We implement a technique to characterize the electromagnetic properties at frequencies 100 to 165 GHz (3 cm-1 to 4.95 cm-1) of oriented smectite samples using an open cavity resonator connected to a submillimeter wave VNA (Vector Network Analyzer). We measured dielectric constants perpendicular to the bedding plane on oriented Na+ ion and Ca++ ion stabilized smectite samples deposited on a glass slide at ambient laboratory conditions (room temperature and room light). The clay layer is much thinner (˜30 μm) than the glass substrate (˜2.18 mm). The real part of dielectric constant, ɛre, is essentially constant over this frequency range but is larger in Na+ ion than in Ca++ ion infused clay. The total electrical conductivity (associated with the imaginary part of dielectric constant, ɛim) of both samples increases monotonically at lower frequencies (<110 GHz) but shows rapid increase for Na+ ions in the regime > 110 GHz. The dispersion of the samples display a dependence on the ionic strength in the clay interlayers, i.e., ζ potential in the Stern layers.

  2. Geology of the Biwabik Iron Formation and Duluth Complex.

    PubMed

    Jirsa, Mark A; Miller, James D; Morey, G B

    2008-10-01

    The Biwabik Iron Formation is a approximately 1.9 billion year-old sequence of iron-rich sedimentary rocks that was metamorphosed at its eastern-most extent by approximately 1.1 billion year-old intrusions of the Duluth Complex. The metamorphic recrystallization of iron-formation locally produced iron-rich amphiboles and other fibrous iron-silicate minerals. The presence of these minerals in iron-formation along the eastern part of what is known as the Mesabi Iron Range, and their potential liberation by iron mining has raised environmental health concerns. We describe here the geologic setting and mineralogic composition of the Biwabik Iron Formation in and adjacent to the contact metamorphic aureole of the Duluth Complex. The effects of metamorphism are most pronounced within a few kilometers of the contact, and decrease progressively away from it. The contact aureole has been divided into four metamorphic zones-each characterized by the composition and crystal structure of the metamorphic minerals it contains. The recrystallization of iron-formation to iron-rich amphibole minerals (grunerite and cummingtonite) and iron-pyroxene minerals (hedenbergite and ferrohypersthene) is best developed in zones that are most proximal to the Duluth Complex contact. PMID:17997209

  3. Geology of the Biwabik Iron Formation and Duluth Complex

    USGS Publications Warehouse

    Jirsa, M.A.; Miller, J.D., Jr.; Morey, G.B.

    2008-01-01

    The Biwabik Iron Formation is a ???1.9 billion year-old sequence of iron-rich sedimentary rocks that was metamorphosed at its eastern-most extent by ???1.1 billion year-old intrusions of the Duluth Complex. The metamorphic recrystallization of iron-formation locally produced iron-rich amphiboles and other fibrous iron-silicate minerals. The presence of these minerals in iron-formation along the eastern part of what is known as the Mesabi Iron Range, and their potential liberation by iron mining has raised environmental health concerns. We describe here the geologic setting and mineralogic composition of the Biwabik Iron Formation in and adjacent to the contact metamorphic aureole of the Duluth Complex. The effects of metamorphism are most pronounced within a few kilometers of the contact, and decrease progressively away from it. The contact aureole has been divided into four metamorphic zones-each characterized by the composition and crystal structure of the metamorphic minerals it contains. The recrystallization of iron-formation to iron-rich amphibole minerals (grunerite and cummingtonite) and iron-pyroxene minerals (hedenbergite and ferrohypersthene) is best developed in zones that are most proximal to the Duluth Complex contact. ?? 2007 Elsevier Inc. All rights reserved.

  4. Synthesis, characterization and thermodynamics of complex formation of some new Schiff base ligands with some transition metal ions and the adduct formation of zinc Schiff base complexes with some organotin chlorides.

    PubMed

    Asadi, Mozaffar; Asadi, Zahra; Torabi, Susan; Lotfi, Najmeh

    2012-08-01

    Four new complexes, [M(Salpyr)] where Salpyr=N,N'-bis(Salicylidene)-2,3- and 3,4-diiminopyridine and M=Co, Cu, Mn, Ni and Zn were synthesized and characterized by (1)H NMR, IR spectroscopy, elemental analysis and UV-vis spectrophotometry. UV-vis spectrophotometric study of the adduct formation of the zinc(II) complexes, [Zn(2,3-Salpyr)] and [Zn(3,4-Salpyr)], as donor with R(2)SnCl(2) (R=methyl, phenyl, n-butyl), PhSnCl(3) and Bu(3)SnCl as acceptors has been investigated in methanol, as solvent. The formation constants and the thermodynamic free energies were measured using UV-vis spectrophotometry. Titration of the organotin chlorides with Zn(II) complexes at various temperatures (T=283-313K) leads to 1:1 adduct formation. The results show that the formation constants were decreased by increasing the temperature. The trend of the reaction of R(n)SnCl(4-n) as acceptors toward given zinc complexes was as follows: PhSnCl3 > Me2SnCl2 > Ph2SnCl2 > Bu2SnCl2 > Bu3SnCl. By considering the formation constants and the ?G of the complex formation for the Schiff base as donor and the M(II) as acceptor, the following conclusion was drawn: the formation constant for a given Schiff base changes according to the following trend: Ni > Cu > Co > Zn > Mn. PMID:22626922

  5. Synthesis, characterization and thermodynamics of complex formation of some new Schiff base ligands with some transition metal ions and the adduct formation of zinc Schiff base complexes with some organotin chlorides

    NASA Astrophysics Data System (ADS)

    Asadi, Mozaffar; Asadi, Zahra; Torabi, Susan; Lotfi, Najmeh

    Four new complexes, [M(Salpyr)] where Salpyr = N,N'-bis(Salicylidene)-2,3- and 3,4-diiminopyridine and M = Co, Cu, Mn, Ni and Zn were synthesized and characterized by 1H NMR, IR spectroscopy, elemental analysis and UV-vis spectrophotometry. UV-vis spectrophotometric study of the adduct formation of the zinc(II) complexes, [Zn(2,3-Salpyr)] and [Zn(3,4-Salpyr)], as donor with R2SnCl2 (R = methyl, phenyl, n-butyl), PhSnCl3 and Bu3SnCl as acceptors has been investigated in methanol, as solvent. The formation constants and the thermodynamic free energies were measured using UV-vis spectrophotometry. Titration of the organotin chlorides with Zn(II) complexes at various temperatures (T = 283-313 K) leads to 1:1 adduct formation. The results show that the formation constants were decreased by increasing the temperature. The trend of the reaction of RnSnCl4-n as acceptors toward given zinc complexes was as follows: PhSnCl3 > Me2SnCl2 > Ph2SnCl2 > Bu2SnCl2 > Bu3SnCl By considering the formation constants and the ?G of the complex formation for the Schiff base as donor and the M(II) as acceptor, the following conclusion was drawn: the formation constant for a given Schiff base changes according to the following trend: Ni > Cu > Co > Zn > Mn

  6. Formation of copper complexes in landfill leachate and their toxicity to zebrafish embryos

    SciTech Connect

    Fraser, J.K.; Butler, C.A.; Timperley, M.H.; Evans, C.W.

    2000-05-01

    Toxic metal organic complexes have not been found in natural waters, although some organic acids form bioavailable lipophilic and metabolite-type metal complexes. Landfill leachates usually contain organic acids and in the urban environment these leachates, when mixed with storm waters containing Cu, could be a source of toxic Cu organic complexes in streams and estuaries. The authors investigated the formation of Cu complexes in the leachate from an active urban landfill and found that some of the complexes formed were toxic to zebrafish embryos. High and low nominal molecular weight (NMWT) fractions; >5,000 Da and <700 Da, of leachate both formed Cu complexes with almost identical Cu complexing characteristics but the toxicity was due solely to the low NMWT complexes formed in the <700 Da fraction. Chemical equilibrium modeling with MINTEQA2 and H and Cu complex conditional association constants and ligand concentrations obtained from pH and Cu titrations with a Cu ion-selective electrode and van den Berg-Ruzic analyses of the titration data was used to calculate the copper speciation in the embryo test solutions. This calculated speciation, which was confirmed by measurements of Cu{sup 2+} in the test solutions, enabled the toxicity due to the free Cu ion and to the Cu complexes to be distinguished.

  7. Determination of the dissociation constants for recombinant c-Myc, Max, and DNA complexes: The inhibitory effect of linoleic acid on the DNA-binding step

    SciTech Connect

    Jung, Kyung Chae; Rhee, Ho Sung; Park, Chi Hoon; Yang, Chul-Hak . E-mail: chulyang@plaza.snu.ac.kr

    2005-08-19

    c-Myc, the protein product of protooncogene c-myc, functions in cell proliferation, differentiation, and neoplastic disease. In this study, recombinant c-Myc and Max proteins, encompassing DNA binding (basic region) and dimerization (helix-loop-helix/leucine zipper) domain of human origin, were expressed in bacteria as Myc87 and Max85. Myc87 was purified under denatured conditions and was renatured again. The dissociation constant for the protein dimers and for dimer/DNA complexes were not detectable by isothermal titration calorimetry because of the low degree of solubility of Myc87 and Max85. Therefore, we set up equations which were used to determine the dissociation constants from the proportion of protein-DNA complexes. The dimer dissociation constants in TBS were 5.90({+-}0.54) x 10{sup -7} M for Max85/Max85 homodimer, 6.85({+-}0.25) x 10{sup -3} M for Myc87/Myc87 homodimer, and 2.55({+-}0.29) x 10{sup -8} M for Myc87/Max85 heterodimer, and the DNA-binding dissociation constants in TBS were 1.33({+-}0.21) x 10{sup -9} M for Max85/Max85/DNA, 2.27({+-}0.08) x 10{sup -12} M for Myc87/Myc87/DNA, and 4.43({+-}0.37) x 10{sup -10} M for Myc87/Max85/DNA. In addition, we revealed that linoleic acid which is known as an inhibitor for the formation of Max/Max/DNA complex reduced the affinity of Max homodimer for DNA. This result indicates that linoleic acid may bind to the DNA-binding region of Max homodimer.

  8. Equilibrium and Formation/Dissociation Kinetics of some Lanthanide(III)-PCTA complexes

    PubMed Central

    Tircs, Gyula; Kovcs, Zoltn; Sherry, A. Dean

    2008-01-01

    The protonation constants (KiH) of 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-3,6,9,-triacetic acid (PCTA) and stability constants of complexes formed between this pyridine containing macrocycle and several different metal ions have been determined in 1.0 M KCl, 25C and compared to previous literature values. The first protonation constant was found to be 0.5-0.6 log units higher than the value reported previously and a total five protonation steps were detected (log KiH = 11.36, 7.35, 3.83, 2.12 and 1.29). The stability constants of complexes formed between PCTA and Mg2+, Ca2+, Cu2+ and Zn2+ were also somewhat higher than those previously reported but this difference could be largely attributed to the higher first protonation constant of the ligand. Stability constants of complexes formed between PCTA and the Ln3+ series of ions and Y3+ were determined by using an out-of-cell potentiometric method. These values ranged from log K = 18.15 for Ce(PCTA) to log K = 20.63 for Yb(PCTA), increasing along the lanthanide series in proportion to decreasing Ln3+ cation size. The rates of complex formation for Ce(PCTA), Eu(PCTA), Y(PCTA) and Yb(PCTA) were followed by conventional UV-VIS spectroscopy in the pH range pH=3.5 - 4.4. First order rate constants (saturation kinetics) obtained for different ligand / metal ion ratios were consistent with rapid formation of a diprotonated intermediate, Ln(H2PCTA)2+. The stabilities of the intermediates as determined from the kinetic data were 2.81, 3.12, 2.97 and 2.69 log K units for Ce(H2PCTA), Eu(H2PCTA), Y(H2PCTA) and Yb(H2PCTA), respectively. Rearrangement of these intermediates to the fully chelated complexes was the rate determining step and the rate constant (kr) for this process was found to be inversely proportional to the proton concentration. The formation rates (kOH) increased with a decrease in lanthanide ion size (9.68107 M-1s-1, 1.74108 M-1s-1, 1.13108 M-1s-1 and 1.11109 M-1s-1 for Ce(PCTA), Eu(PCTA), Y(PCTA) and Yb(PCTA), respectively). These data indicate that the Ln(PCTA) complexes exhibit the fastest formation rates among all lanthanide macrocyclic ligand complexes studied to date. The acid catalyzed dissociation rates (k1) varied with cation from 9.6110-4 M-1s-1, 5.0810-4 M-1s-1, 1.0710-3 M-1s-1 and 2.8010-4 M-1s-1 for Ce(PCTA), Eu(PCTA), Y(PCTA) and Yb(PCTA), respectively. PMID:17083226

  9. Dissection and engineering of the Escherichia coli formate hydrogenlyase complex.

    PubMed

    McDowall, Jennifer S; Hjersing, M Charlotte; Palmer, Tracy; Sargent, Frank

    2015-10-01

    The Escherichia coli formate hydrogenlyase (FHL) complex is produced under fermentative conditions and couples formate oxidation to hydrogen production. In this work, the architecture of FHL has been probed by analysing affinity-tagged complexes from various genetic backgrounds. In a successful attempt to stabilize the complex, a strain encoding a fusion between FdhF and HycB has been engineered and characterised. Finally, site-directed mutagenesis of the hycG gene was performed, which is predicted to encode a hydrogenase subunit important for regulating sensitivity to oxygen. This work helps to define the core components of FHL and provides solutions to improving the stability of the enzyme. PMID:26358294

  10. Solvation effects in complex-forming reactions. I. The effect of solvents on complex formation between seleno and thioanisoles and iodine

    SciTech Connect

    Safin, D.Kh.; Chmutova, G.A.; Solomonov, B.N.

    1986-02-10

    The enthalpies of solution of seleno- and thioanisoles in a large group of solvents, the constants and enthalpies of complex formation between both compounds and iodine, and the spectral characteristics of the complexes in the same solvents were measured and analyzed. In chemically inert solvents there are fairly clear relationships between the spectral and thermodynamic characteristics of the obtained Mulliken-type complexes, both groups of CTC (charge-transfer complex) parameters, and the universal intermolecular interaction functions of the solvent; a series of the characteristics of the complex were analyzed in relation to the behavior of the reagents. Such correlations are not observed in coordinating solvents, but the directions of the change in the enthalpies of complex formation with variation of the solvents can be predicted.

  11. Impact of electric-field dependent dielectric constants on two-dimensional electron gases in complex oxides

    NASA Astrophysics Data System (ADS)

    Peelaers, H.; Krishnaswamy, K.; Gordon, L.; Steiauf, D.; Sarwe, A.; Janotti, A.; Van de Walle, C. G.

    2015-11-01

    High-density two-dimensional electron gas (2DEG) can be formed at complex oxide interfaces such as SrTiO3/GdTiO3 and SrTiO3/LaAlO3. The electric field in the vicinity of the interface depends on the dielectric properties of the material as well as on the electron distribution. However, it is known that electric fields can strongly modify the dielectric constant of SrTiO3 as well as other complex oxides. Solving the electrostatic problem thus requires a self-consistent approach in which the dielectric constant varies according to the local magnitude of the field. We have implemented the field dependence of the dielectric constant in a Schrdinger-Poisson solver in order to study its effect on the electron distribution in a 2DEG. Using the SrTiO3/GdTiO3 interface as an example, we demonstrate that including the field dependence results in the 2DEG being confined closer to the interface compared to assuming a single field-independent value for the dielectric constant. Our conclusions also apply to SrTiO3/LaAlO3 as well as other similar interfaces.

  12. Formation and stability of lanthanide complexes and their encapsulation into polymeric microspheres

    SciTech Connect

    Mumper, R.J.; Jay, M.

    1992-10-15

    The complexation of lanthanides (Ln) with dicarbonyl compounds (acetylacetone, acac; ethyl acetoacetate; 3-ethyl-2,4-pentanedione; 2,4-hexanedione; 3-methyl-2,4-pentanedione; and diethyl malonate) was investigated using a potentiometric titration technique. The ability of a dicarbonyl compound to complex with the lanthanide elements was greatly dependent on its pK{sub a} and on the pH of the titrated solution. Selected lanthanide complexes (Ln complexes) were incorporated into spherical poly(L-lactic acid)(PLA) matrices and irradiated in a nuclear reactor with neutrons to produce short-lived high-energy {Beta}-particle-emitting radioisotopes. The lanthanides investigated (Ho, Dy, Sm, and La) were chosen on the basis of their physical and nuclear properties. A transition element (Re) was also studied. The small decrease in the ionic radii of the lanthanides with increasing atomic number led to (a) greater ability to extract and complex from an aqueous solution with complexing agents, (b) larger formation and stability constants for the Ln complexes, (c) increased solubility of the Ln complexes in chloroform, and (d) increase in the maximum percent incorporation of the stable lanthanides in PLA spheres. Ho(aca) was found to be the most promising candidate of the complexes studied on the basis of the above observations and due to the favorable physical properties of {sup 165}Ho and nuclear properties of {sup 166}Ho. 21 refs., 5 figs., 4 tabs.

  13. Seeking the constant in what is transient: Karl Ernst von Baer's vision of organic formation.

    PubMed

    Vienne, Florence

    2015-03-01

    A well-established narrative in the history of science has it that the years around 1800 saw the end of a purely descriptive, classificatory and static natural history. The emergence of a temporal understanding of nature and the new developmental-history approach, it is thought, permitted the formation of modern biology. This paper questions that historical narrative by closely analysing the concepts of development, history and time set out in Karl Ernst von Baer's study of the mammalian egg (1827). I show that Baer's research on embryogenesis aimed not simply to explain temporal changes, but to inscribe the formation of new individual organisms into a continuous, unending organic process. I confront Baer's views with other explanations of embryogenesis arising in the 1820s and 1830s, especially those of Jean-Baptiste Dumas and Jean-Louis Prévost and of Theodor Schwann. By highlighting divergences between these scientists, especially as to their view of the role of gender differences in reproduction, I argue that biology evolved not from a homogeneous concept of developmental history but out of various, even opposing, views and research programmes. Thus, the birth of biology did not imply the end of all natural history's thought models. PMID:26013434

  14. Holomorphic embedding of complex curves in spaces of constant holomorphic curvature.

    PubMed

    Chavel, I; Rauch, H E

    1972-03-01

    A special case of Wirtinger's theorem asserts that a complex curve (two-dimensional) holomorphically embedded in a Kaehler manifold is a minimal surface. The converse is not necessarily true. Guided by considerations from the theory of moduli of Riemann surfaces, we discover (among other results) sufficient topological and differential-geometric conditions for a minimal (Riemannian) immersion of a 2-manifold in complex projective space with the Fubini-Study metric to be holomorphic. PMID:16591967

  15. Positronium formation studies in crystalline molecular complexes: Triphenylphosphine oxide - Acetanilide

    NASA Astrophysics Data System (ADS)

    Oliveira, F. C.; Denadai, A. M. L.; Guerra, L. D. L.; Fulgêncio, F. H.; Windmöller, D.; Santos, G. C.; Fernandes, N. G.; Yoshida, M. I.; Donnici, C. L.; Magalhães, W. F.; Machado, J. C.

    2013-04-01

    Hydrogen bond formation in the triphenylphosphine oxide (TPPO), acetanilide (ACN) supramolecular heterosynton system, named [TPPO0.5·ACN0.5], has been studied by Positron Annihilation Lifetime Spectroscopy (PALS) and supported by several analytical techniques. In toluene solution, Isothermal Titration Calorimetry (ITC) presented a 1:1 stoichiometry and indicated that the complexation process is driven by entropy, with low enthalpy contribution. X-ray structure determination showed the existence of a three-dimensional network of hydrogen bonds, allowing also the confirmation of the existence of a 1:1 crystalline molecular complex in solid state. The results of thermal analysis (TGA, DTA and DSC) and FTIR spectroscopy showed that the interactions in the complex are relatively weaker than those found in pure precursors, leading to a higher positronium formation probability at [TPPO0.5·ACN0.5]. These weak interactions in the complex enhance the possibility of the n- and π-electrons to interact with positrons and consequently, the probability of positronium formation is higher. Through the present work is shown that PALS is a sensible powerful tool to investigate intermolecular interactions in solid heterosynton supramolecular systems.

  16. Formation of ZnO at zinc oxidation by near- and supercritical water under the constant electric field

    NASA Astrophysics Data System (ADS)

    Shishkin, A. V.; Sokol, M. Ya.; Shatrova, A. V.; Fedyaeva, O. N.; Vostrikov, A. A.

    2014-12-01

    The work has detected an influence of a constant electric field (up to E = 300 kV/m) on the structure of a nanocrystalline layer of zinc oxide, formed on the surface of a planar zinc anode in water under supercritical (673 K and 23 MPa) and near-critical (673 K and 17. 5 MPa) conditions. The effect of an increase of zinc oxidation rate with an increase in E is observed under supercritical conditions and is absent at near-critical ones. Increase in the field strength leads to the formation of a looser structure in the inner part of the zinc oxide layer.

  17. Accelerating procelain formation by incorporating a complex additive

    SciTech Connect

    Maslennikova, G.N.; Dubovitskii, S.A.; Moroz, I.K.

    1986-05-01

    The authors studied the influence of a complex additive consisting of oxides of calcium, zinc, and magnesium on the formaton of porcelain. In order to achieve a more uniform distribution of the complex additive in the porcelain body it was incorporated in the form of water soluble salts-nitrates, which ensured comparability of results and excluded the effect of the different types of anions. The study of the main parameters of sintering (porosity, shrinkage, and mechanical strength) for the test bodies showed that they sinter at lower temperatures and attain zero porosity, maximum shrinkage, and mechanical strength. The most typical bodies indentified in this way were investigated by methods of complex differential thermal analysis and x-ray diffraction. Thus, the introduction of complex additives consisting of calcium, zinc, and magnesium oxides contributes to the earlier formation of porcelain. With the reduction of firing temperatures by 100/sup 0/C the authors observe an improvement in the basic properties of porcelain.

  18. Low temperature rate constants for the N(4S) + CH(X2?r) reaction. Implications for N2 formation cycles in dense interstellar clouds.

    PubMed

    Daranlot, Julien; Hu, Xixi; Xie, Changjian; Loison, Jean-Christophe; Caubet, Philippe; Costes, Michel; Wakelam, Valentine; Xie, Daiqian; Guo, Hua; Hickson, Kevin M

    2013-09-01

    Rate constants for the potentially important interstellar N((4)S) + CH(X(2)?r) reaction have been measured in a continuous supersonic flow reactor over the range 56 K ?T? 296 K using the relative rate technique employing both the N((4)S) + OH(X(2)?i) and N((4)S) + CN(X(2)?(+)) reactions as references. Excess concentrations of atomic nitrogen were produced by the microwave discharge method upstream of the Laval nozzle and CH and OH radicals were created by the in situ pulsed laser photolysis of suitable precursor molecules. In parallel, quantum dynamics calculations of the title reaction have been performed based on accurate global potential energy surfaces for the 1(3)A' and 1(3)A'' states of HCN and HNC, brought about through a hierarchical construction scheme. Both adiabatic potential energy surfaces are barrierless, each one having two deep potential wells suggesting that this reaction is dominated by a complex-forming mechanism. The experimental and theoretical work are in excellent agreement, predicting a positive temperature dependence of the rate constant, in contrast to earlier experimental work at low temperature. The effects of the new low temperature rate constants on interstellar N2 formation are tested using a dense cloud model, yielding N2 abundances 10-20% lower than previously predicted. PMID:23843017

  19. Formation of discharge plasma on the surface of cathodes with different dielectric constants

    NASA Astrophysics Data System (ADS)

    Krasik, Ya. E.; Dunaevsky, A.; Felsteiner, J.

    1999-06-01

    We present a detailed study of the spatial and temporal evolution of visible light emission from plasma formed on the surface of ferroelectrics [Pb(Zr,Ti)O3 and BaTiO3] and a printed-circuit board under the application of a high-voltage pulse. For all samples studied, plasma formation occurs within the first 5 ns from the start of the high-voltage pulse. It is shown that the plasma appears at the edges of the front strip electrodes. Further, the plasma spreads along the dielectric surface covering it partially. It is found that the uniformity of the plasma and the distance of its propagation along the surface depend on the properties of the dielectric, the polarity and amplitude of the high-voltage pulse, and the vacuum conditions. A qualitative model which explains the observed experimental data is suggested.

  20. In vacuo formation of peptide-metal coordination complexes

    NASA Astrophysics Data System (ADS)

    McAlister, Graeme C.; Kiessel, Sharon E. B.; Coon, Joshua J.

    2008-10-01

    Here we report on the reaction of rhenate anions (ReO3-) with multiply protonated peptide cations in a quadrupole linear ion trap mass spectrometerE These reactions effect the formation of an anion-cation complex that, upon collisional activation, dissociates along the peptide backbone rather than by displacement of the anion. Cleavage of the peptide backbone, with anion retention, leads us to conclude the anion-cation complex must be tightly bound, most probably through coordination chemistry. We describe this chemistry and detail the possible application of such ion attachment reactions to the characterization of intact proteins.

  1. Hydrolysis, formation and ionization constants at 25/sup 0/C, and at high temperature-high ionic strength

    SciTech Connect

    Phillips, S.L.; Phillips, C.A.; Skeen, J.

    1985-02-01

    Thermochemical data for nuclear waste disposal are compiled. The resulting computerized database consists of critically evaluated data on Gibbs energy of formation, enthalpy of formation, entropy and heat capacity of selected substances for about 16 elements at 25/sup 0/C and zero ionic strength. Elements covered are Am, As, Br, C, Cl, F, I, Mo, Np, N, O, P, Pu, Si, Sr, S, and U. Values of these thermodynamic properties were used to calculate equilibrium quotients for hydrolysis, complexation and ionization reactions up to 300/sup 0/C and 3 ionic strength, for selected chemical reactions.

  2. Multinuclear complex formation in aqueous solutions of Ca(II) and heptagluconate ions.

    PubMed

    Pallagi, Attila; Csendes, Zita; Kutus, Bence; Czegldi, Eszter; Peintler, Gbor; Forgo, Pter; Plink, Istvn; Sipos, Pl

    2013-06-21

    The equilibria and structure of complexes formed between the Ca(2+) ion and the heptagluconate (Hglu(-)) ion in both neutral and alkaline solutions have been studied. In alkaline solutions an uncharged, multinuclear complex is formed with the composition of Ca3Hglu2(OH)4 (or [Ca3Hglu2H(-4)](0)) with an unexpectedly high stability constant (lg ?(32-4) = 14.09). The formation of the trinuclear complex was deduced from potentiometry and confirmed by freezing-point depression measurements and conductometry as well. The binding sites of Hglu(-) were determined from NMR measurements. Besides the carboxylate group, the O atoms on the second and third carbon atoms proved to be the most probable sites for Ca(2+) binding. PMID:23629045

  3. Dynamics and rate of complex ions formation in comets

    NASA Astrophysics Data System (ADS)

    Shoyoqubov, Shoayub; Shoyoqubov, Shohrukh; Ibrohimov, Alisher

    2015-12-01

    The purpose of this research is to create a laboratory model of comet phenomenon and perform mass spectral analysis of the dynamics and rate of formation of complex ions by bombarding the solid mixture of H2O and CO2 with positive Cs ions with energy of 1.5 keV. Results of previous mass spectral studies of laboratory modeled comet phenomena and emission coefficient proportionality method were used in calculations.

  4. The catalytic role of uranyl in formation of polycatechol complexes

    PubMed Central

    2011-01-01

    To better understand the association of contaminant uranium with natural organic matter (NOM) and the fate of uranium in ground water, spectroscopic studies of uranium complexation with catechol were conducted. Catechol provides a model for ubiquitous functional groups present in NOM. Liquid samples were analyzed using Raman, FTIR, and UV-Vis spectroscopy. Catechol was found to polymerize in presence of uranyl ions. Polymerization in presence of uranyl was compared to reactions in the presence of molybdate, another oxyion, and self polymerization of catechol at high pH. The effect of time and dissolved oxygen were also studied. It was found that oxygen was required for self-polymerization at elevated pH. The potential formation of phenoxy radicals as well as quinones was monitored. The benzene ring was found to be intact after polymerization. No evidence for formation of ether bonds was found, suggesting polymerization was due to formation of C-C bonds between catechol ligands. Uranyl was found to form outer sphere complexes with catechol at initial stages but over time (six months) polycatechol complexes were formed and precipitated from solution (forming humic-like material) while uranyl ions remained in solution. Our studies show that uranyl acts as a catalyst in catechol-polymerization. PMID:21396112

  5. The Dynamics of Coalition Formation on Complex Networks

    PubMed Central

    Auer, S.; Heitzig, J.; Kornek, U.; Schöll, E.; Kurths, J.

    2015-01-01

    Complex networks describe the structure of many socio-economic systems. However, in studies of decision-making processes the evolution of the underlying social relations are disregarded. In this report, we aim to understand the formation of self-organizing domains of cooperation (“coalitions”) on an acquaintance network. We include both the network’s influence on the formation of coalitions and vice versa how the network adapts to the current coalition structure, thus forming a social feedback loop. We increase complexity from simple opinion adaptation processes studied in earlier research to more complex decision-making determined by costs and benefits, and from bilateral to multilateral cooperation. We show how phase transitions emerge from such coevolutionary dynamics, which can be interpreted as processes of great transformations. If the network adaptation rate is high, the social dynamics prevent the formation of a grand coalition and therefore full cooperation. We find some empirical support for our main results: Our model develops a bimodal coalition size distribution over time similar to those found in social structures. Our detection and distinguishing of phase transitions may be exemplary for other models of socio-economic systems with low agent numbers and therefore strong finite-size effects. PMID:26303622

  6. The Dynamics of Coalition Formation on Complex Networks.

    PubMed

    Auer, S; Heitzig, J; Kornek, U; Schöll, E; Kurths, J

    2015-01-01

    Complex networks describe the structure of many socio-economic systems. However, in studies of decision-making processes the evolution of the underlying social relations are disregarded. In this report, we aim to understand the formation of self-organizing domains of cooperation ("coalitions") on an acquaintance network. We include both the network's influence on the formation of coalitions and vice versa how the network adapts to the current coalition structure, thus forming a social feedback loop. We increase complexity from simple opinion adaptation processes studied in earlier research to more complex decision-making determined by costs and benefits, and from bilateral to multilateral cooperation. We show how phase transitions emerge from such coevolutionary dynamics, which can be interpreted as processes of great transformations. If the network adaptation rate is high, the social dynamics prevent the formation of a grand coalition and therefore full cooperation. We find some empirical support for our main results: Our model develops a bimodal coalition size distribution over time similar to those found in social structures. Our detection and distinguishing of phase transitions may be exemplary for other models of socio-economic systems with low agent numbers and therefore strong finite-size effects. PMID:26303622

  7. The Dynamics of Coalition Formation on Complex Networks

    NASA Astrophysics Data System (ADS)

    Auer, S.; Heitzig, J.; Kornek, U.; Schöll, E.; Kurths, J.

    2015-08-01

    Complex networks describe the structure of many socio-economic systems. However, in studies of decision-making processes the evolution of the underlying social relations are disregarded. In this report, we aim to understand the formation of self-organizing domains of cooperation (“coalitions”) on an acquaintance network. We include both the network’s influence on the formation of coalitions and vice versa how the network adapts to the current coalition structure, thus forming a social feedback loop. We increase complexity from simple opinion adaptation processes studied in earlier research to more complex decision-making determined by costs and benefits, and from bilateral to multilateral cooperation. We show how phase transitions emerge from such coevolutionary dynamics, which can be interpreted as processes of great transformations. If the network adaptation rate is high, the social dynamics prevent the formation of a grand coalition and therefore full cooperation. We find some empirical support for our main results: Our model develops a bimodal coalition size distribution over time similar to those found in social structures. Our detection and distinguishing of phase transitions may be exemplary for other models of socio-economic systems with low agent numbers and therefore strong finite-size effects.

  8. Kinetics, binding constant, and activation energy of the 48-kDa protein-rhodopsin complex by extra-metarhodopsin II

    SciTech Connect

    Schleicher, A.; Kuehn, H.H.; Hofmann, K.P.

    1989-02-21

    We have found that the 48-kDa protein (or S-antigen 48k) of the rod photoreceptor enhances the light-induced formation of the photoproduct metarhodopsin II (MII) from prephosphorylated rhodopsin. The effect is analogous to the known enhancement of MII (extra-MII) that results from selective interaction of MII with G-protein. We have determined some parameters of the MII-48k interaction by measuring the extra-MII absorption change induced by the 48-kDa protein. The amplitude saturation yields a dissociation constant for the MII-48k complex on the order of 50 nM. At the technical limit of these measurements, 13.7 degrees C and 12 microM 48-kDa protein, we find a rate of 2.3 s-1 for formation of the 48k-MII complex. Extrapolation of these values to cellular conditions yields an occupation time of phosphorylated MII by 48k less than 200 ms. This is short compared to estimated rates of phosphorylation. The temperature dependence of the MII-48k formation rate is very high (Q10 for 5 degrees C/15 degrees C = 9-10). The related Arrhenius activation energy (165 kJ mol-1) is correspondingly high and indicates a considerable transient chemical change during the binding process.

  9. Demixing-stimulated lane formation in binary complex plasma

    SciTech Connect

    Du, C.-R.; Jiang, K.; Suetterlin, K. R.; Ivlev, A. V.; Morfill, G. E.

    2011-11-29

    Recently lane formation and phase separation have been reported for experiments with binary complex plasmas in the PK3-Plus laboratory onboard the International Space Station (ISS). Positive non-additivity of particle interactions is known to stimulate phase separation (demixing), but its effect on lane formation is unknown. In this work, we used Langevin dynamics (LD) simulation to probe the role of non-additivity interactions on lane formation. The competition between laning and demixing leads to thicker lanes. Analysis based on anisotropic scaling indices reveals a crossover from normal laning mode to a demixing-stimulated laning mode. Extensive numerical simulations enabled us to identify a critical value of the non-additivity parameter {Delta} for the crossover.

  10. Simulation of Titan Haze Formation Using a Photochemical Flow Reactor. Optical Constants of the Simulated Haze

    NASA Astrophysics Data System (ADS)

    Tran, B. N.; Joseph, J. C.; Ferris, J. P.

    2000-10-01

    A photochemical flow reactor has been used for the laboratory simulation of the formation of the volatiles and solids generated photochemically in Titan's stratosphere. These products were formed using mixing ratios of gases that approximated those on Titan (Clarke et al. 2000 Icarus in press). A detailed investigation of the real (n) and imaginary (k) parts of the refractive indices of the polymers formed in the 200 < lambda < 2,500 nm region are reported for comparison with laboratory data (Khare et al.1984, Icarus 60, 127) and observations from the Voyager spacecraft (McKay et al. 1989, Icarus 80, 23). The values of n and k were determined from a combination of transmittance and reflectance measurements in the UV and near IR. The method of calculation of Heavens (Heavans, 1965, Optical Properties of Thin Solid Films, Dover, 1965) was used to calculate n and k. n has a value of 1.5 - 1.6 throughout this wavelength region except for uncertainties in the 800-2,500 nm. The value of k increases throughout the wavelength region and has values consistent with Titan haze measurements (McKay et. al. 1989). The value of k increases from 0.02 to 0.1 in the 2,500- 12,500 nm region indicative of the absorption of functional groups including C-N, C=C and C-H. Some of the structural features of the polymer will be proposed from these and other spectral studies on this Titan haze analog. NASA funding from NAG5-9607 and the NY Center for Studies on the Origins of Life (NAG5-9607).

  11. Kinetics, thermodynamics, and modeling of complex formation between calix[4]biscrowns and cesium.

    PubMed

    Korovitch, Alexandre; Mulon, Jean-Baptiste; Souchon, Vincent; Lion, Claude; Valeur, Bernard; Leray, Isabelle; Ha-Duong, Nguyt-Thanh; El Hage Chahine, Jean-Michel

    2009-10-29

    Complex formations between calix[4]arene-bis(crown-6-ether) calix-COU2 (A1) and the tetrasulfonated species calix-COUSULF (A2) with Cs(+) are investigated in water and ethanol, and in 9:1 (M1) and 1:9 (M2) H(2)O/EtOH v:v mixtures, by chemical relaxation and molecular modeling. In ethanol and M2, two Cs(+) are included in A1 in two kinetic steps, whereas complex formation in M1 becomes controlled by a slow first-order kinetic process, which is accompanied by very fast Cs(+) inclusions, second-order rate constant: k'(1) = (3.4 +/- 0.8) x 10(7) M(-1) s(-1). In water and M1, A2 forms 1:1 and 1:2 cesium complexes in a single kinetic step, whereas in M2, two Cs(+) are included in two kinetic steps. The rate and thermodynamic constants involved are reported. They show that the second-order rate constants increase with the ethanol-to-water ratio, e.g., A2, second-order rate constant for the first Cs(+) in water: k(1A2water) = (9.7 +/- 0.3) x 10(4) M(-1) s(-1) and in M2: k(1A2M2) = (6.3 +/- 0.4) x 10(9) M(-1) s(-1). The affinities of both A1 and A2 for Cs(+) also increase with the ethanol-to-water ratio, e.g., first inclusion of A1 in M1: K(1A1M1) = (5 +/- 1.3) x 10(3) and in ethanol: K(1A1EtOH) = (7 +/- 3) x 10(6). The deviation from the expected mechanism of complex formation with alkali is attributed to the comparatively more difficult access of Cs(+) to the inclusion cavity of the capped calixarene. An analysis of calix-COU2 and calix-COUSULF and their Cs(+) complexes with only one rim capped by the crown ether confirms the thermodynamic and kinetic results, by showing that the inclusion cavity of calix-COUSULF is more adapted to Cs(+) than that of calix-COU2. This added to the presence of the shielding effect of the negative sulfonates can explain that the affinity of calix-COUSULF for Cs(+) is higher than that of calix-COU2. These results can be of interest in the search of an efficient Cs(+) decontaminant. PMID:19799465

  12. Measurement of complexation properties of metal ions in natural conditions by ultrafiltration: measurement of equilibrium constants for complexation of zinc by synthetic and natural ligands

    SciTech Connect

    Buffle, J.; Staub, C.

    1984-12-01

    A new ultrafiltration method is described to measure complexation properties (stability constants) of trace metal ions with natural aquatic ligands. The determination of stability constants is described theoretically and the best operational conditions are discussed theoretically and experimentally. Theory is tested with Zn, known synthetic ligands, and pedogenic fulvic acids of natural waters. The results obtained by this method compare well with the literature data. In particular, for natural mixture of complexing sites like fulvic acids, this method permits the determination of the detailed equilibrium function to be carried out instead of its average value, over a given range of metal to ligand ratio. The most important advantages of this method are the fact that there is no limitation with regard to the nature of metal ions and little for that of the ligands.

  13. Teasing out Simplicity from Complexity: the Law of Constant Bankfull Velocity in Alluvial Rivers

    NASA Astrophysics Data System (ADS)

    Parker, G.

    2014-12-01

    Of interest here are single-tread alluvial channels (or mildly anastomosing reaches with a single dominant channel) which are self-formed within their own floodplain. The 232 reaches considered here cover nearly the entire range of such channels, with bankfull discharge varying from 3.3x10-1 m3/s to 2.6x105 m3/s, characteristic bed material size varying from 0.04 mm to 168 mm, bed slopes varying from 8x7x10-6 to 5.2x10-2 and bankfull depths varying from 2.2x10-1 m to 4.8x101 m. These channels show complexity at every scale, including the organization of bed grains, the existence or absence of bedforms such as dunes and bars, the state of eroding banks (e.g. fallen trees, rooted stumps, or slump blocks) and the species and density of floodplain vegetation. Scientific research can often be broadly classified into two types: a) research that shows that a system formerly thought to be relatively simple is instead much more complex, with an increase in the number of factors which must be considered to obtain understanding; and b) research which extracts general, broad-brush simplicity from complexity. Both approaches can contribute to the advancement of science. Here we consider the second approach. The problem in question pertains to an explanation of an observation from the time of Luna Leopold: the single bankfull parameter that appears to be invariant is bankfull flow velocity. Here we demonstrate this result empirically at first-order, obtaining the estimate of 1.5 m/s across scales. We then derive a single, universal dimensionless number that specifies bankfull velocity, again across scales. The result is independent of bed material grain size, suggesting that previously-ignored wash load plays a major, and perhaps the dominant role as floodplain material load in setting bankfull velocity.

  14. The determination of equilibrium constants for heterogeneous macromolecular interactions. Systems forming 2:1 complexes.

    PubMed

    Crowl-Powers, M L; Zimmerman, J K

    1988-10-01

    In developing a method for analyzing the heterogeneous association nA + mB in equilibrium AnBm, we have specifically investigated the case of n = 2, m = 1 for both the specific case of no appreciable intermediates and the more general case allowing intermediates. Computer-simulated three-dimensional surfaces of the 2:1 model generated from total concentrations of species A and B and the resulting weight-average molecular weights were analyzed with a Gauss-Newton nonlinear least-squares minimization routine. The surfaces generated included normalized random error of varying standard deviations imposed upon both the concentrations and weight-average molecular weights. For comparison purposes, these surfaces were analyzed not only by using the correct 2:1 model, but also by an incorrect (1:1) model and by the other (incorrect) 2:1 model. Except for those situations where the 'experimental' noise was consistently higher than the concentration of one of the species, correct K values were obtained and the correct model was easily distinguished from the incorrect model. The computer routine similarly distinguished between data correctly described as 1:1 and the same data incorrectly analyzed as either 2:1 model. For those cases in which a microscopic Ki value predicts an association such that all species involved for that particular Ki are in appreciable amounts, the Ki value is returned correctly. Correct overall equilibrium constants are also converged upon as long as adequate amounts of A2B, B and A are present. PMID:3233309

  15. Constant p53 pathway inactivation in a large series of soft tissue sarcomas with complex genetics.

    PubMed

    Prot, Galle; Chibon, Frdric; Montero, Audrey; Lagarde, Pauline; de Th, Hugues; Terrier, Philippe; Guillou, Louis; Ranchre, Dominique; Coindre, Jean-Michel; Aurias, Alain

    2010-10-01

    Alterations of the p53 pathway are among the most frequent aberrations observed in human cancers. We have performed an exhaustive analysis of TP53, p14, p15, and p16 status in a large series of 143 soft tissue sarcomas, rare tumors accounting for around 1% of all adult cancers, with complex genetics. For this purpose, we performed genomic studies, combining sequencing, copy number assessment, and expression analyses. TP53 mutations and deletions are more frequent in leiomyosarcomas than in undifferentiated pleomorphic sarcomas. Moreover, 50% of leiomyosarcomas present TP53 biallelic inactivation, whereas most undifferentiated pleomorphic sarcomas retain one wild-type TP53 allele (87.2%). The spectrum of mutations between these two groups of sarcomas is different, particularly with a higher rate of complex mutations in undifferentiated pleomorphic sarcomas. Most tumors without TP53 alteration exhibit a deletion of p14 and/or lack of mRNA expression, suggesting that p14 loss could be an alternative genotype for direct TP53 inactivation. Nevertheless, the fact that even in tumors altered for TP53, we could not detect p14 protein suggests that other p14 functions, independent of p53, could be implicated in sarcoma oncogenesis. In addition, both p15 and p16 are frequently codeleted or transcriptionally co-inhibited with p14, essentially in tumors with two wild-type TP53 alleles. Conversely, in TP53-altered tumors, p15 and p16 are well expressed, a feature not incompatible with an oncogenic process. PMID:20884963

  16. Constant p53 Pathway Inactivation in a Large Series of Soft Tissue Sarcomas with Complex Genetics

    PubMed Central

    Prot, Galle; Chibon, Frdric; Montero, Audrey; Lagarde, Pauline; de Th, Hugues; Terrier, Philippe; Guillou, Louis; Ranchre, Dominique; Coindre, Jean-Michel; Aurias, Alain

    2010-01-01

    Alterations of the p53 pathway are among the most frequent aberrations observed in human cancers. We have performed an exhaustive analysis of TP53, p14, p15, and p16 status in a large series of 143 soft tissue sarcomas, rare tumors accounting for around 1% of all adult cancers, with complex genetics. For this purpose, we performed genomic studies, combining sequencing, copy number assessment, and expression analyses. TP53 mutations and deletions are more frequent in leiomyosarcomas than in undifferentiated pleomorphic sarcomas. Moreover, 50% of leiomyosarcomas present TP53 biallelic inactivation, whereas most undifferentiated pleomorphic sarcomas retain one wild-type TP53 allele (87.2%). The spectrum of mutations between these two groups of sarcomas is different, particularly with a higher rate of complex mutations in undifferentiated pleomorphic sarcomas. Most tumors without TP53 alteration exhibit a deletion of p14 and/or lack of mRNA expression, suggesting that p14 loss could be an alternative genotype for direct TP53 inactivation. Nevertheless, the fact that even in tumors altered for TP53, we could not detect p14 protein suggests that other p14 functions, independent of p53, could be implicated in sarcoma oncogenesis. In addition, both p15 and p16 are frequently codeleted or transcriptionally co-inhibited with p14, essentially in tumors with two wild-type TP53 alleles. Conversely, in TP53-altered tumors, p15 and p16 are well expressed, a feature not incompatible with an oncogenic process. PMID:20884963

  17. Complex effects of melatonin on human circadian rhythms in constant dim light.

    PubMed

    Middleton, B; Arendt, J; Stone, B M

    1997-10-01

    In humans, the pineal hormone melatonin can phase shift a number of circadian rhythms (e.g., "fatigue", endogenous melatonin, core body temperature) together with the timing of prolactin secretion. It is uncertain, however, whether melatonin can fully entrain all human circadian rhythms. In this study, the authors investigated the effects of daily melatonin administration on sighted individuals kept in continuous very dim light. A total of 10 normal, healthy males were maintained in two separate groups in partial temporal isolation under constant dim light (< 8 lux) with attenuated sound and ambient temperature variations but with knowledge of clock time for two periods of 30 days. In these circumstances, the majority of individuals free run with a mean period of 24.3 h. In a double-blind, randomized crossover design, subjects received 5 mg melatonin at 20:00 h on Days 1 to 15 (Melatonin 1st) followed by placebo on Days 16 to 30 (Placebo 2nd) or vice versa (Placebo 1st, Melatonin 2nd) during Leg 1 with treatment reversed in Leg 2. The variables measured were melatonin (as 6-sulphatoxymelatonin), rectal temperature, activity, and sleep (actigraphy and logs). In the experiment, 9 of the 10 subjects free ran with Placebo 1st, whereas Melatonin 1st stabilized the sleep-wake cycle to 24 h in 8 of 10 individuals. In addition, 2 individuals showed irregular sleep with this treatment. In some subjects, there was a shortening of the period of the temperature rhythm without synchronization. Melatonin 2nd induced phase advances (5 of 9 subjects), phase delays (2 of 9 subjects), and stabilization (2 of 9 subjects) of the sleep-wake cycle with subsequent synchronization to 24 h in the majority of individuals (7 of 9). Temperature continued to free run in 4 subjects. Maximum phase advances in core temperature were seen when the first melatonin treatment was given approximately 2 h after the temperature acrophase. These results indicate that melatonin was able to phase shift sleep and core temperature but was unable to synchronize core temperature consistently. In the majority of subjects, the sleep-wake cycle could be synchronized. PMID:9376645

  18. Spectroscopic and thermodynamic study of charge transfer complex formation between cloxacillin sodium and riboflavin in aqueous ethanol media of varying composition.

    PubMed

    Roy, Dalim Kumar; Saha, Avijit; Mukherjee, Asok K

    2006-03-01

    Cloxacillin sodium has been shown to form a charge transfer complex of 2:1 stoichiometry with riboflavin (Vitamin B(2)) in aqueous ethanol medium. The enthalpy and entropy of formation of this complex have been determined by estimating the formation constant spectrophotometrically at five different temperatures in pure water medium. Pronounced effect of dielectric constant of the medium on the magnitude of K has been observed by determining K in aqueous ethanol mixtures of varying composition. This has been rationalized in terms of ionic dissociation of the cloxacillin sodium (D(-)Na(+)), hydrolysis of the anion D(-) and complexation of the free acid, DH with riboflavin. PMID:16150635

  19. Spectroscopic and thermodynamic study of charge transfer complex formation between cloxacillin sodium and riboflavin in aqueous ethanol media of varying composition

    NASA Astrophysics Data System (ADS)

    Roy, Dalim Kumar; Saha, Avijit; Mukherjee, Asok K.

    2006-03-01

    Cloxacillin sodium has been shown to form a charge transfer complex of 2:1 stoichiometry with riboflavin (Vitamin B 2) in aqueous ethanol medium. The enthalpy and entropy of formation of this complex have been determined by estimating the formation constant spectrophotometrically at five different temperatures in pure water medium. Pronounced effect of dielectric constant of the medium on the magnitude of K has been observed by determining K in aqueous ethanol mixtures of varying composition. This has been rationalized in terms of ionic dissociation of the cloxacillin sodium (D -Na +), hydrolysis of the anion D - and complexation of the free acid, DH with riboflavin.

  20. Dynamics of electrical double layer formation in room-temperature ionic liquids under constant-current charging conditions.

    PubMed

    Jiang, Xikai; Huang, Jingsong; Zhao, Hui; Sumpter, Bobby G; Qiao, Rui

    2014-07-16

    We report detailed simulation results on the formation dynamics of an electrical double layer (EDL) inside an electrochemical cell featuring room-temperature ionic liquids (RTILs) enclosed between two planar electrodes. Under relatively small charging currents, the evolution of cell potential from molecular dynamics (MD) simulations during charging can be suitably predicted by the Landau-Ginzburg-type continuum model proposed recently (Bazant et al 2011 Phys. Rev. Lett. 106 046102). Under very large charging currents, the cell potential from MD simulations shows pronounced oscillation during the initial stage of charging, a feature not captured by the continuum model. Such oscillation originates from the sequential growth of the ionic space charge layers near the electrode surface. This allows the evolution of EDLs in RTILs with time, an atomistic process difficult to visualize experimentally, to be studied by analyzing the cell potential under constant-current charging conditions. While the continuum model cannot predict the potential oscillation under such far-from-equilibrium charging conditions, it can nevertheless qualitatively capture the growth of cell potential during the later stage of charging. Improving the continuum model by introducing frequency-dependent dielectric constant and density-dependent ion diffusion coefficients may help to further extend the applicability of the model. The evolution of ion density profiles is also compared between the MD and the continuum model, showing good agreement. PMID:24919471

  1. Dynamics of electrical double layer formation in room-temperature ionic liquids under constant-current charging conditions

    SciTech Connect

    Jiang, Xikai; Huang, Jingsong; Zhao, Hui; Sumpter, Bobby G; Qiao, Rui

    2014-01-01

    We report detailed simulation results on the formation dynamics of an electrical double layer (EDL) inside an electrochemical cell featuring room-temperature ionic liquids (RTILs) enclosed between two planar electrodes. Under relatively small charging currents, the evolution of cell potential during charging can be suitably predicted by the Landau-Ginzburg-type continuum model proposed recently (M. Z. Bazant, B. D. Storey, and A. A. Kornyshev, Phys. Rev. Lett., 106, 046102, 2011). Under very large charging currents, the cell potential shows pronounced oscillation during the initial stage of charging, a feature not captured by the continuum model. Such oscillation originates from the sequential growth of the ionic space charge layers near the electrode surface, allowing the evolution of EDLs in RTILs with time, an atomistic process difficult to visualize experimentally, to be studied by analyzing the cell potential under constant current charging conditions. While the continuum model cannot predict the potential oscillation under such far-from-equilibrium charging conditions, it can nevertheless qualitatively capture the growth of cell potential during the later stage of charging. Improving the continuum model by introducing frequency-dependent dielectric constant and density-dependent ion diffusion coefficients may help to further extend the applicability of the model. Keywords: ionic

  2. The ribosome-associated complex antagonizes prion formation in yeast

    PubMed Central

    Amor, Alvaro J; Castanzo, Dominic T; Delany, Sean P; Selechnik, Daniel M; van Ooy, Alex; Cameron, Dale M

    2015-01-01

    Abstract The number of known fungal proteins capable of switching between alternative stable conformations is steadily increasing, suggesting that a prion-like mechanism may be broadly utilized as a means to propagate altered cellular states. To gain insight into the mechanisms by which cells regulate prion formation and toxicity we examined the role of the yeast ribosome-associated complex (RAC) in modulating both the formation of the [PSI+] prion – an alternative conformer of Sup35 protein – and the toxicity of aggregation-prone polypeptides. The Hsp40 RAC chaperone Zuo1 anchors the RAC to ribosomes and stimulates the ATPase activity of the Hsp70 chaperone Ssb. We found that cells lacking Zuo1 are sensitive to over-expression of some aggregation-prone proteins, including the Sup35 prion domain, suggesting that co-translational protein misfolding increases in Δzuo1 strains. Consistent with this finding, Δzuo1 cells exhibit higher frequencies of spontaneous and induced prion formation. Cells expressing mutant forms of Zuo1 lacking either a C-terminal charged region required for ribosome association, or the J-domain responsible for Ssb ATPase stimulation, exhibit similarly high frequencies of prion formation. Our findings are consistent with a role for the RAC in chaperoning nascent Sup35 to regulate folding of the N-terminal prion domain as it emerges from the ribosome. PMID:25739058

  3. The ribosome-associated complex antagonizes prion formation in yeast.

    PubMed

    Amor, Alvaro J; Castanzo, Dominic T; Delany, Sean P; Selechnik, Daniel M; van Ooy, Alex; Cameron, Dale M

    2015-01-01

    The number of known fungal proteins capable of switching between alternative stable conformations is steadily increasing, suggesting that a prion-like mechanism may be broadly utilized as a means to propagate altered cellular states. To gain insight into the mechanisms by which cells regulate prion formation and toxicity we examined the role of the yeast ribosome-associated complex (RAC) in modulating both the formation of the [PSI(+)] prion - an alternative conformer of Sup35 protein - and the toxicity of aggregation-prone polypeptides. The Hsp40 RAC chaperone Zuo1 anchors the RAC to ribosomes and stimulates the ATPase activity of the Hsp70 chaperone Ssb. We found that cells lacking Zuo1 are sensitive to over-expression of some aggregation-prone proteins, including the Sup35 prion domain, suggesting that co-translational protein misfolding increases in ?zuo1 strains. Consistent with this finding, ?zuo1 cells exhibit higher frequencies of spontaneous and induced prion formation. Cells expressing mutant forms of Zuo1 lacking either a C-terminal charged region required for ribosome association, or the J-domain responsible for Ssb ATPase stimulation, exhibit similarly high frequencies of prion formation. Our findings are consistent with a role for the RAC in chaperoning nascent Sup35 to regulate folding of the N-terminal prion domain as it emerges from the ribosome. PMID:25739058

  4. Ion wake formation with dust charge fluctuation in complex plasma

    SciTech Connect

    Bhattacharjee, Saurav; Das, Nilakshi

    2013-11-15

    In complex plasma, the interaction mechanism among dust grains near the plasma sheath is significantly influenced by the downward ion flow towards the sheath and dust charge fluctuation over grain surface. Asymmetric ion flow towards the sheath gives rise to well known attractive wake potential in addition to repulsive Yukawa type of potential. The present work shows that the charging dynamics play a significant role in modification of plasma dielectric response function and hence the interaction mechanism among test dust particulates. The effective Debye length is found to be a characteristic of dust size and background plasma response towards the grain along with ion flow speed. The potentials thus obtained show a damping in strength of interaction in the presence of dynamical charging of dust as compared to that of constant charge dust grains. The result also shows decrease in focal length of ion lensing with increase in grain size.

  5. Complex interactions between formative assessment, technology, and classroom practices

    NASA Astrophysics Data System (ADS)

    Price, Edward

    2012-02-01

    Interactive engagement (IE) methods provide instructors with evidence of student thinking that can guide instructional decisions across a range of timescales: facilitating an activity, determining the flow of activities, or modifying the curriculum. Thus, from the instructor's perspective, IE activities can function as formative assessments. As a practical matter, the ability to utilize this potential depends on how the activities are implemented. This paper describes different tools for small group problem solving, including whiteboards, Tablet PCs, digital cameras, and photo-sharing websites. These tools provide the instructor with varying levels of access to student work during and after class, and therefore provide a range of support for formative assessment. Furthermore, the tools differ in physical size, ease of use, and the roles for students and instructor. These differences lead to complex, often surprising interactions with classroom practices.

  6. Formation of polyelectrolyte complexes with diethylaminoethyl dextran: charge ratio and molar mass effect.

    PubMed

    Le Cerf, Didier; Pepin, Anne Sophie; Niang, Pape Momar; Cristea, Mariana; Karakasyan-Dia, Carole; Picton, Luc

    2014-11-26

    The formation of polyelectrolyte complexes (PECs) between carboxymethyl pullulan and DEAE Dextran, was investigated, in dilute solution, with emphasis on the effect of charge density (molar ratio or pH) and molar masses. Electrophoretic mobility measurements have evidenced that insoluble PECs (neutral electrophoretic mobility) occurs for charge ratio between 0.6 (excess of polycation) and 1 (stoichiometry usual value) according to the pH. This atypical result is explained by the inaccessibility of some permanent cationic charge when screened by pH dependant cationic ones (due to the Hoffman alkylation). Isothermal titration calorimetry (ITC) indicates an endothermic formation of PEC with a binding constant around 10(5) L mol(-1). Finally asymmetrical flow field flow fractionation coupled on line with static multi angle light scattering (AF4/MALS) evidences soluble PECs with very large average molar masses and size around 100 nm, in agreement with scrambled eggs multi-association between various polyelectrolyte chains. PMID:25256478

  7. In vacuo formation of peptide-metal coordination complexes.

    PubMed

    McAlister, Graeme C; Kiessel, Sharon E B; Coon, Joshua J

    2008-10-01

    Here we report on the reaction of rhenate anions (ReO(3) (-)) with multiply protonated peptide cations in a quadrupole linear ion trap mass spectrometer. These reactions effect the formation of an anion-cation complex that, upon collisional activation, dissociates along the peptide backbone rather than by displacement of the anion. Cleavage of the peptide backbone, with anion retention, leads us to conclude the anion-cationcomplexmust be tightly bound, most probably through coordination chemistry. We describe this chemistry and detail the possible application of such ion attachment reactions to the characterization of intact proteins. PMID:19424441

  8. In vacuo formation of peptidemetal coordination complexes

    PubMed Central

    McAlister, Graeme C.; Kiessel, Sharon E.B.; Coon, Joshua J.

    2009-01-01

    Here we report on the reaction of rhenate anions (ReO3?) with multiply protonated peptide cations in a quadrupole linear ion trap mass spectrometer. These reactions effect the formation of an anioncation complex that, upon collisional activation, dissociates along the peptide backbone rather than by displacement of the anion. Cleavage of the peptide backbone, with anion retention, leads us to conclude the anioncationcomplexmust be tightly bound, most probably through coordination chemistry. We describe this chemistry and detail the possible application of such ion attachment reactions to the characterization of intact proteins. PMID:19424441

  9. Formation mechanism of complex pattern on fishes' skin

    NASA Astrophysics Data System (ADS)

    Li, Xia; Liu, Shuhua

    2009-10-01

    In this paper, the formation mechanism of the complex patterns observed on the skin of fishes has been investigated by a two-coupled reaction diffusion model. The effects of coupling strength between two layers play an important role in the pattern-forming process. It is found that only the epidermis layer can produce complicated patterns that have structures on more than one length scale. These complicated patterns including super-stripe pattern, mixture of spots and stripe, and white-eye pattern are similar to the pigmentation patterns on fishes' skin.

  10. Redox reactions and complex formation of transplutonium elements in solutions

    SciTech Connect

    Krot, N.N.; Myasoedov, B.F.

    1986-01-01

    This paper gives a brief analysis of the kinetics and mechanism of a number of redox processes and the complex formation of transplutonium elements in unusual oxidation states. The composition and strength of complexes of TPE with various addends have been determined. The new experimental data on the oxidation potentials of americium and berkelium ions in solutions are cited in abbreviated form. It follows from the data that in phosphoric acid solutions, when the H/sub 3/PO/sub 4/ concentration is increased from 10 to 15 M, the oxidation potential of the couple Am(IV)-Am(III) decreases. The oxidation potentials of the couples Am(VI)-Am(V), Cm(V)-Cm(IV), and Bk(IV)Bk(III) are also presented.

  11. Molecular determinants of orexin receptor-arrestinubiquitin complex formation

    PubMed Central

    Jaeger, Werner C; Seeber, Ruth M; Eidne, Karin A; Pfleger, Kevin DG

    2014-01-01

    Background and Purpose: The orexin system regulates a multitude of key physiological processes, particularly involving maintenance of metabolic homeostasis. Consequently, there is considerable potential for pharmaceutical development for the treatment of disorders from narcolepsy to metabolic syndrome. It acts through the hormonal activity of two endogenous peptides, orexin A binding to orexin receptors 1 and 2 (OX1 and OX2) with similar affinity, and orexin B binding to OX2 with higher affinity than OX1 receptors. We have previously revealed data differentiating orexin receptor subtypes with respect to their relative stability in forming orexin receptor-arrestin-ubiquitin complexes measured by BRET. Recycling and cellular signalling distinctions were also observed. Here, we have investigated, using BRET, the molecular determinants involved in providing OX2 receptors with greater β-arrestin-ubiquitin complex stability. Experimental Approach: The contribution of the C-terminal tail of the OX receptors was investigated by bulk substitution and site-specific mutagenesis using BRET and inositol phosphate assays. Key Results: Replacement of the OX1 receptor C-terminus with that of the OX2 receptor did not result in the expected gain of function, indicating a role for intracellular domain configuration in addition to primary structure. Furthermore, two out of the three putative serine/threonine clusters in the C-terminus were found to be involved in OX2 receptor-β-arrestin-ubiquitin complex formation. Conclusions and Implications: This study provides fundamental insights into the molecular elements that influence receptor-arrestin-ubiquitin complex formation. Understanding how and why the orexin receptors can be functionally differentiated brings us closer to exploiting these receptors as drug targets. Linked Articles: This article is part of a themed section on Orexin Receptors. To view the other articles in this section visit http://dx.doi.org/10.1111/bph.2014.171.issue-2 PMID:24206104

  12. Constant speed control for complex cross-section welding using robot based on angle self-test

    NASA Astrophysics Data System (ADS)

    Xue, Long; Zou, Yong; Huang, Jiqiang; Huang, Junfen; Tao, Xinghua; Hu, Yanfeng

    2014-03-01

    Expandable profile liner(EPL) is a promising new oil well casing cementing technique, and welding is a major EPLs connection technology. Connection of EPL is still in the stage of manual welding so far, automatic welding technology is a hotspot of EPL which is one of the key technologies to be solved. A robot for automatic welding of "8" type EPL is studied. Four quadrants of mathematical equations of the 8-shaped cross-section track of EPL, consisting of multiple arcs, are established. Mechanism program for complex cross-section welding of EPL based on angle detection is proposed according to characteristics of small size, small valleys, and large forming errors, etc. A welding velocity vector control model is established by linkage control of a welding vehicle, a small driven actuator, and a height tracking mechanism. A constant speed control model based on an angle and symmetrical analysis model of rectangular coordinate system for EPL is built. Constraint conditions of constant speed control between each section are analyzed with 4 sections in first quadrant as an example, and cooperation work mechanism of the welding vehicle and the small tracking actuator is established based on pressure detection. The constant speed control model using angle self-test can be used to avoid the need for a precise mathematical model for tracking control and to adapt manufacture and installation deviation of EPL workpiece. The model is able to solve constant speed and trajectory tracking problems of EPL cross-section welding. EPL seams welded by the studied robot are good in appearance, and non-destructive testing(NDT) shows the seams are good in quality with no welding defects. Bulge tests show that the maximum pressure of welded EPL is 35 MPa, which can fulfill expansion performance requirements.

  13. Characterization of Hydrogen Complex Formation in III-V Semiconductors

    SciTech Connect

    Williams, Michael D

    2006-09-28

    Atomic hydrogen has been found to react with some impurity species in semiconductors. Hydrogenation is a methodology for the introduction of atomic hydrogen into the semiconductor for the express purpose of forming complexes within the material. Efforts to develop hydrogenation as an isolation technique for AlGaAs and Si based devices failed to demonstrate its commercial viability. This was due in large measure to the low activation energies of the formed complexes. Recent studies of dopant passivation in long wavelength (0.98 - 1.55m) materials suggested that for the appropriate choice of dopants much higher activation energies can be obtained. This effort studied the formation of these complexes in InP, This material is extensively used in optoelectronics, i.e., lasers, modulators and detectors. The experimental techniques were general to the extent that the results can be applied to other areas such as sensor technology, photovoltaics and to other material systems. The activation energies for the complexes have been determined and are reported in the scientific literature. The hydrogenation process has been shown by us to have a profound effect on the electronic structure of the materials and was thoroughly investigated. The information obtained will be useful in assessing the long term reliability of device structures fabricated using this phenomenon and in determining new device functionalities.

  14. Formation of transition metal-doxorubicin complexes inside liposomes.

    PubMed

    Abraham, Sheela Ann; Edwards, Katarina; Karlsson, Göran; MacIntosh, Scott; Mayer, Lawrence D; McKenzie, Cheryl; Bally, Marcel B

    2002-09-20

    Doxorubicin complexation with the transition metal manganese (Mn(2+)) has been characterized, differentiating between the formation of a doxorubicin-metal complex and doxorubicin fibrous-bundle aggregates typically generated following ion gradient-based loading procedures that rely on liposome encapsulated citrate or sulfate salts. The physical and chemical characteristics of the encapsulated drug were assessed using cryo-electron microscopy, circular dichroism (CD) and absorbance spectrophotometric analysis. In addition, in vitro and in vivo drug loading and release characteristics of the liposomal formulations were investigated. Finally, the internal pH after drug loading was measured with the aim of linking formation of the Mn(2+) complex to the presence or absence of a transmembrane pH gradient. Doxorubicin was encapsulated into either 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC)/cholesterol (Chol) or 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC)/Chol liposomes, where the entrapped salts were citrate, MnSO(4) or MnCl(2). In response to a pH gradient or a Mn(2+) ion gradient, doxorubicin accumulated inside to achieve a drug-to-lipid ratio of approximately 0.2:1 (wt/wt). Absorbance and CD spectra of doxorubicin in the presence of Mn(2+) suggested that there are two distinct structures captured within the liposomes. In the absence of added ionophore A23187, drug loading is initiated on the basis of an established pH gradient; however, efficient drug uptake is not dependent on maintenance of the pH gradient. Drug release from DMPC/Chol is comparable regardless of whether doxorubicin is entrapped as a citrate-based aggregate or a Mn(2+) complex. However, in vivo drug release from DSPC/Chol liposomes indicate less than 5% or greater than 50% drug loss over a 24-h time course when the drug was encapsulated as an aggregate or a Mn(2+) complex, respectively. These studies define a method for entrapping drugs possessing coordination sites capable of complexing transition metals and suggest that drug release is dependent on lipid composition, internal pH, as well as the nature of the crystalline precipitate, which forms following encapsulation. PMID:12225851

  15. DFT calculations of 15N NMR shielding constants, chemical shifts and complexation shifts in complexes of rhodium(II) tetraformate with some nitrogenous organic ligands

    NASA Astrophysics Data System (ADS)

    Leniak, Arkadiusz; Jaźwiński, Jarosław

    2015-03-01

    Benchmark calculations of 15N NMR shielding constants for a set of model complexes of rhodium(II) tetraformate with nine organic ligands using the Density Functional Theory (DFT) methods have been carried out. The calculations were performed by means of several methods: the non-relativistic, relativistic scalar ZORA, and spin-orbit ZORA approaches at the CGA-PBE/QZ4P theory level, and the GIAO NMR method using the B3PW91 functional with the 6-311++G(2d,p) basis set for C, H, N, O atoms and the Stuttgart basis set for the Rh atom. The geometry of compounds was optimised either by the same basis set as for the NMR calculations or applying the B3LYP functional with the 6-31G(2d) basis set for C, H, N, O atoms and LANL2DZ for the Rh atom. Computed 15N NMR shielding constants σ were compatible with experimental 15N chemical shifts δ of complexes exhibiting similar structure and fulfil the linear equation δ = aσ + b. The a and b parameters for all data sets have been estimated by means of linear regression analysis. In contrast to the correlation method giving "scaled" chemical shifts, the conversion of shielding constants to chemical shifts with respect to the reference shielding of CH3NO2 provided very inaccurate "raw" δ values. The application of the former to the calculation of complexation shifts Δδ (Δδ = δcompl - δlig) reproduced experimental values qualitatively or semi-quantitatively. The non-relativistic B3PW91/[6-311++G(2d,p), Stuttgart] theory level reproduced the NMR parameters as good as the more expensive relativistic CGA-PBE//QZ4P ZORA approaches.

  16. Incipient species formation in salamanders of the Ensatina?complex

    PubMed Central

    Wake, David B.

    1997-01-01

    The Ensatina eschscholtzii complex of plethodontid salamanders, a well-known ring species, is thought to illustrate stages in the speciation process. Early research, based on morphology and coloration, has been extended by the incorporation of studies of protein variation and mitochondrial DNA sequences. The new data show that the complex includes a number of geographically and genetically distinct components that are at or near the species level. The complex is old and apparently has undergone instances of range contraction, isolation, differentiation, and then expansion and secondary contact. While the hypothesis that speciation is retarded by gene flow around the ring is not supported by molecular data, the general biogeographical hypothesis is supported. There is evidence of a north to south range expansion along two axes, with secondary contact and completion of the ring in southern California. Current research targets regions once thought to show primary intergradation, but which molecular markers reveal to be zones of secondary contact. Here emphasis is on the subspecies E. e. xanthoptica, which is involved in four distinct secondary contacts in central California. There is evidence of renewed genetic interactions upon recontact, with greater genetic differentiation within xanthoptica than between it and some of the interacting populations. The complex presents a full array of intermediate conditions between well-marked species and geographically variable populations. Geographically differentiated segments represent a diversity of depths of time of isolation and admixture, reflecting the complicated geomorphological history of California. Ensatina illustrates the continuing difficulty in making taxonomic assignments in complexes studied during species formation. PMID:9223261

  17. Spectrophotometric, FTIR and theoretical studies of the charge-transfer complexes between isoniazid (pyridine-4-carboxylic acid hydrazide) and the acceptors (p-chloranil, chloranilic acid and tetracyanoethylene) in acetonitrile, their association constants, thermodynamic properties and other related properties

    NASA Astrophysics Data System (ADS)

    Bagchi (Chattaraj), Seema; Sharma, Kakali; Chakrabortty, Ashutosh; Lahiri, Sujit Chandra

    Spectrophotometric, FTIR and theoretical studies of the charge-transfer complexes between Isoniazid (pyridine-4-carboxylic acid hydrazide) and the acceptors (p-chloranil, chloranilic acid and tetracyanoethylene) in acetonitrile, their association constants, thermodynamic properties and other related properties were studied. Isoniazid (INH), a widely used anti tubercular agent was found to form beautifully colored charge-transfer complexes with p-chloranil, chloranilic acid and tetracyanoethylene in acetonitrile. The absorption maxima of the complexes were 484, 519 and 479 nm, respectively (isoniazid had no absorption, but the acceptors had absorption in these regions). The composition of the complexes were determined to be 1:1 from Job's method of continuous variations depending on the time period of experiments as the stability of some of the complexes (p-chloranil and tetracyanoethylene complexes) was time dependent. Solid complexes formed between isoniazid and the acceptors were isolated but p-chloranil was found to form two different complexes. FTIR spectra of the complexes and the acceptors were measured. FTIR spectra of the complexes showed considerable shift in absorption peaks, changes in intensities of the peaks and formation of the new band (probably due to hydrogen bonding) on complexation. The thermodynamic association constants and other thermodynamic parameters of the complexes were determined spectrophotometrically taking D and A in varying ratios (2:8-8:2) and also in equimolar ratios. The complex formation was found to be spontaneous and associated with negative changes of ?G0, ?H0 and ?S0. The energies h?CT of the charge-transfer complexes were compared with the theoretical values of h?CT of the complexes obtained from HOMO and LUMO of the donor and the acceptors. Density function theory utilizing different basis sets was used for calculation. h?CT (experimental) values of the transition energies of the complexes in acetonitrile differed from h?CT (theoretical) values in the gaseous state. IDV value of isoniazid was calculated. Charge-transfer complexes were assumed to be partial electrovalent compounds with organic dative ions D+ and A- (in the excited state) and attempts had been made to correlate the energy changes for the formation of the complexes with the energy changes for the formation of electrovalent compounds between M+ and X- ions.

  18. Spectrophotometric, FTIR and theoretical studies of the charge-transfer complexes between isoniazid (pyridine-4-carboxylic acid hydrazide) and the acceptors (p-chloranil, chloranilic acid and tetracyanoethylene) in acetonitrile, their association constants, thermodynamic properties and other related properties.

    PubMed

    Bagchi Chattaraj, Seema; Sharma, Kakali; Chakrabortty, Ashutosh; Lahiri, Sujit Chandra

    2012-09-01

    Spectrophotometric, FTIR and theoretical studies of the charge-transfer complexes between Isoniazid (pyridine-4-carboxylic acid hydrazide) and the acceptors (p-chloranil, chloranilic acid and tetracyanoethylene) in acetonitrile, their association constants, thermodynamic properties and other related properties were studied. Isoniazid (INH), a widely used anti tubercular agent was found to form beautifully colored charge-transfer complexes with p-chloranil, chloranilic acid and tetracyanoethylene in acetonitrile. The absorption maxima of the complexes were 484, 519 and 479 nm, respectively (isoniazid had no absorption, but the acceptors had absorption in these regions). The composition of the complexes were determined to be 1:1 from Job's method of continuous variations depending on the time period of experiments as the stability of some of the complexes (p-chloranil and tetracyanoethylene complexes) was time dependent. Solid complexes formed between isoniazid and the acceptors were isolated but p-chloranil was found to form two different complexes. FTIR spectra of the complexes and the acceptors were measured. FTIR spectra of the complexes showed considerable shift in absorption peaks, changes in intensities of the peaks and formation of the new band (probably due to hydrogen bonding) on complexation. The thermodynamic association constants and other thermodynamic parameters of the complexes were determined spectrophotometrically taking D and A in varying ratios (2:8-8:2) and also in equimolar ratios. The complex formation was found to be spontaneous and associated with negative changes of ?G(0), ?H(0) and ?S(0). The energies h?(CT) of the charge-transfer complexes were compared with the theoretical values of h?(CT) of the complexes obtained from HOMO and LUMO of the donor and the acceptors. Density function theory utilizing different basis sets was used for calculation. h?(CT) (experimental) values of the transition energies of the complexes in acetonitrile differed from h?(CT) (theoretical) values in the gaseous state. I(D)(V) value of isoniazid was calculated. Charge-transfer complexes were assumed to be partial electrovalent compounds with organic dative ions D(+) and A(-) (in the excited state) and attempts had been made to correlate the energy changes for the formation of the complexes with the energy changes for the formation of electrovalent compounds between M(+) and X(-) ions. PMID:22580135

  19. A dramatic change in the interaction of Cu(II) with bio-peptides promoted by SDS--a model for complex formation on a membrane surface.

    PubMed

    Bal, W; Kozlowski, H; Lisowski, M; Pettit, L; Robbins, R; Safavi, A

    1994-07-01

    The extent of complex formation between Cu(II) and many biologically active oligopeptides has been shown to change significantly in the presence of SDS micelles, a recognized model for cell lipid membranes. Protonation constants of peptides can be increased by up to 2 log unit, especially when they contain hydrophobic side chains. Metal complex formation is generally less extensive and the conformations of peptides can be altered dramatically when compared to those in simple aqueous solution. PMID:7519253

  20. Thermodynamics of adduct formation of cobalt(II) tetraaza Schiff base complexes with organotin(IV)trichlorides.

    PubMed

    Asadi, Zahra; Asadi, Mozaffar; Setoodehkhah, Moslem

    2013-08-01

    UV-Vis. spectrophotometric study of the adduct formation of organotin(IV)trichlorides i.e. PhSnCl3 and MeSnCl3 as acceptors with Co(II) tetraaza complexes, such as [Co(ampen)] [N,N'-ethylenebis-(o-amino-?-phenylbenzylideneiminato)cobalt(II)], [Co(campen)] [N,N'-ethylenebis-(5-chloro-o-amino-?-phenylbenzylideneiminato)cobalt(II)], [Co(amaen)] [N,N'-ethylenebis-(o-amino-?-methylbenzylideneiminato)cobalt(II)], [Co(amppn)] [N,N'-propylene bis-(5-chloro-o-amino-?-phenylbenzylideneiminato)cobalt(II)] and [Co(camppn)] [N,N'-propylenebis-(5-chloro-o-amino-?-phenylbenzylideneiminato)cobalt(II)] as donors were studied spectrophotometrically under N2 atmosphere and in N,N'-dimethylformamide solvent. The formation constants and thermodynamic parameters were measured using spectrophotometric titration of adduct formation at various temperatures. The trend of the adduct formations of the cobalt(II) tetraaza complexes with a given organotintrichloride acceptor decreases as follow: [Co(amaen)]>[Co(amppn)]>[Co(ampen)]>[Co(camppn)]>[Co(campen)]. The trend of the formation constants for the studied organotintrichlorides with a given cobalt(II) tetraaza complexes is as follow: PhSnCl3>MeSnCl3. PMID:23666357

  1. Thermodynamics of adduct formation of cobalt(II) tetraaza Schiff base complexes with organotin(IV)trichlorides

    NASA Astrophysics Data System (ADS)

    Asadi, Zahra; Asadi, Mozaffar; Setoodehkhah, Moslem

    2013-08-01

    UV-Vis. spectrophotometric study of the adduct formation of organotin(IV)trichlorides i.e. PhSnCl3 and MeSnCl3 as acceptors with Co(II) tetraaza complexes, such as [Co(ampen)] [N,N'-ethylenebis-(o-amino-?-phenylbenzylideneiminato)cobalt(II)], [Co(campen)] [N,N'-ethylenebis-(5-chloro-o-amino-?-phenylbenzylideneiminato)cobalt(II)], [Co(amaen)] [N,N'-ethylenebis-(o-amino-?-methylbenzylideneiminato)cobalt(II)], [Co(amppn)] [N,N'-propylene bis-(5-chloro-o-amino-?-phenylbenzylideneiminato)cobalt(II)] and [Co(camppn)] [N,N'-propylenebis-(5-chloro-o-amino-?-phenylbenzylideneiminato)cobalt(II)] as donors were studied spectrophotometrically under N2 atmosphere and in N,N'-dimethylformamide solvent. The formation constants and thermodynamic parameters were measured using spectrophotometric titration of adduct formation at various temperatures. The trend of the adduct formations of the cobalt(II) tetraaza complexes with a given organotintrichloride acceptor decreases as follow: [Co(amaen)] > [Co(amppn)] > [Co(ampen)] > [Co(camppn)] > [Co(campen)]. The trend of the formation constants for the studied organotintrichlorides with a given cobalt(II) tetraaza complexes is as follow: PhSnCl3 > MeSnCl3.

  2. Microcalorimetric determination of thermodynamic parameters for ionophore-siderophore host-guest complex formation.

    PubMed

    Trzaska, S M; Toone, E J; Crumbliss, A L

    2000-03-20

    Thermodynamic parameters (delta H, delta S, and delta G) were determined by microcalorimetry in wet chloroform for host-guest assembly formation involving second-sphere complexation of the siderophore ferrioxamine B by crown ether (18-crown-6, cis-dicyclohexano-18-crown-6, benzo-18-crown-6) and cryptand (2.2.2 cryptand) hosts. Similar data were also collected for the same hosts with the pentylammonium ion guest, which corresponds to the pendant pentylamine side chain of ferroxamine B. Host-guest assembly formation constants (Ka) obtained from microcalorimetry agree with values obtained indirectly from chloroform/water extraction studies in those cases where comparable data are available. On the basis of a trend established by the pentylammonium guest, an enhanced stability relative to the crown ethers is observed for the assembly composed of ferrioxamine B and 2.2.2 cryptand that is due to entropic effects. Trends in delta H and delta S with changes in host and guest structure are discussed and attributed directly to host-guest complex formation, as solvation effects were determined to be insignificant (delta Cp = 0). PMID:12526393

  3. Quantitative serine protease assays based on formation of copper(II)-oligopeptide complexes.

    PubMed

    Ding, Xiaokang; Yang, Kun-Lin

    2015-01-01

    A quantitative protease assay based on the formation of a copper-oligopeptide complex is developed. In this assay, when a tripeptide GGH fragment is cleaved from an oligopeptide chain by serine proteases, the tripeptide quickly forms a pink GGH/Cu(2+) complex whose concentration can be determined quantitatively by using UV-Vis spectroscopy. Therefore, activities of serine proteases can be determined from the formation rate of the GGH/Cu(2+) complex. This principle can be used to detect the presence of serine protease in a real-time manner, or measure proteolytic activities of serine protease cleaving different oligopeptide substrates. For example, by using this assay, we demonstrate that trypsin, a model serine protease, is able to cleave two oligopeptides GGGGKGGH () and GGGGRGGH (). However, the specificity constant (kcat/Km) for is higher than that of (6.4 10(3) mM(-1) min(-1)vs. 1.3 10(3) mM(-1) min(-1)). This result shows that trypsin is more specific toward arginine (R) than lysine (K) in the oligopeptide sequence. PMID:25386732

  4. Influence of structural features of carrageenan on the formation of polyelectrolyte complexes with chitosan.

    PubMed

    Volod'ko, A V; Davydova, V N; Glazunov, V P; Likhatskaya, G N; Yermak, I M

    2016-03-01

    The polyelectrolyte complexes (PEC) of carrageenans (CG)-?-, ?/?-, ?-and x-CG with chitosan were obtained. The formation of PEC was detected by Fourier-transform infrared (FTIR) spectroscopy and by centrifugation in a Percoll gradient. The influence of the structural peculiarities of CG on its interaction with chitosan was studied. The results of centrifugation showed that x-CG with a high degree of sulphation (SD) was completely bound to chitosan, unlike low SD ?-CG and ?/?-CG. Binding constant values showed there was a high affinity of CG for chitosan. CG with flexible macromolecule conformation and high SD exhibited the greatest binding affinity for chitosan. The full-atomic 3D-structures of the PEC ?-CG: chitosan in solution have been obtained by the experiments in silico for the first time. The amino groups of chitosan make the largest contribution to the energy of the complex formation by means of hydrogen and ionic bonds. The most probable complexes have stoichiometries of 1:1 and 1:1.5. PMID:26712704

  5. Salt effect on the complex formation between cationic gemini surfactant and anionic polyelectrolyte in aqueous solution.

    PubMed

    Wang, Xiaoyong; Wang, Jinben; Wang, Yilin; Yan, Haike

    2004-10-12

    Salt effect on the interaction of anionic polyelectrolyte sodium carboxymethylcellulose (NaCMC) with cationic gemini surfactant hexamethylene-1,6-bis(dodecyldimethylammonium bromide) [C12H25(CH3)2N(CH2)6N(CH3)2C12H25]Br2 (C12C6C12Br2) has been investigated using turbidimetric titration, steady-state fluorescence, and mobility measurement. It is found that the critical aggregation concentration(cac) for C12C6C12Br2/NaCMC complexes depends little on addition of sodium bromide (NaBr). However, in the presence of nonionic surfactant Triton X-100 (TX100), the critical ionic surfactant mole fraction for the onset of complex formation (Yc) increases markedly with increasing NaBr concentration. These salt effects are supposed as the overall result from competition between the increase of interaction and the screening of interaction. The increase of interaction is referred to as the effect that the larger micelle with higher surface charge density induced by salt has a stronger interaction with oppositely charged polyelectrolyte. The screening of interaction is referred to as the salt screening of electrostatic attraction between the polymer chain and the surfactant. For complex formation between C12C6C12Br2 and NaCMC, the increase of interaction probably compensates the screening of interaction, leading to constant cac values at different salt concentrations. For complex formation between the C12C6C12Br2/TX100 mixed micelle and NaCMC, the screening of interaction probably plays a dominant role, leading to higher suppression of electrostatic binding of micelles to polyelectrolyte. PMID:15461481

  6. Single Nucleoprotein Residue Modulates Arenavirus Replication Complex Formation

    PubMed Central

    Knopp, Kristeene A.; Ngo, Tuan; Gershon, Paul D.

    2015-01-01

    ABSTRACT The Arenaviridae are enveloped, negative-sense RNA viruses with several family members that cause hemorrhagic fevers. This work provides immunofluorescence evidence that, unlike those of New World arenaviruses, the replication and transcription complexes (RTC) of lymphocytic choriomeningitis virus (LCMV) colocalize with eukaryotic initiation factor 4E (eIF4E) and that eIF4E may participate in the translation of LCMV mRNA. Additionally, we identify two residues in the LCMV nucleoprotein (NP) that are conserved in every mammalian arenavirus and are required for recombinant LCMV recovery. One of these sites, Y125, was confirmed to be phosphorylated by using liquid chromatography-tandem mass spectrometry (LC-MS/MS). NP Y125 is located in the N-terminal region of NP that is disordered when RNA is bound. The other site, NP T206, was predicted to be a phosphorylation site. Immunofluorescence analysis demonstrated that NP T206 is required for the formation of the punctate RTC that are typically observed during LCMV infection. A minigenome reporter assay using NP mutants, as well as Northern blot analysis, demonstrated that although NP T206A does not form punctate RTC, it can transcribe and replicate a minigenome. However, in the presence of matrix protein (Z) and glycoprotein (GP), translation of the minigenome message with NP T206A was inhibited, suggesting that punctate RTC formation is required to regulate viral replication. Together, these results highlight a significant difference between New and Old World arenaviruses and demonstrate the importance of RTC formation and translation priming in RTC for Old World arenaviruses. PMID:25922393

  7. Thermodynamic study of complex formation between Ce3+ and cryptand 222 in some binary mixed nonaqueous solvents

    NASA Astrophysics Data System (ADS)

    Rounaghi, G. H.; Dolatshahi, S.; Tarahomi, S.

    2014-12-01

    The stoichiometry, stability and the thermodynamic parameters of complex formation between cerium(III) cation and cryptand 222 (4,7,13,16,21,24-hexaoxa-1,10-diazabycyclo[8.8.8]-hexacosane) were studied by conductometric titration method in some binary solvent mixtures of dimethylformamide (DMF), 1,2-dichloroethane (DCE), ethyl acetate (EtOAc) and methyl acetate (MeOAc) with methanol (MeOH), at 288, 298, 308, and 318 K. A model based on 1: 1 stoichiometry has been used to analyze the conductivity data. The data have been fitted according to a non-linear least-squares analysis that provide the stability constant, K f, for the cation-ligand inclusion complex. The results revealed that the stability order of [Ce(cryptand 222)]3+ complex changes with the nature and composition of the solvent system. A non-linear relationship was observed between the stability constant (log K f) of [Ce(cryptand 222)]3+ complex versus the composition of the binary mixed solvent. Standard thermodynamic values were obtained from temperature dependence of the stability constant of the complex, show that the studied complexation process is mainly entropy governed and are influenced by the nature and composition of the binary mixed solvent solutions.

  8. Image formation in the eye: very specified complexity

    NASA Astrophysics Data System (ADS)

    Stoltzmann, David E.

    2005-08-01

    The formation of an image, and its correct interpretation by sighted living creatures, is a unique example of specified complexity unlike anything else in nature. While many of the functional aspects of living organisms are extremely complex, only an image requires a unique mapping process by the eye-brain system to be useful to the organism. The transfer of light from an object scene to a visual detection system (eye + brain) conveys an enormous amount of information. But unless that information is correctly organized into a useful image, the exchange of information is degraded and of questionable use. This paper examines the "connections" necessary for images to be interpreted correctly, as well as addressing the additional complexity requirement of dual-image mapping for stereovision capabilities. Statistics are presented for "simple eyes" consisting of a few pixels to illustrate the daunting task that random chance has to produce any form of a functional eye. For example, a 12-pixel eye (or camera) has 12! (479,001,600) possible pixel-to-brain (computer) wiring combinations, which can then be compared to the 126 million rods/cones of the actual human eye. If one tries to "connect the wires" (correctly interpret the information contained) in a 12-pixel image by random processes, by the time 6 pixels become correctly connected, over 99.9% of all the trials are incorrect, producing "noise" rather than a recognizable image. Higher numbers of pixels quickly make the problem astronomically worse for achieving any kind of useful image. This paper concludes that random-chance purposeless undirected processes cannot account for how images are perceived by living organisms.

  9. Cyclodextrins in pharmaceutical formulations I: structure and physicochemical properties, formation of complexes, and types of complex.

    PubMed

    Jambhekar, Sunil S; Breen, Philip

    2016-02-01

    Cyclodextrins are cyclic oligosaccharides that have been recognized as pharmaceutical adjuvants for the past 20 years. The molecular structure of these glucose derivatives, which approximates a truncated cone, bucket, or torus, generates a hydrophilic exterior surface and a nonpolar interior cavity. Cyclodextrins can interact with appropriately sized drug molecules to yield an inclusion complex. These noncovalent inclusion complexes offer a variety of advantages over the noncomplexed form of a drug. Cyclodextrins are primarily used to enhance the aqueous solubility, physical chemical stability, and bioavailability of drugs. Their other applications include preventing drug-drug interactions, converting liquid drugs into microcrystalline powders, minimizing gastrointestinal and ocular irritation, and reducing or eliminating unpleasant taste and smell. Here, we discuss the physical chemical properties of various cyclodextrins, including the effects of substitutions on these properties. Additionally, we report on the regulatory status of their use, commercial products containing cyclodextrins, toxicological considerations, and the forces involved in complex formation. We also highlight the types of complex formed and discuss the methods used to determine the types of complex present. PMID:26686054

  10. Formation of complexes of antimicrobial agent norfloxacin with antitumor antibiotics of anthracycline series

    NASA Astrophysics Data System (ADS)

    Evstigneev, M. P.; Rybakova, K. A.; Davies, D. B.

    2007-05-01

    The formation of complexes in solutions of the norfloxacin antimicrobial agent (NOR) with daunomycin (DAU) and nogalamycin (NOG), antitumor anthracycline antibiotics, was studied using 1H NMR spectroscopy. Based on the concentration and temperature dependences of the chemical shifts of the protons of interacting molecules, the equilibrium constants and thermodynamic parameters (enthalpy and entropy) of heteroassociation of the antibiotics were calculated. It was shown that NOR interacts with DAU (NOG) in aqueous solutions forming stacked heterocomplexes with parallel orientation of the molecular chromophores. The conclusion was drawn that such interactions should be taken into account when anthracyclines and quinolones are jointly administered during combined chemotherapy, since they can contribute to the medico-biological synergistic effect of these antibiotics.

  11. Electronic structure of solid molecular complexes evaluated by positronium formation studies at low temperature

    NASA Astrophysics Data System (ADS)

    Oliveira, F. C.; Denadai, A. M. L.; Fulgncio, F. H.; Windmller, D.; Yoshida, M. I.; Magalhes, W. F.

    2015-03-01

    Electronic structure of solid molecular complexes [TPPO1-x?TPMx] and [TPPO1-x?ACNx] at low temperature (80 K) was investigated by positronium annihilation lifetime spectroscopy (PALS) in order to evaluate the positronium formation at this condition and compare with our previous study recently reported at 294 K. Temporal dependence of the ?3 (ortho-positronium lifetime/ns) and I3 (ortho-positronium relative intensity/%) at 80 K remained constant throughout the measurement time (10 h), suggesting non-occurrence of electron trapping. The dependence of I3 with molar fraction at 80 K showed a decrease of I3 when compared with the values obtained at 294 K (?I3 = 8% for [TPPO0.5?TPM0.5] and ?I3 = 37% for [TPPO0.5?ACN0.5]. These results were rationalized in terms of reduction of electronic availability upon lowering of temperature.

  12. Changes in protein structure at the interface accompanying complex formation

    PubMed Central

    Chakravarty, Devlina; Janin, Joël; Robert, Charles H.; Chakrabarti, Pinak

    2015-01-01

    Protein interactions are essential in all biological processes. The changes brought about in the structure when a free component forms a complex with another molecule need to be characterized for a proper understanding of molecular recognition as well as for the successful implementation of docking algorithms. Here, unbound (U) and bound (B) forms of protein structures from the Protein–Protein Interaction Affinity Database are compared in order to enumerate the changes that occur at the interface atoms/residues in terms of the solvent-accessible surface area (ASA), secondary structure, temperature factors (B factors) and disorder-to-order transitions. It is found that the interface atoms optimize contacts with the atoms in the partner protein, which leads to an increase in their ASA in the bound interface in the majority (69%) of the proteins when compared with the unbound interface, and this is independent of the root-mean-square deviation between the U and B forms. Changes in secondary structure during the transition indicate a likely extension of helices and strands at the expense of turns and coils. A reduction in flexibility during complex formation is reflected in the decrease in B factors of the interface residues on going from the U form to the B form. There is, however, no distinction in flexibility between the interface and the surface in the monomeric structure, thereby highlighting the potential problem of using B factors for the prediction of binding sites in the unbound form for docking another protein. 16% of the proteins have missing (disordered) residues in the U form which are observed (ordered) in the B form, mostly with an irregular conformation; the data set also shows differences in the composition of interface and non-interface residues in the disordered polypeptide segments as well as differences in their surface burial. PMID:26594372

  13. Changes in protein structure at the interface accompanying complex formation.

    PubMed

    Chakravarty, Devlina; Janin, Joël; Robert, Charles H; Chakrabarti, Pinak

    2015-11-01

    Protein interactions are essential in all biological processes. The changes brought about in the structure when a free component forms a complex with another molecule need to be characterized for a proper understanding of molecular recognition as well as for the successful implementation of docking algorithms. Here, unbound (U) and bound (B) forms of protein structures from the Protein-Protein Interaction Affinity Database are compared in order to enumerate the changes that occur at the interface atoms/residues in terms of the solvent-accessible surface area (ASA), secondary structure, temperature factors (B factors) and disorder-to-order transitions. It is found that the interface atoms optimize contacts with the atoms in the partner protein, which leads to an increase in their ASA in the bound interface in the majority (69%) of the proteins when compared with the unbound interface, and this is independent of the root-mean-square deviation between the U and B forms. Changes in secondary structure during the transition indicate a likely extension of helices and strands at the expense of turns and coils. A reduction in flexibility during complex formation is reflected in the decrease in B factors of the interface residues on going from the U form to the B form. There is, however, no distinction in flexibility between the interface and the surface in the monomeric structure, thereby highlighting the potential problem of using B factors for the prediction of binding sites in the unbound form for docking another protein. 16% of the proteins have missing (disordered) residues in the U form which are observed (ordered) in the B form, mostly with an irregular conformation; the data set also shows differences in the composition of interface and non-interface residues in the disordered polypeptide segments as well as differences in their surface burial. PMID:26594372

  14. Deciphering complex soil/site formation in sands

    NASA Astrophysics Data System (ADS)

    Johnson, D. L.; Johnson, D. N.; Benn, D. W.; Bettis, E. A., III

    2008-10-01

    This paper summarizes aspects of the geoarchaeological research at two adjacent multi-component archaeological sites, 13JP86 and 13JP87, along Indian Creek in central Iowa, USA. The sites, both recently salvaged but now destroyed, formed in late Pleistocene sands reworked from glacial sediments that emanated from the wasting Des Moines Lobe glacier some 13,000-14,000 years ago. The soils contained shallowly dispersed and mixed artifacts that span the Paleoindian-to-historic cultural spectrum. In open areas, as at Indian Creek, site formation processes equate to natural soil genetic processes, plus human imprints. Cultural materials, once deposited, become part of the soil and subject to dynamic soil processes. These soils had reasonably well expressed Ap, A, and E horizons that collectively formed thick one-layered biomantles, underlain by well expressed argillic Bt horizons. The biomantles had been well bioturbated, deeply in some pedons, but still exhibited organized A and E horizons. The Bt horizons were also bioturbated, though less so, and consisted of multiple thin to thick sandy clay bands, termed illuvial clay lamellae (icl's). The icl's contained modest to appreciable amounts of illuvial clay as bridges between grains, and as diffuse splotches and blebs separated by less clayey, E horizon-like interlamellar sandy zones. Deeper and less bioturbated E-like sandy zones had accumulated so much clay that they had coalesced with icl's into thick, complexly banded argillic Bt horizons. The process histories of the sandy pedons were obviously extremely complex. The geoarchaeological aspects of the project, which were mainly complex pedologic ones, were largely interpreted by drawing on the genetic principles of dynamic denudation to explain soil/site evolution. Many questions were raised, and most were answered under these principles. New concepts and perspectives were gained in this study, and the resulting interpretive scenarios carry explanatory implications for sandy soils everywhere, whether charged with cultural materials or not.

  15. Probing the Formation of Complex Organic Molecules in Interstellar Ices - Beyond the FTIR - RGA Limitation

    NASA Astrophysics Data System (ADS)

    Kaiser, Ralf I.

    2015-08-01

    An understanding of the formation of key classes of complex organic molecules (COMs) within interstellar ices is of core value to the laboratory astrophysics community with structural isomers - molecules with the same molecular formula but different connectivities of atoms - serving as a molecular clock and tracers in defining the evolutionary stage of cold molecular clouds and star forming regions. Here, the lack of data on products, branching ratios, and rate constants of their formation and how they depend on the ice temperature and composition limits the understanding how COMs are synthesized. Classically, infrared spectroscopy combined with mass spectrometry of the irradiated and subliming ices have been exploited for the last decades, but the usefulness of these methods has reached the limits when it comes to the identification of CMS in those ices. Here, infrared spectroscopy can only untangle the functional groups of COMs; mass spectrometry coupled with electron impact ionization cannot discriminate structural isomers and suffers from extensive fragmentation. This talk presents a novel approach to elucidate the formation of COMs by exploiting - besides classical infrared, Raman, and ultraviolet-visual spectroscopy - reflectron time-of-flight mass spectrometry (ReTOF) coupled with tunable vacuum ultraviolet (VUV) soft photoionization (ReTOF-PI). This technique has the unique power to identify the molecules based on a cross correlation of their mass-to-charge ratios, their ionization energies (IE), and their sublimation temperatures ultimately unraveling an inventory of individual COMs molecules formed upon interaction of ionizing radiation with interstellar analog ices.

  16. Variation in DNA binding constants with a change in geometry of ternary copper(II) complexes with N2O donor Schiff base and cyanate or dicyanamide

    NASA Astrophysics Data System (ADS)

    Jana, Subrata; Santra, Ramesh Chandra; Das, Saurabh; Chattopadhyay, Shouvik

    2014-09-01

    Two new copper(II) complexes, [Cu(L)(OCN)] (1) and [CuL(dca)]n (2), where HL = 2-(-(2-(diethylamino)ethylimino)methyl)naphthalen-1-ol, dca = N(CN)2-, have been synthesized and characterized by elemental analysis, IR, UV-VIS spectroscopy and single crystal X-ray diffraction studies. Complex 1 has square planar and complex 2 square pyramidal geometries in solid state around metal centre. Interactions of the complexes with calf thymus DNA (CT DNA) were studied by UV-VIS spectroscopy. Binding constant and site size of interaction were determined. Binding site size and intrinsic binding constant K revealed complex 1 interacted with calf thymus DNA better than complex 2.

  17. Structural basis of complement membrane attack complex formation

    PubMed Central

    Serna, Marina; Giles, Joanna L.; Morgan, B. Paul; Bubeck, Doryen

    2016-01-01

    In response to complement activation, the membrane attack complex (MAC) assembles from fluid-phase proteins to form pores in lipid bilayers. MAC directly lyses pathogens by a ‘multi-hit' mechanism; however, sublytic MAC pores on host cells activate signalling pathways. Previous studies have described the structures of individual MAC components and subcomplexes; however, the molecular details of its assembly and mechanism of action remain unresolved. Here we report the electron cryo-microscopy structure of human MAC at subnanometre resolution. Structural analyses define the stoichiometry of the complete pore and identify a network of interaction interfaces that determine its assembly mechanism. MAC adopts a ‘split-washer' configuration, in contrast to the predicted closed ring observed for perforin and cholesterol-dependent cytolysins. Assembly precursors partially penetrate the lipid bilayer, resulting in an irregular β-barrel pore. Our results demonstrate how differences in symmetric and asymmetric components of the MAC underpin a molecular basis for pore formation and suggest a mechanism of action that extends beyond membrane penetration. PMID:26841837

  18. Structural basis of complement membrane attack complex formation

    NASA Astrophysics Data System (ADS)

    Serna, Marina; Giles, Joanna L.; Morgan, B. Paul; Bubeck, Doryen

    2016-02-01

    In response to complement activation, the membrane attack complex (MAC) assembles from fluid-phase proteins to form pores in lipid bilayers. MAC directly lyses pathogens by a `multi-hit' mechanism; however, sublytic MAC pores on host cells activate signalling pathways. Previous studies have described the structures of individual MAC components and subcomplexes; however, the molecular details of its assembly and mechanism of action remain unresolved. Here we report the electron cryo-microscopy structure of human MAC at subnanometre resolution. Structural analyses define the stoichiometry of the complete pore and identify a network of interaction interfaces that determine its assembly mechanism. MAC adopts a `split-washer' configuration, in contrast to the predicted closed ring observed for perforin and cholesterol-dependent cytolysins. Assembly precursors partially penetrate the lipid bilayer, resulting in an irregular β-barrel pore. Our results demonstrate how differences in symmetric and asymmetric components of the MAC underpin a molecular basis for pore formation and suggest a mechanism of action that extends beyond membrane penetration.

  19. Structural basis of complement membrane attack complex formation.

    PubMed

    Serna, Marina; Giles, Joanna L; Morgan, B Paul; Bubeck, Doryen

    2016-01-01

    In response to complement activation, the membrane attack complex (MAC) assembles from fluid-phase proteins to form pores in lipid bilayers. MAC directly lyses pathogens by a 'multi-hit' mechanism; however, sublytic MAC pores on host cells activate signalling pathways. Previous studies have described the structures of individual MAC components and subcomplexes; however, the molecular details of its assembly and mechanism of action remain unresolved. Here we report the electron cryo-microscopy structure of human MAC at subnanometre resolution. Structural analyses define the stoichiometry of the complete pore and identify a network of interaction interfaces that determine its assembly mechanism. MAC adopts a 'split-washer' configuration, in contrast to the predicted closed ring observed for perforin and cholesterol-dependent cytolysins. Assembly precursors partially penetrate the lipid bilayer, resulting in an irregular ?-barrel pore. Our results demonstrate how differences in symmetric and asymmetric components of the MAC underpin a molecular basis for pore formation and suggest a mechanism of action that extends beyond membrane penetration. PMID:26841837

  20. Adhesion and formation of microbial biofilms in complex microfluidic devices

    SciTech Connect

    Kumar, Aloke; Karig, David K; Neethirajan, Suresh; Suresh, Anil K; Srijanto, Bernadeta R; Mukherjee, Partha P; Retterer, Scott T; Doktycz, Mitchel John

    2012-01-01

    Shewanella oneidensis is a metal reducing bacterium, which is of interest for bioremediation and clean energy applications. S. oneidensis biofilms play a critical role in several situations such as in microbial energy harvesting devices. Here, we use a microfluidic device to quantify the effects of hydrodynamics on the biofilm morphology of S. oneidensis. For different rates of fluid flow through a complex microfluidic device, we studied the spatiotemporal dynamics of biofilms, and we quantified several morphological features such as spatial distribution, cluster formation and surface coverage. We found that hydrodynamics resulted in significant differences in biofilm dynamics. The baffles in the device created regions of low and high flow in the same device. At higher flow rates, a nonuniform biofilm develops, due to unequal advection in different regions of the microchannel. However, at lower flow rates, a more uniform biofilm evolved. This depicts competition between adhesion events, growth and fluid advection. Atomic force microscopy (AFM) revealed that higher production of extra-cellular polymeric substances (EPS) occurred at higher flow velocities.

  1. Integrin activation and focal complex formation in cardiac hypertrophy

    NASA Technical Reports Server (NTRS)

    Laser, M.; Willey, C. D.; Jiang, W.; Cooper, G. 4th; Menick, D. R.; Zile, M. R.; Kuppuswamy, D.

    2000-01-01

    Cardiac hypertrophy is characterized by both remodeling of the extracellular matrix (ECM) and hypertrophic growth of the cardiocytes. Here we show increased expression and cytoskeletal association of the ECM proteins fibronectin and vitronectin in pressure-overloaded feline myocardium. These changes are accompanied by cytoskeletal binding and phosphorylation of focal adhesion kinase (FAK) at Tyr-397 and Tyr-925, c-Src at Tyr-416, recruitment of the adapter proteins p130(Cas), Shc, and Nck, and activation of the extracellular-regulated kinases ERK1/2. A synthetic peptide containing the Arg-Gly-Asp (RGD) motif of fibronectin and vitronectin was used to stimulate adult feline cardiomyocytes cultured on laminin or within a type-I collagen matrix. Whereas cardiocytes under both conditions showed RGD-stimulated ERK1/2 activation, only collagen-embedded cells exhibited cytoskeletal assembly of FAK, c-Src, Nck, and Shc. In RGD-stimulated collagen-embedded cells, FAK was phosphorylated only at Tyr-397 and c-Src association occurred without Tyr-416 phosphorylation and p130(Cas) association. Therefore, c-Src activation is not required for its cytoskeletal binding but may be important for additional phosphorylation of FAK. Overall, our study suggests that multiple signaling pathways originate in pressure-overloaded heart following integrin engagement with ECM proteins, including focal complex formation and ERK1/2 activation, and many of these pathways can be activated in cardiomyocytes via RGD-stimulated integrin activation.

  2. Selectivity of lithium electrodes: correlation with ion-lonophore complex stability constants and with interfacial exchange current densities.

    PubMed

    Mikhelson, Konstantin M; Bobacka, Johan; Ivaska, Ari; Lewenstam, Andrzej; Bochenska, Maria

    2002-02-01

    Lithium-selective electrodes with solvent polymeric membranes based on two different dicyclohexylamide neutral ionophores are studied systematically. The selectivity of lithium response is studied by means of the ordinary potentiometric experiments. Stability constants of lithium, sodium, and potassium ions with the neutral ionophores are measured by means of the segmented sandwich membrane method. Charge transfer through the membrane bulk and across the membrane/solution interface is studied by means of electrochemical impedance spectroscopy. Well-resolved Faradaic impedance semicircles are obtained, allowing calculation of exchange current densities for lithium, sodium, and potassium. It is clearly demonstrated that the potentiometric selectivity coefficients correlate well with thermodynamic equilibrium parameters. The correlation with exchange current densities also exists, although it is low, and seems rather qualitative than quantitative. The results are treated in favor of equilibrium at the membrane/solution interface. It is also concluded (tentatively) that the kinetic description is equivalent to the equilibrium one, giving evidence that ion-ionophore complexes form directly at the interface. PMID:11838669

  3. Determination of Effective Stability Constants of Ion-Carrier Complexes in Ion Selective Nanospheres with Charged Solvatochromic Dyes.

    PubMed

    Xie, Xiaojiang; Bakker, Eric

    2015-11-17

    Ionophores are widely used ion carriers in ion selective sensors. The effective stability constant (?) is a key physical parameter providing valuable guidelines to the design of ionophores and carrier-based ion selective sensors. The ? value of ion-carrier complex in plasticized poly(vinyl chloride) (PVC) membranes and solutions have been determined in the past by various techniques, but most of them are difficult to implement at the nanoscale owing to the ultrasmall sample volume. A new methodology based on charged solvatochromic dyes is introduced here for the first time to determine ? values directly within ion selective nanospheres. Four ionophores with different selectivities toward Na(+), K(+), Ca(2+), and H(+), respectively, are successfully characterized in nanospheres composed of triblock copolymer Pluronic F-127 and bis(2-ethylhexyl) sebacate. The values determined in the nanospheres are smaller compared with those in plasticized PVC membranes, indicating a more polar nanosphere microenvironment and possible uneven distribution of the sensing components in the interfacial region. PMID:26502342

  4. Determination of plasma frequency, damping constant, and size distribution from the complex dielectric function of noble metal nanoparticles

    SciTech Connect

    Mendoza Herrera, Luis J.; Arboleda, David Muñetón; Schinca, Daniel C.; Scaffardi, Lucía B.

    2014-12-21

    This paper develops a novel method for simultaneously determining the plasma frequency ω{sub P}   and the damping constant γ{sub free} in the bulk damped oscillator Drude model, based on experimentally measured real and imaginary parts of the metal refractive index in the IR wavelength range, lifting the usual approximation that restricts frequency values to the UV-deep UV region. Our method was applied to gold, silver, and copper, improving the relative uncertainties in the final values for ω{sub p} (0.5%–1.6%) and for γ{sub free} (3%–8%), which are smaller than those reported in the literature. These small uncertainties in ω{sub p} and γ{sub free} determination yield a much better fit of the experimental complex dielectric function. For the case of nanoparticles (Nps), a series expansion of the Drude expression (which includes ω{sub p} and γ{sub free} determined using our method) enables size-dependent dielectric function to be written as the sum of three terms: the experimental bulk dielectric function plus two size corrective terms, one for free electron, and the other for bound-electron contributions. Finally, size distribution of nanometric and subnanometric gold Nps in colloidal suspension was determined through fitting its experimental optical extinction spectrum using Mie theory based on the previously determined dielectric function. Results are compared with size histogram obtained from Transmission Electron Microscopy (TEM)

  5. Reactions of a Dinitrogen Complex of Molybdenum: Formation of a Carbon-Nitrogen Bond.

    ERIC Educational Resources Information Center

    Busby, David C.; And Others

    1981-01-01

    Reports a procedure for the formation of alkyldiazenido complexes of molybdenum in the absence of dioxygen, suitable for inclusion in an advanced inorganic chemistry laboratory. Includes background information and experimental procedures for two complexes. (SK)

  6. Complex formation during dissolution of metal oxides in molten alkali carbonates

    SciTech Connect

    Li Qingfeng; Borup, F.; Petrushina, I.; Bjerrum, N.J.

    1999-07-01

    Dissolution of metal oxides in molten carbonates relates directly to the stability of materials for electrodes and construction of molten carbonate fuel cells. In the present work the solubilities of PbO, NiO, Fe{sub 2}O{sub 3}, and Bi{sub 2}O{sub 3} in molten Li/K carbonates have been measured at 650 C under carbon dioxide atmosphere. It is found that the solubilities of NiO and PbO decrease while those of Fe{sub 2}O{sub 3} and Bi{sub 2}O{sub 3} remain approximately constant as the lithium mole fraction increases from 0.43 to 0.62 in the melt. At a fixed composition of the melt, NiO and PbO display both acidic and basic dissolution as the partial pressure of carbon dioxide varies. By combination of solubility and electromotive force measurements, a model is constructed assuming the dissolution involves complex formation. The possible species for lead are proposed to be [Pb(CO{sub 3}){sub 2}]{sup {minus}2} and/or [Pb(CO{sub 3}){sub 3}]{sup {minus}4}. A similar complex chemistry for nickel oxide dissolution might be expected.

  7. Ethanol oxidation by imidorhenium(V) complexes: formation of amidorhenium(III) complexes.

    PubMed

    Suing, A L; Dewan, C R; White, P S; Thorp, H H

    2000-12-25

    The reaction of Re(NC6H4R)Cl3(PPh3)2 (R = H, 4-Cl, 4-OMe) with 1,2-bis(diphenylphosphino)ethane (dppe) is investigated in refluxing ethanol. The reaction produces two major products, Re(NC6H4R)Cl(dppe)(2)2+ (R = H, 1-H; R = Cl, 1-Cl; R = OMe, 1-OMe) and the rhenium(III) species Re(NHC6H4R)Cl(dppe)2+ (R = H, 2-H; R = Cl, 2-Cl). Complexes 1-H (orthorhombic, Pcab, a = 22.3075(10) A, b = 23.1271(10) A, c = 23.3584(10) A, Z = 8), 1-Cl (triclinic, P1, a = 11.9403(6) A, b = 14.6673(8) A, c = 17.2664(9) A, alpha = 92.019(1) degrees, beta = 97.379(1) degrees, gamma = 90.134(1) degrees, Z = 2), and 1-OMe (triclinic, P1, a = 11.340(3) A, b = 13.134(4) A, c = 13.3796(25) A, alpha = 102.370(20) degrees, beta = 107.688(17) degrees, gamma = 114.408(20) degrees, Z = 1) are crystallographically characterized and show an average Re-N bond length (1.71 A) typical of imidorhenium(V) complexes. There is a small systematic decrease in the Re-N bond length on going from Cl to H to OMe. Complex 2-Cl (monoclinic, Cc, a = 24.2381(11) A, b = 13.4504(6) A, c = 17.466(8) A, beta = 97.06900(0) degrees, Z = 4) is also crystallographically characterized and shows a Re-N bond length (1.98 A) suggestive of amidorhenium(III). The rhenium(III) complexes exhibit unusual proton NMR spectra where all of the resonances are found at expected locations except those for the amido protons, which are at 37.8 ppm for 2-Cl and 37.3 ppm for 1-H. The phosphorus resonances are also unremarkable, but the 13C spectrum of 2-Cl shows a significantly shifted resonance at 177.3 ppm, which is assigned to the ipso carbon of the phenylamido ligand. The extraordinary shifts of the amido hydrogen and ipso carbon are attributed to second-order magnetism that is strongly focused along the axially compressed amido axis. The reducing equivalents for the formation of the Re(III) product are provided by oxidation of the ethanol solvent, which produces acetal and acetaldehyde in amounts as much as 30 equiv based on the quantity of rhenium starting material. Equal amounts of hydrogen gas are produced, suggesting that the catalyzed reaction is the dehydrogenation of ethanol to produce acetaldehyde and hydrogen gas. Metal hydrides are detected in the reaction solution, suggesting a mechanism involving beta-elimination of ethanol at the metal center. Formation of the amidorhenium(III) product possibly arises from migration of a metal hydride in the imidorhenium(V) complex. PMID:11151507

  8. Double layer formation at the interface of complex plasmas

    SciTech Connect

    Yaroshenko, V. V.; Thoma, M. H.; Thomas, H. M.; Morfill, G. E.

    2008-08-15

    Necessary conditions are formulated for the generation of a double layer at the interface of a complex plasma and a particle-free electron-ion plasma in a weakly collisional discharge. Examples are calculated for realistic observed complex plasmas, and it is shown that situations of both ''smooth'' transitions and 'sharp' transitions can exist. The model can explain the abrupt boundaries observed.

  9. IR spectroscopic study of the complex formation between ammonia and water molecules in a KBr matrix

    NASA Astrophysics Data System (ADS)

    Vorotyntsev, I. V.; Grinvald, I. I.; Kagalaev, I. Yu.; Petukhov, A. N.; Sutyagina, E. A.; Vorotyntsev, A. V.; Derbisher, E. V.; Petukhova, N. A.; Vorotyntsev, V. M.

    2014-04-01

    The formation of complexes of ammonia and water molecules in a potassium bromide matrix is studied by means of IR spectroscopy. Ammonia and water complexes of variable composition are stabilized in a solid matrix using different approaches to saturating KBr powder with the initial components. Proton transfer can occur, leading to the formation of ammonium salts.

  10. Salting Constants of Small Organic Molecules in Aerosol-Relevant Salts and Application to Aerosol Formation in the Southeastern United States

    NASA Astrophysics Data System (ADS)

    Waxman, E.; Carlton, A. M. G.; Ziemann, P. J.; Volkamer, R. M.

    2014-12-01

    Secondary organic aerosol (SOA) formation from small water-soluble molecules such as glyoxal and methyl glyoxal is a topic of emerging interest. Results from recent field campaigns, e.g. Waxman et al. (2013, GRL) and Knote et al. (2014, ACP), show that these molecules can form significant SOA mass as a result of 'salting-in'. Salting-in happens when a molecule's solubility increases with salt concentration and salting-out is the reverse. Salting effects modify the solubility exponentially with increasing salt concentration, and thus the effective Henry's law constant can strongly modify partitioning, and multiphase chemical reaction rates in aerosol water. Moreover, the solubility in aerosol water cannot easily inferred based on the solubility in cloud water, as the salting effects could change the solubility by a factor of 104 or more. In this work, we have devised and applied a novel experimental setup to measure salting constants using an ion trap mass spectrometer. We focus on small, water soluble molecules like methyl glyoxal and similar compounds and measure salting constants for aerosol-relevant salts including ammonium sulfate, ammonium nitrate, and sodium chloride. The Setschenow salting-constant values are then used to parameterize the effects of salting in CMAQ. We present a series of sensitivity studies of the effects that inorganic aerosols have on the SOA formation from small soluble molecules in the southeastern United States.

  11. Positronium formation studies in solid molecular complexes: Triphenylphosphine oxide-triphenylmethanol

    NASA Astrophysics Data System (ADS)

    Oliveira, F. C.; Denadai, A. M. L.; Fulgncio, F. H.; Magalhes, W. F.; Alcntara, A. F. C.; Windmller, D.; Machado, J. C.

    2012-06-01

    Positronium formation in triphenylphosphine oxide (TPPO), triphenylmethanol (TPM), and systems [TPPO(1-X)?TPMX] has been studied. The low probability of positronium formation in complex [TPPO0.5?TPM0.5] was attributed to strong hydrogen bond and sixfold phenyl embrace interactions. These strong interactions in complex reduce the possibility of the n- and ?-electrons to interact with positrons on the spur and consequently, the probability of positronium formation is lower. The ?3 parameter and free volume (correlated to ?3) were also sensitive to the formation of hydrogen bonds and sixfold phenyl embrace interactions within the complex. For physical mixture the positron annihilation parameters remained unchanged throughout the composition range.

  12. On the formation of dynamic structures in the form of rotating rings and vortices in a thin layer of a magnetodielectric colloid subjected to a constant electric field

    NASA Astrophysics Data System (ADS)

    Danilov, M. I.; Yastrebov, S. S.

    2012-04-01

    Experimental data on the electrical and optical properties of a thin layer of a magnetodielectric colloid obtained by Kozhevnikov et al. (Tech. Phys. 51 (7), 946 (2006)), are analyzed. Using a three-layer hierarchical model, the possible structure and properties of near-electrode layers are determined, the formation mechanisms of dynamic structures are described, and the variation of the electrical properties of the magnetodielectric colloid layer with time and constant electric field strength are discussed.

  13. Determining resistivity of a formation adjacent to a borehole having casing by generating constant current flow in portion of casing and using at least two voltage measurement electrodes

    DOEpatents

    Vail, III, William Banning (Bothell, WA)

    2000-01-01

    Methods of operation of different types of multiple electrode apparatus vertically disposed in a cased well to measure information related to the resistivity of adjacent geological formations from within the cased well are described. The multiple electrode apparatus has a minimum of two spaced apart voltage measurement electrodes that electrically engage a first portion of the interior of the cased well and that provide at least first voltage information. Current control means are used to control the magnitude of any selected current that flows along a second portion of the interior of the casing to be equal to a predetermined selected constant. The first portion of the interior of the cased well is spaced apart from the second portion of the interior of the cased well. The first voltage information and the predetermined selected constant value of any selected current flowing along the casing are used in part to determine a magnitude related to the formation resistivity adjacent to the first portion of the interior of the cased well. Methods and apparatus having a plurality of voltage measurement electrodes are disclosed that provide voltage related information in the presence of constant currents flowing along the casing which is used to provide formation resistivity.

  14. Inhibitory mechanism of pancreatic amyloid fibril formation: formation of the complex between tea catechins and the fragment of residues 22-27.

    PubMed

    Kamihira-Ishijima, Miya; Nakazawa, Hiromi; Kira, Atsushi; Naito, Akira; Nakayama, Tsutomu

    2012-12-21

    Islet amyloid polypeptide (IAPP) is a major component of pancreatic amyloid deposits associated with type 2 diabetes. Polyphenols contained in plant foods have been found to inhibit amyloid fibril formation of proteins and/or peptides. However, the inhibition mechanism is not clear for a variety of systems. Here the inhibition mechanism of green tea polyphenols, catechins, on amyloid fibril formation of the IAPP fragment (IAPP22-27), which is of sufficient length for formation of ?-sheet-containing amyloid fibrils, was investigated by means of kinetic analysis. A quartz crystal microbalance (QCM) determined that the association constants of gallate-type catechins [epicatechin 3-gallate (ECg) and epigallocatechin 3-gallate] for binding to IAPP22-27 immobilized on the gold plate in QCM were 1 order of magnitude larger than those of the free IAPP22-27 peptide, and also those of epicatechin and epigallocatechin. Kinetic analysis using a two-step autocatalytic reaction mechanism revealed that ECg significantly reduced the rate constants of the first nucleation step of amyloid fibril formation, while the rate of autocatalytic growth was less retarded. (1)H nuclear magnetic resonance studies clarified that a IAPP22-27/ECg complex clearly forms as viewed from the (1)H chemical shift changes and line broadening. Our study suggests that tea catechins specifically inhibit the early stages of amyloid fibril formation to form amyloid nuclei by interacting with the unstructured peptide and that this inhibition mechanism is of great therapeutic value because stabilization of the native state could delay the pathogenesis of amyloid diseases and also the toxicity of the small oligomer (protofibril) is reported to be greater than that of the mature fibril. PMID:23205879

  15. A direct nitrogen-15 NMR study of praseodymium(III)-nitrate complex formation in aqueous solvent mixtures

    SciTech Connect

    Fratiello, A.; Kubo-Anderson, V.; Azimi, S.; Chavez, O.; Laghaei, F.; Perrigan, R.D. )

    1993-06-01

    A direct, low-temperature nitrogen-15([sup 15]N) NMR technique has been applied to the study of inner-shell complex formation between praseodymium(III) and nitrate ion in aqueous solvent mixtures. In water-acetone mixtures at [minus]95[degrees]C, ligand exchange is slow enough to permit the observation of [sup 15]N NMR signals for uncomplexed and coordinated nitrate ion, but satisfactory resolution is obtained only by the addition of Freon-12 to these systems for study at [minus]110 to [minus]115[degrees]C. Four coordinated nitrate signals are generally observed and a very small signal for an additional complex, or an isomer of one of the others, appears at the highest nitrate concentrations. Signals for the mono- and dinitrato complexes are unambiguously identified, but with the exception of the trinitrato complex, several possibilities exist for the remaining peaks. To overcome excessive viscosity signal broadening, measurements in methanol and ethanol are possible only with praseodymium trifluoromethanesulfonate (triflate). Coordinated nitrate signals in aqueous and anhydrous methanol are observed only for the mono- and dinitrato species, and signal areas indicate a maximum of two moles of nitrate per Pr(III) are complexes. A third signal is evident in the ethanol solution spectra, and the presence of this higher complex was confirmed by area measurement of the fraction of bound nitrate. The extent of complex formation in these solvent systems is attributed to differences in the dielectric constant. A comparison of the complexing tendencies of Pr(III) to other ions studied by this NMR method suggests that possibility of a coordination number change across the lanthanide series. Preliminary [sup 15]N NMR results for metal-ion complexes with the isothiocyanate ion are presented. 63 refs., 3 figs., 1 tab.

  16. Chiral recognition by formation of paramagnetic diastereomeric complexes

    NASA Astrophysics Data System (ADS)

    Scheffler, K.; Hfler, U.; Schuler, P.; Stegmann, H. B.

    The chiral 4-(?-hydroxy-benzyl)-2,6-di-tert. butyl-phenoxyl has been examined in its racemic form in toluene and carbontetrachloride. On adding of chiral auxiliaries (R)-resp. (S)-N,N-dimethyl-1-phenylethylamine or (S)-phenylethyl-amine two different couplings of the ?-proton are recorded by ENDOR spectroscopy. The experimental results are interpreted by a ternary equilibrium between radical, solvent and auxiliary. A model for the suggested association processes is given and equilibrium constants and corresponding enthalpies are calculated.

  17. Crystal structures of complexes of NAD+-dependent formate dehydrogenase from methylotrophic bacterium Pseudomonas sp. 101 with formate

    NASA Astrophysics Data System (ADS)

    Filippova, E. V.; Polyakov, K. M.; Tikhonova, T. V.; Stekhanova, T. N.; Boiko, K. M.; Sadykhov, I. G.; Tishkov, V. I.; Popov, V. O.; Labru, N.

    2006-07-01

    Formate dehydrogenase (FDH) from the methylotrophic bacterium Pseudomonas sp. 101 catalyzes oxidation of formate to NI2 with the coupled reduction of nicotinamide adenine dinucleotide (NAD+). The three-dimensional structures of the apo form (the free enzyme) and the holo form (the ternary FDH-NAD+-azide complex) of FDH have been established earlier. In the present study, the structures of FDH complexes with formate are solved at 2.19 and 2.28 resolution by the molecular replacement method and refined to the R factors of 22.3 and 20.5%, respectively. Both crystal structures contain four protein molecules per asymmetric unit. These molecules form two dimers identical to the dimer of the apo form of FDH. Two possible formatebinding sites are found in the active site of the FDH structure. In the complexes the sulfur atom of residue Cys354 exists in the oxidized state.

  18. Crystal structures of complexes of NAD{sup +}-dependent formate dehydrogenase from methylotrophic bacterium Pseudomonas sp. 101 with formate

    SciTech Connect

    Filippova, E. V. Polyakov, K. M.; Tikhonova, T. V.; Stekhanova, T. N.; Boiko, K. M.; Sadykhov, I. G.; Tishkov, V. I.; Popov, V. O.; Labru, N.

    2006-07-15

    Formate dehydrogenase (FDH) from the methylotrophic bacterium Pseudomonas sp. 101 catalyzes oxidation of formate to NI{sub 2} with the coupled reduction of nicotinamide adenine dinucleotide (NAD{sup +}). The three-dimensional structures of the apo form (the free enzyme) and the holo form (the ternary FDH-NAD{sup +}-azide complex) of FDH have been established earlier. In the present study, the structures of FDH complexes with formate are solved at 2.19 and 2.28 A resolution by the molecular replacement method and refined to the R factors of 22.3 and 20.5%, respectively. Both crystal structures contain four protein molecules per asymmetric unit. These molecules form two dimers identical to the dimer of the apo form of FDH. Two possible formatebinding sites are found in the active site of the FDH structure. In the complexes the sulfur atom of residue Cys354 exists in the oxidized state.

  19. Metallic film formation using direct micropatterning with photoreactive metal complexes.

    PubMed

    Cordonier, Christopher E J; Nakamura, Akimasa; Shimada, Kazuhiko; Fujishima, Akira

    2012-09-18

    Palladium, cobalt, and nickel in complex with photoacid-generating ligands, 4-(2-nitrobenzyloxycarbonyl)catechol and 4-(6-nitroveratryloxycarbonyl)catechol, were prepared in solution. Films formed from the metal complex solutions perform as positive-tone, directly photopatternable palladium, cobalt, nickel oxide, or composite film precursors. After exposure, acid-bearing selectively soluble complexes could be removed to give patterned films upon developing in aqueous base, which were transformable to the corresponding pattern-preserving metal/metal oxide film. The photodynamics of photoinduced solubility and direct micropatterning of palladium, cobalt, nickel, and palladium/nickel oxide composite films were investigated. Employing palladium as the initiator for autocatalytic chemical plating, selective direct copper plating on palladium film on polyethylene naphthalate and palladium/nickel oxide composite film on glass was accomplished. PMID:22892024

  20. An Efficient Format for Nearly Constant-Time Access to Arbitrary Time Intervals in Large Trace Files

    DOE PAGESBeta

    Chan, Anthony; Gropp, William; Lusk, Ewing

    2008-01-01

    A powerful method to aid in understanding the performance of parallel applications uses log or trace files containing time-stamped events and states (pairs of events). These trace files can be very large, often hundreds or even thousands of megabytes. Because of the cost of accessing and displaying such files, other methods are often used that reduce the size of the tracefiles at the cost of sacrificing detail or other information. This paper describes a hierarchical trace file format that provides for display of an arbitrary time window in a time independent of the total size of the file andmore » roughly proportional to the number of events within the time window. This format eliminates the need to sacrifice data to achieve a smaller trace file size (since storage is inexpensive, it is necessary only to make efficient use of bandwidth to that storage). The format can be used to organize a trace file or to create a separate file of annotations that may be used with conventional trace files. We present an analysis of the time to access all of the events relevant to an interval of time and we describe experiments demonstrating the performance of this file format.« less

  1. Dimeric interactions and complex formation using direct coevolutionary couplings.

    PubMed

    dos Santos, Ricardo N; Morcos, Faruck; Jana, Biman; Andricopulo, Adriano D; Onuchic, Jos N

    2015-01-01

    We develop a procedure to characterize the association of protein structures into homodimers using coevolutionary couplings extracted from Direct Coupling Analysis (DCA) in combination with Structure Based Models (SBM). Identification of dimerization contacts using DCA is more challenging than intradomain contacts since direct couplings are mixed with monomeric contacts. Therefore a systematic way to extract dimerization signals has been elusive. We provide evidence that the prediction of homodimeric complexes is possible with high accuracy for all the cases we studied which have rich sequence information. For the most accurate conformations of the structurally diverse dimeric complexes studied the mean and interfacial RMSDs are 1.95 and 1.44, respectively. This methodology is also able to identify distinct dimerization conformations as for the case of the family of response regulators, which dimerize upon activation. The identification of dimeric complexes can provide interesting molecular insights in the construction of large oligomeric complexes and be useful in the study of aggregation related diseases like Alzheimer's or Parkinson's. PMID:26338201

  2. Dimeric interactions and complex formation using direct coevolutionary couplings

    PubMed Central

    dos Santos, Ricardo N.; Morcos, Faruck; Jana, Biman; Andricopulo, Adriano D.; Onuchic, José N.

    2015-01-01

    We develop a procedure to characterize the association of protein structures into homodimers using coevolutionary couplings extracted from Direct Coupling Analysis (DCA) in combination with Structure Based Models (SBM). Identification of dimerization contacts using DCA is more challenging than intradomain contacts since direct couplings are mixed with monomeric contacts. Therefore a systematic way to extract dimerization signals has been elusive. We provide evidence that the prediction of homodimeric complexes is possible with high accuracy for all the cases we studied which have rich sequence information. For the most accurate conformations of the structurally diverse dimeric complexes studied the mean and interfacial RMSDs are 1.95Å and 1.44Å, respectively. This methodology is also able to identify distinct dimerization conformations as for the case of the family of response regulators, which dimerize upon activation. The identification of dimeric complexes can provide interesting molecular insights in the construction of large oligomeric complexes and be useful in the study of aggregation related diseases like Alzheimer’s or Parkinson’s. PMID:26338201

  3. Base Flipping in Open Complex Formation at Bacterial Promoters

    PubMed Central

    Karpen, Mary E.; deHaseth, Pieter L.

    2015-01-01

    In the process of transcription initiation, the bacterial RNA polymerase binds double-stranded (ds) promoter DNA and subsequently effects strand separation of 12 to 14 base pairs (bp), including the start site of transcription, to form the so-called open complex (also referred to as RPo). This complex is competent to initiate RNA synthesis. Here we will review the role of ?70 and its homologs in the strand separation process, and evidence that strand separation is initiated at the ?11A (the A of the non-template strand that is 11 bp upstream from the transcription start site) of the promoter. By using the fluorescent adenine analog, 2-aminopurine, it was demonstrated that the ?11A on the non-template strand flips out of the DNA helix and into a hydrophobic pocket where it stacks with tyrosine 430 of ?70. Open complexes are remarkably stable, even though in vivo, and under most experimental conditions in vitro, dsDNA is much more stable than its strand-separated form. Subsequent structural studies of other researchers have confirmed that in the open complex the ?11A has flipped into a hydrophobic pocket of ?70. It was also revealed that RPo was stabilized by three additional bases of the non-template strand being flipped out of the helix and into hydrophobic pockets, further preventing re-annealing of the two complementary DNA strands. PMID:25927327

  4. Atomic force spectroscopy in biological complex formation: strategies and perspectives.

    PubMed

    Bizzarri, Anna Rita; Cannistraro, Salvatore

    2009-12-31

    Atomic force spectroscopy has become a widely used technique for investigating forces, energies, and dynamics of biomolecular interactions. These studies provide dissociation kinetic parameters by pulling apart proteins involved in a complex. Biological complexes are studied under near-physiological conditions, without labeling procedures, and are probed one at time, the latter allowing to one obtain results which are not averaged over the ensemble. However, to gain reliable information, some experimental aspects have to be carefully controlled. In particular, the immobilization of molecular partners to AFM tips and supports, required to force the molecular dissociation, plays a crucial role in determining the success of the experiments. To actually resolve single interactions, multiple simultaneous complex dissociations have to be avoided, and nonspecific adhesions, commonly found in these studies, have to be recognized and discarded. This article is aimed at offering a critical revisitation of the atomic force spectroscopy technique applied to the study of biomolecular interactions, highlighting the critical points, identifying strategies to be adopted for a more reliable data extraction and interpretation, and pointing out the experimental and theoretical aspects which still need to be refined. To this purpose, we take advantage of the vast landscape of literature and then proceed into the details of our works. In this respect, we describe the general principles of the technique, the procedures for protein immobilization, and how they can affect the results. We emphasize the use of computational docking to predict molecular complex configurations, when unknown, as a useful approach to select proper anchorage architectures. Additionally, we deal with data acquirement and analysis, with regard to the force curve selection, to the force histograms interpretation, and to the theoretical frameworks used to extract kinetic parameters. Through this, we outline that AFS can be successfully used both to investigate complexes having very different affinities and also to reveal competitive binding mechanisms, thus gaining deeper information about molecular interactions. PMID:19904973

  5. Complex satellite systems: a general model of formation from rings

    NASA Astrophysics Data System (ADS)

    Crida, Aurlien; Charnoz, Sbastien

    2014-07-01

    Summary of the Abstract We present our model of formation of regular satellites by the spreading of a cold debris disk beyond the Roche radius. By numerical simulations and analytical calculations, we show that this process explains the peculiar properties of Saturn's small and mid-sized moons, in particular their mass - distance distribution. This process seems to also account for the structures of the satellite systems of Uranus, Neptune, and the Earth, suggesting that they used to have massive rings.

  6. Dynamics of Research Team Formation in Complex Networks

    NASA Astrophysics Data System (ADS)

    Sun, Caihong; Wan, Yuzi; Chen, Yu

    Most organizations encourage the formation of teams to accomplish complicated tasks, and vice verse, effective teams could bring lots benefits and profits for organizations. Network structure plays an important role in forming teams. In this paper, we specifically study the dynamics of team formation in large research communities in which knowledge of individuals plays an important role on team performance and individual utility. An agent-based model is proposed, in which heterogeneous agents from research communities are described and empirically tested. Each agent has a knowledge endowment and a preference for both income and leisure. Agents provide a variable input (effort) and their knowledge endowments to production. They could learn from others in their team and those who are not in their team but have private connections in community to adjust their own knowledge endowment. They are allowed to join other teams or work alone when it is welfare maximizing to do so. Various simulation experiments are conducted to examine the impacts of network topology, knowledge diffusion among community network, and team output sharing mechanisms on the dynamics of team formation.

  7. Structural Basis of Clostridium perfringens Toxin Complex Formation

    SciTech Connect

    Adams,J.; Gregg, K.; Bayer, E.; Boraston, A.; Smith, S.

    2008-01-01

    The virulent properties of the common human and livestock pathogen Clostridium perfringens are attributable to a formidable battery of toxins. Among these are a number of large and highly modular carbohydrate-active enzymes, including the {mu}-toxin and sialidases, whose catalytic properties are consistent with degradation of the mucosal layer of the human gut, glycosaminoglycans, and other cellular glycans found throughout the body. The conservation of noncatalytic ancillary modules among these enzymes suggests they make significant contributions to the overall functionality of the toxins. Here, we describe the structural basis of an ultra-tight interaction (Ka = 1.44 x 1011 M-1) between the X82 and dockerin modules, which are found throughout numerous C. perfringens carbohydrate-active enzymes. Extensive hydrogen-bonding and van der Waals contacts between the X82 and dockerin modules give rise to the observed high affinity. The {mu}-toxin dockerin module in this complex is positioned {approx}180 relative to the orientation of the dockerin modules on the cohesin module surface within cellulolytic complexes. These observations represent a unique property of these clostridial toxins whereby they can associate into large, noncovalent multitoxin complexes that allow potentiation of the activities of the individual toxins by combining complementary toxin specificities.

  8. Hard- and soft-modeling approaches for resolution of complex formation of Co2+ and Ni2+ with glycine.

    PubMed

    Shariati-Rad, Masoud; Hasani, Masoumeh; Shamsipur, Mojtaba

    2012-04-01

    Principal component analysis (PCA) was used to obtain information about the number of components in the complex formation equilibria of Co(2+) and Ni(2+) with glycine (Gly). In order to obtain a clearer insight into these complex formation systems, multivariate curve resolution-alternating least squares (MCR-ALS) was used. Using MCR-ALS as a soft-modeling method, well-defined concentration and spectral profiles were obtained under unimodality, non-negativity, and closure constraints. Based on the obtained results, an equilibrium model was proposed and subsequently, a hard-modeling method was used to resolve the complex formation equilibria completely. Due to the presence of multiple equilibria, the resolution of such systems is very difficult. The Co-Gly system was best described by a model consisting of M(GlyH), M(Gly), M(Gly)(2), M(Gly)(2)H, and M(Gly)(3) (M = Co(2+)) with the overall stability constants determined to be 7.10 0.011, 5.14 0.006, 9.28 0.009, 13.75 0.016, and 11.10 0.010, respectively. On the other hand, the system of Ni-Gly was best fitted by a model containing M(GlyH), M(Gly), M(Gly)(2), M(Gly)(3), and M(Gly)(2)(OH) (M = Ni(2+)) with overall stability constants of 10.95 0.04, 6.41 0.03, 11.31 0.03, 15.39 0.06, and 14.32 0.02, respectively. PMID:22449325

  9. Chemical physics behind formation of efficient charge-separated state for complexation between PC70BM and designed diporphyrin in solution.

    PubMed

    Ray, Anamika; Banerjee, Shrabanti; Ghosh, Shalini; Bauri, Ajoy K; Bhattacharya, Sumanta

    2016-01-01

    The present work reports supramolecular interaction of [6,6]-phenyl C71 butyric acid methyl ester (PC70BM) with two designed diporphyrin molecules having dithiophene (1) and carbazole (2) spacer in solvent having varying polarity. Studies on complex formation reveal relatively higher binding constant for PC70BM/2 complex in all the solvent studied. Solvent dependence of charge separation and charge recombination processes in PC70BM/diporphyrin non-covalent complexes has been well established in present work. Donor-acceptor geometry and stabilization of the singlet excited state of the diporphyrin during charge recombination are considered to be the possible reasons for this behavior. PMID:26189161

  10. Chemical physics behind formation of efficient charge-separated state for complexation between PC70BM and designed diporphyrin in solution

    NASA Astrophysics Data System (ADS)

    Ray, Anamika; Banerjee, Shrabanti; Ghosh, Shalini; Bauri, Ajoy K.; Bhattacharya, Sumanta

    2016-01-01

    The present work reports supramolecular interaction of [6,6]-phenyl C71 butyric acid methyl ester (PC70BM) with two designed diporphyrin molecules having dithiophene (1) and carbazole (2) spacer in solvent having varying polarity. Studies on complex formation reveal relatively higher binding constant for PC70BM/2 complex in all the solvent studied. Solvent dependence of charge separation and charge recombination processes in PC70BM/diporphyrin non-covalent complexes has been well established in present work. Donor-acceptor geometry and stabilization of the singlet excited state of the diporphyrin during charge recombination are considered to be the possible reasons for this behavior.

  11. Biological pattern formation: from basic mechanisms to complex structures

    NASA Astrophysics Data System (ADS)

    Koch, A. J.; Meinhardt, H.

    1994-10-01

    The reliable development of highly complex organisms is an intriguing and fascinating problem. The genetic material is, as a rule, the same in each cell of an organism. How then do cells, under the influence of their common genes, produce spatial patterns? Simple models are discussed that describe the generation of patterns out of an initially nearly homogeneous state. They are based on nonlinear interactions of at least two chemicals and on their diffusion. The concepts of local autocatalysis and of long-range inhibition play a fundamental role. Numerical simulations show that the models account for many basic biological observations such as the regeneration of a pattern after excision of tissue or the production of regular (or nearly regular) arrays of organs during (or after) completion of growth. Very complex patterns can be generated in a reproducible way by hierarchical coupling of several such elementary reactions. Applications to animal coats and to the generation of polygonally shaped patterns are provided. It is further shown how to generate a strictly periodic pattern of units that themselves exhibit a complex and polar fine structure. This is illustrated by two examples: the assembly of photoreceptor cells in the eye of Drosophila and the positioning of leaves and axillary buds in a growing shoot. In both cases, the substructures have to achieve an internal polarity under the influence of some primary pattern-forming system existing in the fly's eye or in the plant. The fact that similar models can describe essential steps in organisms as distantly related as animals and plants suggests that they reveal some universal mechanisms.

  12. Biological pattern formation: from basic mechanisms to complex structures

    SciTech Connect

    Koch, A.J.; Meinhardt, H. )

    1994-10-01

    The reliable development of highly complex organisms is an intriguing and fascinating problem. The genetic material is, as a rule, the same in each cell of an organism. How then do cells, under the influence of their common genes, produce spatial patterns Simple models are discussed that describe the generation of patterns out of an initially nearly homogeneous state. They are based on nonlinear interactions of at least two chemicals and on their diffusion. The concepts of local autocatalysis and of long-range inhibition play a fundamental role. Numerical simulations show that the models account for many basic biological observations such as the regeneration of a pattern after excision of tissue or the production of regular (or nearly regular) arrays of organs during (or after) completion of growth. Very complex patterns can be generated in a reproducible way by hierarchical coupling of several such elementary reactions. Applications to animal coats and to the generation of polygonally shaped patterns are provided. It is further shown how to generate a strictly periodic pattern of units that themselves exhibit a complex and polar fine structure. This is illustrated by two examples: the assembly of photoreceptor cells in the eye of [ital Drosophila] and the positioning of leaves and axillary buds in a growing shoot. In both cases, the substructures have to achieve an internal polarity under the influence of some primary pattern-forming system existing in the fly's eye or in the plant. The fact that similar models can describe essential steps in organisms as distantly related as animals and plants suggests that they reveal some universal mechanisms.

  13. Module Based Complexity Formation: Periodic Patterning in Feathers and Hairs

    PubMed Central

    Chuong, Cheng-Ming; Yeh, Chao-Yuan; Jiang, Ting-Xin; Widelitz, Randall

    2012-01-01

    Patterns describe order which emerges from homogeneity. Complex patterns on the integument are striking because of their visibility throughout an organism's lifespan. Periodic patterning is an effective design because the ensemble of hair or feather follicles (modules) allows the generation of complexity, including regional variations and cyclic regeneration, giving the skin appendages a new lease on life. Spatial patterns include the arrangements of feathers and hairs in specified number, size, and spacing. We explore how a field of equivalent progenitor cells can generate periodically arranged modules based on genetic information, physical-chemical rules and developmental timing. Reconstitution experiments suggest a competitive equilibrium regulated by activators / inhibitors involving Turing reaction-diffusion. Temporal patterns result from oscillating stem cell activities within each module (micro-environment regulation), reflected as growth (anagen) and resting (telogen) phases during the cycling of feather and hair follicles. Stimulating modules with activators initiates the spread of regenerative hair waves, while global inhibitors outside each module (macro-environment) prevent this. Different wave patterns can be simulated by Cellular Automata principles. Hormonal status and seasonal changes can modulate appendage phenotypes, leading to organ metamorphosis, with multiple ectodermal organ phenotypes generated from the same precursors. We discuss potential evolutionary novel steps using this module based complexity in several amniote integument organs, exemplified by the spectacular peacock feather pattern. We thus explore the application of the acquired knowledge of patterning in tissue engineering. New hair follicles can be generated after wounding. Hairs and feathers can be reconstituted through self-organization of dissociated progenitor cells. PMID:23539312

  14. Structural and spectroscopic study of Al(III)-3-hydroxyflavone complex: Determination of the stability constants in water-methanol mixtures

    NASA Astrophysics Data System (ADS)

    Davila, Y. A.; Sancho, M. I.; Almandoz, M. C.; Blanco, S. E.

    2012-09-01

    Stoichiometry and apparent stability constant (KC) of the complex formed between Al(III) and 3-hydroxyflavone were determined in methanol and water-methanol mixtures (% water w/w: 3.11; 6.15; 10.4; 15.2; 19.9 and 25.3) by UV-vis spectroscopy at 25.0 °C and constant ionic strength (0.05 M, sodium chloride). Stoichiometry of the complex (1:2, metal:ligand) is not modified with an increase in water percentage in the analyzed interval. The value of KC in methanol is greater than in the binary solutions. The effects of changing solvent composition on KC data were explained by linear solvation free energy relationships using the solvatochromic parameter of Kamlet and Taft (α, β and π*). Multiple linear regression analysis indicates that the hydrogen bond donating ability (α) of the solvent and non-specific interactions (π*) play an important role in the degree of occurrence of the reaction. The effect of temperature on KC was also analyzed by assessing standard entropy and enthalpy variations of the reaction in methanol. Finally, the structure of the complex was investigated using FTIR spectroscopy and DFT calculations. The ligand exhibits small structural changes upon complexation, localized on the chelating site. The calculated vibrational frequencies of the complex were successfully compared against the experimental values.

  15. Structural and spectroscopic study of Al(III)-3-hydroxyflavone complex: determination of the stability constants in water-methanol mixtures.

    PubMed

    Davila, Y A; Sancho, M I; Almandoz, M C; Blanco, S E

    2012-09-01

    Stoichiometry and apparent stability constant (K(C)) of the complex formed between Al(III) and 3-hydroxyflavone were determined in methanol and water-methanol mixtures (% water w/w: 3.11; 6.15; 10.4; 15.2; 19.9 and 25.3) by UV-vis spectroscopy at 25.0C and constant ionic strength (0.05 M, sodium chloride). Stoichiometry of the complex (1:2, metal:ligand) is not modified with an increase in water percentage in the analyzed interval. The value of K(C) in methanol is greater than in the binary solutions. The effects of changing solvent composition on K(C) data were explained by linear solvation free energy relationships using the solvatochromic parameter of Kamlet and Taft (?, ? and ?(*)). Multiple linear regression analysis indicates that the hydrogen bond donating ability (?) of the solvent and non-specific interactions (?(*)) play an important role in the degree of occurrence of the reaction. The effect of temperature on K(C) was also analyzed by assessing standard entropy and enthalpy variations of the reaction in methanol. Finally, the structure of the complex was investigated using FTIR spectroscopy and DFT calculations. The ligand exhibits small structural changes upon complexation, localized on the chelating site. The calculated vibrational frequencies of the complex were successfully compared against the experimental values. PMID:22609565

  16. The formation and study of titanium, zirconium, and hafnium complexes

    NASA Technical Reports Server (NTRS)

    Wilson, Bobby; Sarin, Sam; Smith, Laverne; Wilson, Melanie

    1989-01-01

    Research involves the preparation and characterization of a series of Ti, Zr, Hf, TiO, and HfO complexes using the poly(pyrazole) borates as ligands. The study will provide increased understanding of the decomposition of these coordination compounds which may lead to the production of molecular oxygen on the Moon from lunar materials such as ilmenite and rutile. The model compounds are investigated under reducing conditions of molecular hydrogen by use of a high temperature/pressure stainless steel autoclave reactor and by thermogravimetric analysis.

  17. Formation of Au and tetrapyridyl porphyrin complexes in superfluid helium.

    PubMed

    Feng, Cheng; Latimer, Elspeth; Spence, Daniel; Al Hindawi, Aula M A A; Bullen, Shem; Boatwright, Adrian; Ellis, Andrew M; Yang, Shengfu

    2015-07-14

    Binary clusters containing a large organic molecule and metal atoms have been formed by the co-addition of 5,10,15,20-tetra(4-pyridyl)porphyrin (H2TPyP) molecules and gold atoms to superfluid helium nanodroplets, and the resulting complexes were then investigated by electron impact mass spectrometry. In addition to the parent ion H2TPyP yields fragments mainly from pyrrole, pyridine and methylpyridine ions because of the stability of their ring structures. When Au is co-added to the droplets the mass spectra are dominated by H2TPyP fragment ions with one or more Au atoms attached. We also show that by switching the order in which Au and H2TPyP are added to the helium droplets, different types of H2TPyP-Au complexes are clearly evident from the mass spectra. This study suggests a new route for the control over the growth of metal-organic compounds inside superfluid helium nanodroplets. PMID:26059415

  18. New Pathways for the Formation of Complex Organics and Prebiotic Synthesis in the Gas Phase

    NASA Astrophysics Data System (ADS)

    El-Shall, M. S.

    2010-04-01

    We study the formation mechanisms of complex organics that are present in interstellar clouds. The reaction of acetylene ion with water produces vinyl alcohol while the reaction of benzene ion with acetylene produces naphthalene-type ion.

  19. The complex interplay between semantics and grammar in impression formation.

    PubMed

    Shreves, Wyley B; Hart, William; Adams, John M; Guadagno, Rosanna E; Eno, Cassie A

    2014-09-01

    We sought to bridge findings showing that (a) describing a person's behavior with the perfective verb aspect (did), compared to the imperfective aspect (was doing), increases processing of semantic knowledge unrelated to the target's action such as stereotypes and (b) an increased recognition of stereotypical thoughts often promotes a judgment correction for the stereotypes. We hypothesized an interplay between grammar (verb conjugation) and semantic information (gender) in impression-formation. Participants read a resume, attributed to a male or female, for a traditionally masculine job. When the resume was written in the imperfective, people rated a male (vs. female) more positively. When the resume was in the perfective, this pattern reversed. Only these latter effects of gender were influenced by cognitive load. Further, people more quickly indicated the applicant's gender in the perfective condition, suggesting an enhanced focus on gender during processing. PMID:24950389

  20. The Chodura layer formation in an active and collisional plasma under the action of a constant magnetic field

    NASA Astrophysics Data System (ADS)

    Morales Crespo, R.

    2016-04-01

    This paper studies the multi-layer structure of the plasma-sheath transition for an electropositive plasma under the action of a constant and oblique magnetic field. The introduction of the Chodura-scale allows us to introduce the concepts of Chodura-layer, Chodura-edge and Chodura-solution in a natural way as a consequence of a boundary layer structure formalism—in a similar manner to what happens in the plasma-sheath transition. Therefore, the region from the plasma bulk to the wall can be divided in three regions: (i) the plasma-presheath, a quasineutral space region dominated by ionization and/or collisions, (ii) the Chodura-layer, a quasineutral region also dominated by the action of the magnetic field though the drift term and finally (iii) the sheath region. It is shown that if magnetization is the dominant presheath mechanism, it is only located in the Chodura-layer, and this causes the electric field to become singular at the Chodura-edge, between two quasineutral regions—i.e. the plasma-presheath and the Chodura-layer.

  1. Study of magnetic field effect on Py-DMA exciplex luminescence in THF-DMF binary solvents: Evidence of multiple exciplex formation at higher bulk dielectric constant

    NASA Astrophysics Data System (ADS)

    Roy, Partha; Jana, Amit Kumar; Das, Doyel; Nath, Deb Narayan

    2009-06-01

    Magnetic field effects (MFE) on pyrene-DMA (N,N-dimethylaniline) exciplex system in THF-DMF binary solvents of varying bulk dielectric constant ( ?) has been studied. The MFE has been wavelength resolved over the emission band of the exciplex. The data indicates formation of two types of exciplexes at higher bulk value of ?. At lower value of ? ( ? < 9) essentially there is a single type of exciplex which is supported by the wavelength resolved MFE and life-time ( ?) measurements. However, at higher value of ? ( ? > 15) when the solvent reorganization energy is more prominent; the wavelength resolved MFE and life-time studies show evidence of two types of exciplexes.

  2. Subcellular location for the formation of the retinol/retinol-binding protein complex in rat liver

    SciTech Connect

    Crumbaugh, L.M.; Green, E.L.; Smith, J.E.

    1986-03-01

    Retinol complexes with retinol-binding protein (RBP) within the hepatocyte, however the subcellular location where complex formation occurs has not previously been identified. A model similar to that of lipoproteins formation has been hypothesized. The authors have identified the initial site of retinol/RBP complex formation. Furthermore, the authors have elucidated the progression of the complex through the subcellular organelles. Intravenous injections of /sup 3/H-retinol suspended in Tween 40 were administered to vitamin A depleted rats. After intervals of 2, 3, 4, 5, 10, 15, 20, and 30 minutes the rat livers were removed and fractions enriched in rough and smooth microsomes and Golgi apparatus were prepared. Extracts of these subcellular fractions were chromatographed on Sephadex G-100. Simultaneous elution of /sup 3/H-retinol and immunoreactive RBP indicated the presence of the complex. The retinol/RBP complex was observed in rough microsomes 2 minute after the injection of /sup 3/H-retinal. The complex appeared subsequently in smooth microsomes and Golgi apparatus. The complex was first detected serum around 10 minutes after injection. Based on the data, they believe that the retinol/RBP complex formation occurs in rough microsomes.

  3. Determination of the Physical Constants of Ferric and Ferrous Complexes of Phytic Acid by Proton Nuclear Magnetic Resonance and Resistance of Complexes to Enzymatic Dephosphoralation by Aspergillus ficcum

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Understanding the fate and transport of organic forms of phosphate requires in the case of myo-inositol hex kis phosphate (phytate) knowledge charge speciation as a function of pH and affinity of mineral cations such as soluble iron for phytate. Twelve acidity constants exist for phytic acid becau...

  4. Molar absorption coefficients and stability constants of metal complexes of 4-(2-pyridylazo)resorcinol (PAR): Revisiting common chelating probe for the study of metalloproteins.

    PubMed

    Kocy?a, Anna; Pomorski, Adam; Kr??el, Artur

    2015-11-01

    4-(2-Pyridylazo)resorcinol (PAR) is one of the most popular chromogenic chelator used in the determination of the concentrations of various metal ions from the d, p and f blocks and their affinities for metal ion-binding biomolecules. The most important characteristics of such a sensor are the molar absorption coefficient and the metal-ligand complex dissociation constant. However, it must be remembered that these values are dependent on the specific experimental conditions (e.g. pH, solvent components, and reactant ratios). If one uses these values to process data obtained in different conditions, the final result can be under- or overestimated. We aimed to establish the spectral properties and the stability of PAR and its complexes accurately with Zn(2+), Cd(2+), Hg(2+), Co(2+), Ni(2+), Cu(2+), Mn(2+) and Pb(2+) at a multiple pH values. The obtained results account for the presence of different species of metal-PAR complexes in the physiological pH range of 5 to 8 and have been frequently neglected in previous studies. The effective molar absorption coefficient at 492nm for the ZnHx(PAR)2 complex at pH7.4 in buffered water solution is 71,500M(-1)cm(-1), and the dissociation constant of the complex in these conditions is 7.0810(-13)M(2). To confirm these values and estimate the range of the dissociation constants of zinc-binding biomolecules that can be measured using PAR, we performed several titrations of zinc finger peptides and zinc chelators. Taken together, our results provide the updated parameters that are applicable to any experiment conducted using inexpensive and commercially available PAR. PMID:26364130

  5. Carbonheteroatom bond formation catalysed by organometallic complexes

    PubMed Central

    Hartwig, John F.

    2010-01-01

    At one time the synthetic chemists last resort, reactions catalysed by transition metals are now the preferred method for synthesizing many types of organic molecule. A recent success in this type of catalysis is the discovery of reactions that form bonds between carbon and heteroatoms (such as nitrogen, oxygen, sulphur, silicon and boron) via complexes of transition metals with amides, alkoxides, thiolates, silyl groups or boryl groups. The development of these catalytic processes has been supported by the discovery of new elementary reactions that occur at metalheteroatom bonds and by the identification of factors that control these reactions. Together, these findings have led to new synthetic processes that are in daily use and have formed a foundation for the development of processes that are likely to be central to synthetic chemistry in the future. PMID:18800130

  6. Effects of salt on intermolecular polyelectrolyte complexes formation between cationic microgel and polyanion.

    PubMed

    Ogawa, Kazuyoshi

    2015-12-01

    The study of interpolyelectrolyte complex (IPEC) formation between cationic microgel and polyanion was presented. The size and molecular weight of cationic microgel are much larger than those of linear anionic polyelectrolyte. The resulting IPEC was divided by dynamic light scattering (DLS), static light scattering (SLS), and turbidity or spectrometry; (i) water-soluble intra-particle complexes consisting of one microgel to which linear polyelectrolytes bind; (ii) complex coacervates (inter-particle complexes composed of aggregated intra-particle complexes); and (iii) insoluble amorphous precipitates. These types depended on not only the mixing ratio of polyanion to cationic microgel but also salt concentration. This trend was discussed from IPEC's composition, thermodynamics of IPEC formation and the salt effect on intermolecular interactions which were expected in IPEC formation. The results obtained from the use of microgel in IPEC's study suggested that not only electrostatic interaction but also hydrophobic interaction play an important role in the aggregation or association of IPEC. PMID:26472211

  7. Formation, Migration, and Reactivity of Au CO Complexes on Gold Surfaces

    DOE PAGESBeta

    Wang, Jun; McEntee, Monica; Tang, Wenjie; Neurock, Matthew; Baddorf, Arthur P.; Maksymovych, Petro; Yates, Jr, John T.

    2016-01-12

    Here, we report experimental as well as theoretical evidence that suggests Au CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10^ 8 to 10^ 4 Torr (dosage up to 10^6 langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au CO complex formation and diffusion, and Aumore » adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au CO complex result from the reduced Au Au bonding at elbows and step edges leading to stronger Au CO bonding and to the formation of a more positively charged CO (CO +) on Au. These studies indicate that the mobile Au CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers.« less

  8. Formation, Migration, and Reactivity of Au-CO Complexes on Gold Surfaces.

    PubMed

    Wang, Jun; McEntee, Monica; Tang, Wenjie; Neurock, Matthew; Baddorf, Arthur P; Maksymovych, Petro; Yates, John T

    2016-02-10

    We report experimental as well as theoretical evidence that suggests Au-CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au-CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10(-8) to 10(-4) Torr (dosage up to 10(6) langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au-CO complex formation and diffusion, and Au adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au-CO complex result from the reduced Au-Au bonding at elbows and step edges leading to stronger Au-CO bonding and to the formation of a more positively charged CO (CO(δ+)) on Au. Our studies indicate that the mobile Au-CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers. PMID:26754257

  9. Glutathione Complex Formation With Mercury(Ii) in Aqueous Solution at Physiological Ph

    SciTech Connect

    Mah, V.; Jalilehvand, F.; /SLAC

    2012-08-23

    The mercury(II) complexes formed in neutral aqueous solution with glutathione (GSH, here denoted AH{sub 3} in its triprotonated form) were studied using Hg L{sub III}-edge extended X-ray absorption fine structure (EXAFS) and {sup 199}Hg NMR spectroscopy, complemented with electrospray ionization mass spectrometric (ESI-MS) analyses. The [Hg(AH){sub 2}]{sup 2-} complex, with the Hg-S bond distances at 2.325 {+-} 0.01 {angstrom} in linear S-Hg-S coordination, and the {sup 199}Hg NMR chemical shift at -984 ppm, dominates except at high excess of glutathione. In a series of solutions with C{sub Hg(II)} {approx} 17 mM and GSH/Hg(II) mole ratios rising from 2.4 to 11.8, the gradually increasing mean Hg-S bond distance corresponds to an increasing amount of the [Hg(AH){sub 3}]{sup 4-} complex. ESI-MS peaks appear at -m/z values of 1208 and 1230 corresponding to the [Na{sub 4}Hg(AH){sub 2}(A)]{sup -} and [Na{sub 5}Hg(AH)(A){sub 2}]{sup -} species, respectively. In another series of solutions at pH 7.0 with CHg(II) 50 mM and GSH/Hg(II) ratios from 2.0 to 10.0, the Hg L{sub III}-edge EXAFS and {sup 199}Hg NMR spectra show that at high excess of glutathione (0.35 M) about 70% of the total mercury(II) concentration is present as the [Hg(AH){sub 3}]4- complex, with the average Hg-S bond distance 2.42 {+-} 0.02 {angstrom} in trigonal HgS{sub 3} coordination. The proportions of HgSn species, n = 2, 3, and 4, quantified by fitting linear combinations of model EXAFS oscillations to the experimental EXAFS data in our present and previous studies were used to obtain stability constants for the [Hg(AH){sub 3}]{sup 4-} complex and also for the [Hg(A){sub 4}]{sup 10-} complex that is present at high pH. For Hg(II) in low concentration at physiological conditions (pH 7.4, C{sub GSH} = 2.2 mM), the relative amounts of the HgS{sub 2} species [Hg(AH){sub 2}]{sup 2-}, [Hg(AH)(A)]{sup 3-}, and the HgS{sub 3} complex [Hg(AH){sub 3}]{sup 4-} were calculated to be 95:2:3. Our results are not consistent with the formation of dimeric Hg(II)-GSH complexes proposed in a recent EXAFS study.

  10. Norfloxacin Zn(II)-based complexes: acid base ionization constant determination, DNA and albumin binding properties and the biological effect against Trypanosoma cruzi.

    PubMed

    Gouvea, Ligiane R; Martins, Darliane A; Batista, Denise da Gama Jean; Soeiro, Maria de Nazar C; Louro, Sonia R W; Barbeira, Paulo J S; Teixeira, Letcia R

    2013-10-01

    Zn(II) complexes with norfloxacin (NOR) in the absence or in the presence of 1,10-phenanthroline (phen) were obtained and characterized. In both complexes, the ligand NOR was coordinated through a keto and a carboxyl oxygen. Tetrahedral and octahedral geometries were proposed for [ZnCl2(NOR)]H2O (1) and [ZnCl2(NOR)(phen)]2H2O (2), respectively. Since the biological activity of the chemicals depends on the pH value, pH titrations of the Zn(II) complexes were performed. UV spectroscopic studies of the interaction of the complexes with calf-thymus DNA (CT DNA) have suggested that they can bind to CT DNA with moderate affinity in an intercalative mode. The interactions between the Zn(II) complexes and bovine serum albumin (BSA) were investigated by steady-state and time-resolved fluorescence spectroscopy at pH 7.4. The experimental data showed static quenching of BSA fluorescence, indicating that both complexes bind to BSA. A modified Stern-Volmer plot for the quenching by complex 2 demonstrated preferential binding near one of the two tryptophan residues of BSA. The binding constants obtained (K b ) showed that BSA had a two orders of magnitude higher affinity for complex 2 than for 1. The results also showed that the affinity of both complexes for BSA was much higher than for DNA. This preferential interaction with protein sites could be important to their biological mechanisms of action. The analysis in vitro of the Zn(II) complexes and corresponding ligand were assayed against Trypanosoma cruzi, the causative agent of Chagas disease and the data showed that complex 2 was the most active against bloodstream trypomastigotes. PMID:23897315

  11. Reversible carbon-carbon bond formation between carbonyl compounds and a ruthenium pincer complex.

    PubMed

    Huff, Chelsea A; Kampf, Jeff W; Sanford, Melanie S

    2013-08-18

    This communication describes the reversible reaction of a ruthenium pincer complex with a variety of carbonyl compounds. Both NMR spectroscopic and X-ray crystallographic characterization of isomeric carbonyl adducts are reported, and the equilibrium constants for carbonyl binding have been determined. PMID:23832007

  12. {sup 13}C and {sup 17}O NMR binding constant studies of uranyl carbonate complexes in near-neutral aqueous solution. Yucca Mountain Project Milestone Report 3351

    SciTech Connect

    Clark, D.L.; Newton, T.W.; Palmer, P.D.; Zwick, B.D.

    1995-01-01

    Valuable structural information, much of it unavailable by other methods, can be obtained about complexes in solution through NMR spectroscopy. From chemical shift and intensity measurements of complexed species, NMR can serve as a species-specific structural probe for molecules in solution and can be used to validate thermodynamic constants used in geochemical modeling. Fourier-transform nuclear magnetic resonance (FT-NMR) spectroscopy has been employed to study the speciation of uranium(VI) ions in aqueous carbonate solutions as a function of pH, ionic strength, carbonate concentration, uranium concentration, and temperature. Carbon-13 and oxygen-17 NMR spectroscopy were used to monitor the fractions, and hence thermodynamic binding constants of two different uranyl species U0{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} and (UO{sub 2}){sub 3}(CO{sub 3}){sub 6}{sup 6{minus}} in aqueous solution. Synthetic buffer solutions were prepared under the ionic strength conditions used in the NMR studies in order to obtain an accurate measure of the hydrogen ion concentration, and a discussion of pH = {minus}log(a{sub H}{sup +}) versus p[H] = {minus}log[H+] is provided. It is shown that for quantitative studies, the quantity p[H] needs to be used. Fourteen uranium(VI) binding constants recommended by the OECD NEA literature review were corrected to the ionic strengths employed in the NMR study using specific ion interaction theory (SIT), and the predicted species distributions were compared with the actual species observed by multinuclear NMR. Agreement between observed and predicted stability fields is excellent. This establishes the utility of multinuclear NMR as a species-specific tool for the study of the actinide carbonate complexation constants, and serves as a means for validating the recommendations provided by the OECD NEA.

  13. Complex Formation History of Highly Evolved Basaltic Shergottite, Zagami

    NASA Technical Reports Server (NTRS)

    Niihara, T.; Misawa, K.; Mikouchi, T.; Nyquist, L. E.; Park, J.; Hirata, D.

    2012-01-01

    Zagami, a basaltic shergottite, contains several kinds of lithologies such as Normal Zagami consisting of Fine-grained (FG) and Coarse-grained (CG), Dark Mottled lithology (DML), and Olivine-rich late-stage melt pocket (DN). Treiman and Sutton concluded that Zagami (Normal Zagami) is a fractional crystallization product from a single magma. It has been suggested that there were two igneous stages (deep magma chamber and shallow magma chamber or surface lava flow) on the basis of chemical zoning features of pyroxenes which have homogeneous Mg-rich cores and FeO, CaO zoning at the rims. Nyquist et al. reported that FG has a different initial Sr isotopic ratio than CG and DML, and suggested the possibility of magma mixing on Mars. Here we report new results of petrology and mineralogy for DML and the Olivine-rich lithology (we do not use DN here), the most evolved lithology in this rock, to understand the relationship among lithologies and reveal Zagami s formation history

  14. Oxidative peptide /and amide/ formation from Schiff base complexes

    NASA Technical Reports Server (NTRS)

    Strehler, B. L.; Li, M. P.; Martin, K.; Fliss, H.; Schmid, P.

    1982-01-01

    One hypothesis of the origin of pre-modern forms of life is that the original replicating molecules were specific polypeptides which acted as templates for the assembly of poly-Schiff bases complementary to the template, and that these polymers were then oxidized to peptide linkages, probably by photo-produced oxidants. A double cycle of such anti-parallel complementary replication would yield the original peptide polymer. If this model were valid, the Schiff base between an N-acyl alpha mino aldehyde and an amino acid should yield a dipeptide in aqueous solution in the presence of an appropriate oxidant. In the present study it is shown that the substituted dipeptide, N-acetyl-tyrosyl-tyrosine, is produced in high yield in aqueous solution at pH 9 through the action of H2O2 on the Schiff-base complex between N-acetyl-tyrosinal and tyrosine and that a great variety of N-acyl amino acids are formed from amino acids and aliphatic aldehydes under similar conditions.

  15. Interferogram formation in the presence of complex and large deformation

    USGS Publications Warehouse

    Yun, S.-H.; Zebker, H.; Segall, P.; Hooper, A.; Poland, M.

    2007-01-01

    Sierra Negra volcano in Isabela island, Gala??pagos, erupted from October 22 to October 30 in 2005. During the 8 days of eruption, the center of Sierra Negra's caldera subsided about 5.4 meters. Three hours prior to the onset of the eruption, an earthquake (Mw 5.4) occurred, near the caldera. Because of the large and complex phase gradient due to the huge subsidence and the earthquake, it is difficult to form an interferogram inside the caldera that spans the eruption. The deformation is so large and spatially variable that the approximations used in existing InSAR software (ROI, ROI_PAC, DORIS, GAMMA) cannot properly coregister SAR image pairs spanning the eruption. We have developed here a two-step algorithm that can form intra-caldera interferograms from these data. The first step involves a "rubber-sheeting" SAR image coregistration. In the second step we use range offset estimates to mitigate the steep phase gradient. Using this new algorithm, we retrieve an interferogram with the best coverage to date inside the caldera of Sierra Negra. Copyright 2007 by the American Geophysical Union.

  16. Factors leading to the formation of arc cloud complexes

    NASA Technical Reports Server (NTRS)

    Welshinger, Mark John; Brundidge, Kenneth C.

    1987-01-01

    A total of 12 mesoscale convective systems (MCSs) were investigated. The duration of the gust front, produced by each MCS, was used to classify the MCSs. Category 1 MCSs were defined as ones that produced a gust front and the gust front lasted for more than 6 h. There were 7 category 1 MCSs in the sample. Category 2 MCSs were defined as ones that produced a gust front and the gust front lasted for 6 h or less. There were 4 category 2 MCSs. The MCS of Case 12 was not categorized because the precipitation characteristics were similar to a squall line, rather than an MCS. All of the category 1 MCSs produced arc cloud complexes (ACCs), while only one of the category 2 MCSs produced an ACC. To determine if there were any differences in the characteristics between the MCSs of the two categories, composite analyses were accomplished. The analyses showed that there were significant differences in the characteristics of category 1 and 2 MCSs. Category 1 MCSs, on average, had higher thunderstorm heights, greater precipitation intensities, colder cloud top temperatures and produced larger magnitudes of surface divergence than category 2 MCSs.

  17. Structure of soybean serine acetyltransferase and formation of the cysteine regulatory complex as a molecular chaperone

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Serine acetyltransferase (SAT) catalyzes the limiting reaction in plant and microbial biosynthesis of cysteine. In addition to its enzymatic function, SAT forms a macromolecular complex with O-acetylserine sulfhydrylase (OASS). Formation of the cysteine regulatory complex (CRC) is a critical biochem...

  18. Intervalence charge transfer in mixed valence compound modified by the formation of a supramolecular complex.

    PubMed

    Mechouet, Mourad; Perruchot, Christian; Maurel, François; Aeiyach, Salah; Bucher, Christophe; Chardon, Sylvie; Jouini, Mohamed

    2012-01-26

    The electrochemical and spectroelectrochemical properties of N,N-diphenyl-1,4-phenylenediamine (PDA) were investigated in the absence and in the presence of 18-crown-6-ether (18C6) or dibenzo 24-crown-8-ether (DB24C8), in a solution of tetrabutylammonium hexafluorophosphate (TBAPF6) in acetonitrile and in the presence of trifluoroacetic acid (TFA) only for 18C6. In neutral acetonitrile, PDA undergoes two reversible oxidation processes, which lead first to the formation of the cation-radical considered as mixed valence (MV) compound, and then to the dicationic species. When 18C6 is added in the medium and depending on 18C6 concentration, cyclic voltammetry shows a marked shift to more cathodic potentials of the current waves of the second redox process only. This is attributed to a strong interaction between the PDA(+2) dication and two 18C6 molecules, leading to the formation of a supramolecular complex with an association constant value K(a) = 7.0 × 10(7) M(-2). The interaction of 18C6 with PDA(+2) dication has a direct effect on the PDA(+.) cation-radical corresponding to a decrease in the lifetime of the MV compound and of the intramolecular electron transfer rate when 18C6 is present. Indeed, it results in a large decrease in the intervalence charge transfer (IV-CT) between the two amine centers in the MV compound (k(th) = 1.35 × 10(10) s(-1) in 18C6-free neutral solution containing 5.0 × 10(-4) M PDA, and k(th) = 3.6 × 10(9) s(-1) in the same medium at [18C6]/[PDA] = 20/1). And the comproportionation constant K(co) falls from 6.0 × 10(6) in 18C6-free solution to 1.6 × 10(3) at [18C6]/[PDA] = 20/1. In acidified acetonitrile and when TFA concentration is increased, PDA still shows the two successive and reversible oxidation processes, but both are shifted to more anodic potentials. However, when 18C6 is added, the two oxidation waves shift to more cathodic potentials, indicating an interaction of all protonated PDA redox states with 18C6, resulting in the formation of supramolecular complexes. In the presence of TFA, the value of K(co) is decreased to 4.3 × 10(4), but it remains unchanged when 18C6 is added, indicating no change in the lifetime of the MV compound. In this medium, IV-CT in the MV compound is greater with 18C6 (k(th) = 2.3 × 10(10) s(-1) for [18C6]/[PDA] = 20/1) than without (k(th) = 1.4 × 10(9) s(-1)), which indicates a more important IV-CT rate when 18C6 is present. The results show for the first time that is it possible to control the IV-CT rate, through the lifetime and the potential range where the MV compound is the most important. This control is not obtained as usual by chemical modification of the structure of the starting molecule, but by varying either the acidity or the 18C6 concentration as external stimuli, which lead to reversible formation/dissociation of a supramolecular complex species. Moreover, we also studied the electrochemical properties of PDA in the presence of wider crown ether such as DB24C8. We showed that PDA undergoes the same electrochemical behavior with DB24C8 than with 18C6 in neutral organic medium (K(a) = 2.9 × 10(3) M(-1)). This result suggests that the complexation between the electrogenerated PDA(+2) dication and the crown ethers may occur through face-to-face mode rather than rotaxane mode even with DB24C8 which is supposed to form inclusion complexes. PMID:22175529

  19. Complex formation between organotin chlorides and bis(1-pyrazolyl) methane ligand

    NASA Astrophysics Data System (ADS)

    Mesubi, M. Adediran; Enemo, R. E.

    The complex formation between organotin chloride and bis(1-pyrazolyl)methane, H 2CPz 2 has been investigated. Complexes of formula R 2SnCl 2H 2CPz 2 or RSnCl 3H 2CPz 2 have been isolated and characterised by elemental analysis, i.r. and 1H-NMR spectra. On the basis of their spectral properties, the complexes have been assigned an octahedral structure with the chlorides in the cis-position.

  20. [Protein isolation by means of complexing agents. 2. Formation of insoluble complexes of sunflower albumins with alginate or pectin].

    PubMed

    Schwenke, K D; Kracht, E; Mieth, G; Freimuth, U

    1977-01-01

    The formation of insoluble complexes of sunflower seed albumin and alginate or pectin is studied by means of turbidimetric titration and by determining the pH-dependent precipitability of protein. The complex formation that is based on electrostatic interaction is a function of the pH value and the protein-polyanion ratio. Consequently, it is affected by the neutral salt content of the solutions. 90% and more of the dissolved protein may be precipitated if the proportion of the precipitant amounts to 20%. A sodium chloride content of 0.6% reduces the precipitability by alginate to 74%. In the presence of 0.3% sodium chloride, at most 55% of protein are still precipitated by pectin. The difference in strength between the albumin-alginate and the albumin-pectin complex is also expressed by the dye-binding power. Albumin-pectin complexes bind the same amount of amido black as free protein. On the contrary, albumin-alginate complexes exhibit reduced dye-binding power due to stronger binding of the protein to the polyanion. The results obtained by turbidimetric titration of model systems can, in principle, be extrapolated to the precipitation of albumins from protein extracts. In accordance with the heterogenicity of the protein, the turbidimetric titration of the albumin-alginate and the albumin-pectin complexes exhibits two maxima. PMID:895835

  1. Thermodynamics of the formation of nickel(II) complexes with L-histidine in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Gorboletova, G. G.; Metlin, A. A.

    2014-09-01

    The heat effects of the formation of Ni(II) complexes with L-histidine in an aqueous solution are determined via direct calorimetry at 298.15 K and ionic strengths of 0.2, 0.5, and 1.0 (KNO3). The standard thermodynamic characteristics (?r H ?, ?r G ?, ?r S ?) of complex formation in the investigated system are calculated. It is concluded that the resulting values are consistent with the results from studying the structure of L-histidine complexes with Ni2+ ions by various spectral methods.

  2. The chitosan-gelatin (bio)polyelectrolyte complexes formation in an acidic medium.

    PubMed

    Voron'ko, Nicolay G; Derkach, Svetlana R; Kuchina, Yuliya A; Sokolan, Nina I

    2016-03-15

    The interaction of cationic polysaccharide chitosan and gelatin accompanied by the stoichiometric (bio)polyelectrolyte complexes formation has been studied by the methods of capillary viscometry, UV and FTIR spectroscopy and dispersion of light scattering. Complexes were formed in the aqueous phase, with pH being less than the isoelectric point of gelatin (pIgel). The particle size of the disperse phase increases along with the growth of the relative viscosity in comparison with sols of the individual components-polysaccharide and gelatin. Possible models and mechanism of (bio)polyelectrolyte complexes formation have been discussed. It was shown that the complex formation takes place not only due to the hydrogen bonds, but also due to the electrostatic interactions between the positively charged amino-groups of chitosan and negatively charged amino acid residues (glutamic Glu and aspartic Asp acids) of gelatin. PMID:26794762

  3. On-line dynamic titration: determination of dissociation constants for noncovalent complexes using Gaussian concentration profiles by electrospray ionization mass spectrometry.

    PubMed

    Fryck, Petr; Schug, Kevin A

    2007-07-15

    A new method for determination of dissociation constants (Kd) using on-line titration by electrospray ionization mass spectrometry is presented. Unlike in common titration experiments, where a set of discrete solutions with a fixed concentration of host and increasing concentration of guest is measured, here a continuous Gaussian concentration profile of guest, formed by band-broadening dispersion during passage through a long tubing, is utilized. An equation allowing access to dissociation constant values from experimental data fit to a 1:1 binding model was derived and incorporated into an in-house-written computer program for automated data processing. The new method is demonstrated for noncovalent complexes of cinchona alkaloid carbamate chiral selectors with N-dinitrobenzoylleucine enantiomers and a series of cyclodextrins with sulfonated azo dyes. PMID:17542559

  4. Smog chamber experiments to investigate Henry's law constants of glyoxal using different seed aerosols as well as imidazole formation in the presence of ammonia

    NASA Astrophysics Data System (ADS)

    Jakob, Ronit

    2015-04-01

    Aerosols play an important role in the chemistry and physics of the atmosphere. Hence, they have a direct as well as an indirect impact on the earth's climate. Depending on their formation, one distinguishes between primary and secondary aerosols[1]. Important groups within the secondary aerosols are the secondary organic aerosols (SOAs). In order to improve predictions about these impacts on the earth's climate the existing models need to be optimized, because they still underestimate SOA formation[2]. Glyoxal, the smallest α-dicarbonyl, not only acts as a tracer for SOA formation but also as a direct contributor to SOA. Because glyoxal has such a high vapour pressure, it was common knowledge that it does not take part in gas-particle partitioning and therefore has no impact on direct SOA formation. However, the Henry's law constant for glyoxal is surprisingly high. This has been explained by the hydration of the aldehyde groups, which means that a species with a lower vapour pressure is produced. Therefore the distribution of glyoxal between gas- and particle phase is atmospherically relevant and the direct contribution of glyoxal to SOA can no longer be neglected[3]. Besides this particulate glyoxal is able to undergo heterogeneous chemistry with gaseous ammonia to form imidazoles. This plays an important role for regions with aerosols exhibiting alkaline pH values for example from lifestock or soil dust because imidazoles as nitrogen containing compounds change the optical properties of aerosols[4]. A high salt concentration present in chamber seed aerosols leads to an enhanced glyoxal uptake into the particle. This effect is called "salting-in". The salting effect depends on the composition of the seed aerosol as well as the soluble compound. For very polar compounds, like glyoxal, a "salting-in" is observed[3]. Glyoxal particle formation during a smog chamber campaign at Paul-Scherrer-Institut (PSI) in Switzerland was examined using different seed aerosols such as ammonium sulfate, sodium chloride and sodium nitrate. The aim of this campaign was to investigate Henry's law constants for different seed aerosols. Additionally imidazole formation was studied. During the campaign filter samples were taken to investigate the amount of glyoxal and imidazole in the particle phase. After filter extraction and derivatisation of glyoxal, the compounds were measured using UHPLC-ESI-HR-MS. Additionally, gas-phase glyoxal has been analysed during the campaign. The results will be used to calculate the Henry's law constants. In this work, results of the glyoxal study as well as imidazole formation are presented. [1] J. Schnelle-Kreis, M. Sklorz, H. Herrmann, R. Zimmermann, Chem. Unserer Zeit, 2007, 41, 220-230 [2] M. M. Galloway, P. S. Chhabra, A. W. H. Chan, J. D. Surratt, R. C. Flagan, J. H. Seinfeld, F. N. Keutsch, Atmos. Chem. Phys, 9, 3331-3345, 2009 [3] C. J. Kampf, E. M. Waxman, J. G. Slowik, J. Dommen, L. Pfaffenberger, A. P. Praplan, A. S. H. Prévôt, U. Baltensperger, T. Hoffmann, R. Volkamer, Environ. Sci. Technol., 2013, 47, 4236-4244 [4] C. J. Kampf, R. Jakob, T. Hoffmann, Atmos. Chem. Phys., 12, 6323-6333, 2012

  5. Inhibitory effects of NAMI-A-like ruthenium complexes on prion neuropeptide fibril formation.

    PubMed

    Wang, Xuesong; Zhu, Dengsen; Zhao, Cong; He, Lei; Du, Weihong

    2015-05-01

    Prion diseases are a group of infectious and fatal neurodegenerative disorders caused by the conformational conversion of a cellular prion protein (PrP) into its abnormal isoform PrP(Sc). PrP106-126 resembles PrP(Sc) in terms of physicochemical and biological characteristics and is used as a common model for the treatment of prion diseases. Inhibitory effects on fibril formation and neurotoxicity of the prion neuropeptide PrP106-126 have been investigated using metal complexes as potential inhibitors. Nevertheless, the binding mechanism between metal complexes and the peptide remains unclear. The present study is focused on the interaction of PrP106-126 with NAMI-A and NAMI-A-like ruthenium complexes, including KP418, KP1019, and KP1019-2. Results demonstrated that these ruthenium complexes could bind to PrP106-126 in a distinctive binding mode through electrostatic and hydrophobic interactions. NAMI-A-like ruthenium complexes can also effectively inhibit the aggregation and fibril formation of PrP106-126. The complex KP1019 demonstrated the optimal inhibitory ability upon peptide aggregation, and cytotoxicity because of its large aromatic ligand contribution. The studied complexes could also regulate the copper redox chemistry of PrP106-126 and effectually inhibit the formation of reactive oxygen species. Given these findings, ruthenium complexes with relatively low cellular toxicity may be used to develop potential pharmaceutical products against prion diseases. PMID:25856332

  6. Constantes de stabilit de complexes organo-minraux. Interactions des ions plombeux avec les composs organiques hydrosolubles des eaux gravitaires de podzol

    NASA Astrophysics Data System (ADS)

    Bizri, Y.; Cromer, M.; Scharff, J. P.; Guillet, B.; Rouiller, J.

    1984-02-01

    The complexation of lead(II) ions by water-soluble soil organic matter as ligand (recovered by percolating water through a A2 horizon of a podzolic soil) has been studied by potentiometric methods at 25C in 0.1 M NaClO 4 medium. The total acidity of these solutions was resolved into strong, weak and very weak acidity. During the alkali titration, the dissociation of humic samples was characterized by an ? coefficient that may be determined according to a procedure derived from Irving-Rossotti's method. The so-called Henderson-Hasselbalch equation was used to obtain pK A values for each of the two weak acidities ( pKA = 4.80 (COOH) and pKA = 8.85 (OH)). For the determination of stability constants of metal-humate complexes (HA) in the acidic range, three methods have been investigated: - an approach using only pH measurements. - direct estimation of the free metal ion concentrations from ISE determinations. - application of Marinsky's method accounting for complications arising from the electric field at the surface of the polyelectrolyte which determines the effective concentration [A]. In these experiments typical values used for total lead(II) ion concentrations and total ligand concentrations are respectively in the range 4.10 -5 M to 4.10 -4 M and 0,33 to 0,57 meq1 -1. All results agree with the existence of mono and bis-complexes PbA and PbA 2 with stability constants (protometric determinations): logK1 = 4.2 and logK2 = 3.7. The values obtained by direct estimation of free lead(II) concentration are slightly lower. An increase in stability constants was observed with increase in pH and also with decrease in total metal ion concentration (at constant pH). Ligand conformational properties are expected to be of great importance in the complexation phenomena.

  7. Cleavage and formation of molecular dinitrogen in a single system assisted by molybdenum complexes bearing ferrocenyldiphosphine.

    PubMed

    Miyazaki, Takamasa; Tanaka, Hiromasa; Tanabe, Yoshiaki; Yuki, Masahiro; Nakajima, Kazunari; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki

    2014-10-20

    The N≡N bond of molecular dinitrogen bridging two molybdenum atoms in the pentamethylcyclopentadienyl molybdenum complexes that bear ferrocenyldiphosphine as an auxiliary ligand is homolytically cleaved under visible light irradiation at room temperature to afford two molar molybdenum nitride complexes. Conversely, the bridging molecular dinitrogen is reformed by the oxidation of the molybdenum nitride complex at room temperature. This result provides a successful example of the cleavage and formation of molecular dinitrogen induced by a pair of two different external stimuli using a single system assisted by molybdenum complexes bearing ferrocenyldiphosphine under ambient conditions. PMID:25214300

  8. A study of molecular complex formation between propyl gallate and ascorbic acid in the microemulsion phase of sodium dodecyl sulfate, pentanol and water system.

    PubMed

    Szymula, M; Radzki, S

    2004-06-01

    The association between two water-soluble antioxidants, i.e. ascorbic acid and propyl gallate have been studied by absorption spectroscopy in microemulsion formed in sodium dodecyl sulfate/pentanol/water micellar system. It has been shown that propyl gallate forms 1:1 molecular complex with ascorbic acid in every solution. Evolution of the absorption spectra during the study of molecular complex formation goes through well-defined isosbestic points. The association constants were calculated using curve-fitting procedure. The observed interactions are stronger in the less polar solvents. PMID:15261038

  9. Substituent effect on the electron acceptor property of 1,4-benzoquinone towards the formation of molecular complex with sulfamethoxazole

    NASA Astrophysics Data System (ADS)

    Ganesh, K.; Satheshkumar, A.; Balraj, C.; Elango, K. P.

    2013-04-01

    UV-Vis, 1H NMR, FT-IR, LC-MS and fluorescence spectral techniques were employed to investigate the mechanism of interaction of sulfamethoxazole with varying number of methoxy/chloro substituted 1,4-benzoquinones (MQ1-4) and to characterize the reaction products. The interactions of MQ1-4 with sulfamethoxazole (SULF) were found to proceed through the formation of a donor-acceptor complex, containing radical anion and its conversion to the product. Fluorescence quenching studies showed that the interaction between the donor and the acceptors are spontaneous. The results indicated that the progressive replacement of chlorine atom (-I effect) by methoxy group (+M effect) in the quinone decreased the electron acceptor property of the quinone. The results of the correlation of experimentally measured binding constants with electrochemical data and ab initio DFT calculations supported these observations.

  10. Effects of chemical and enzymatic modifications on starch-oleic acid complex formation.

    PubMed

    Arijaje, Emily Oluwaseun; Wang, Ya-Jane

    2015-04-29

    The solubility of starch-inclusion complexes affects the digestibility and bioavailability of the included molecules. Acetylation with two degrees of substitution, 0.041 (low) and 0.091 (high), combined without or with a β-amylase treatment was employed to improve the yield and solubility of the inclusion complex between debranched potato starch and oleic acid. Both soluble and insoluble complexes were recovered and analyzed for their degree of acetylation, complexation yields, molecular size distributions, X-ray diffraction patterns, and thermal properties. Acetylation significantly increased the amount of recovered soluble complexes as well as the complexed oleic acid in both soluble and insoluble complexes. High-acetylated debranched-only starch complexed the highest amount of oleic acid (38.0 mg/g) in the soluble complexes; low-acetylated starch with or without the β-amylase treatment resulted in the highest complexed oleic acid in the insoluble complexes (37.6-42.9 mg/g). All acetylated starches displayed the V-type X-ray pattern, and the melting temperature generally decreased with acetylation. The results indicate that starch acetylation with or without the β-amylase treatment can improve the formation and solubility of the starch-oleic acid complex. PMID:25877005

  11. Radiosensitization of DNA by Cisplatin Adducts Results from an Increase in the Rate Constant for the Reaction with Hydrated Electrons and Formation of Pt(I).

    PubMed

    Behmand, B; Marignier, J-L; Mostafavi, M; Wagner, J R; Hunting, D J; Sanche, L

    2015-07-30

    Pulse radiolysis measurements of the decay of hydrated electrons in solutions containing different concentrations of the oligonucleotide GTG with and without a cisplatin adduct show that the presence of a cisplatin moiety accelerates the reaction between hydrated electrons and the oligonucleotide. The rate constant of the reaction is found to be 2.23 10(10) mol(-1) L s(-1), which indicates that it is diffusion controlled. In addition, we show for the first time the formation of a Pt(I) intermediate as a result of the reaction of hydrated electrons with GTG-cisplatin. A putative reaction mechanism is proposed, which may form the basis of the radiosensitization of cancer cells in concomitant chemoradiation therapy with cisplatin. PMID:26098937

  12. Thermodynamics of the formation of copper(II) complexes with L-histidine in aqueous solution

    NASA Astrophysics Data System (ADS)

    Gorboletova, G. G.; Metlin, A. A.

    2015-02-01

    The heat effects from the reaction between L-histidine solutions and Cu(NO3)2 solutions at 298.15 K in the 0.2 to 1.0 (KNO3) range of ionic strength are measured by means of direct calorimetry. The experimental data is treated with allowance for the simultaneous proceeding of several processes. The heat effects of the formation of complexes Cu(His)+, Cu(His)2, CuHHis2+, CuH(His){2/+} and CuH2(His){2/2+} are calculated from calorimetric measurements. The standard enthalpies of formation for complexes of L-histidine with Cu2+ ions are obtained via extrapolation to zero ionic strength. The relationship between the thermodynamic characteristics of the formation of complexes of copper(II) with L-histidine and their structure is determined.

  13. The application of the constants of motion to nonlinear stationary waves in complex plasmas: a unified fluid dynamic viewpoint

    NASA Astrophysics Data System (ADS)

    McKenzie, J. F.; Dubinin, E.; Sauer, K.; Doyle, T. B.

    2004-08-01

    Perturbation reductive procedures, as used to analyse various weakly nonlinear plasma waves (solitons and periodic waves), normally lead to the dynamical system being described by KdV, Burgers' or a nonlinear Schrdinger-type equation, with properties that can be deduced from an array of mathematical techniques. Here we develop a fully nonlinear theory of one-dimensional stationary plasma waves, which elucidates the common nature of various diverse wave phenomena. This is accomplished by adopting an essentially fluid dynamic viewpoint. In this unified treatment the constants of the motion (for mass, momentum and energy) lead naturally to the construction of the wave structure equations. It is shown, for example, that electrostatic, Hall magnetohydrodynamic and ion cyclotron acoustic nonlinear waves all obey first-order differential equations of the same generic type for the longitudinal flow field of the wave. The equilibrium points, which define the soliton amplitude, are given by the compressive and/or rarefactive roots of a total plasma energy or momentum function characterizing the wave type. This energy function, which is an algebraic combination of the Bernoulli momentum and energy functions for the longitudinal flow field, is the fluid dynamic counterpart of the pseudo-potentials, which are characteristic of system structure equations formulated in other than fluid variables. Another general feature of the structure equation is the phenomenon of choked flow, which occurs when the flow speed becomes sonic. It is this trans-sonic property that limits the soliton amplitudes and defines the critical collective Mach numbers of the waves. These features are also obtained in multi-component plasmas where, for example, in a bi-ion plasma, momentum exchanges between protons and heavier ions are mediated by the Maxwell magnetic stresses. With a suitable generalization of the concept of a sonic point in a bi-ion system and the corresponding choked flow feature, the wave structures, although now more complicated, can also be understood within this overall fluid framework. Particularly useful tools in this context are the momentum hodograph (an algebraic relation between the bi-ion speeds and the electron speed, or magnetic field, which follows from the conservation of mass, momentum and charge-neutrality) and a generalized Bernoulli energy density for each species. Analysis shows that the bi-ion solitons are essentially compressive, but contain the remarkable feature of the presence of a proton rarefactive core. A new type of soliton, called an oscilliton because embedded spatial oscillations are superimposed on the classical soliton, is also described and discussed. A necessary condition for the existence of this type of wave is that the linear phase velocity must exhibit an extremum where the phase speed matches the group speed. The remarkable properties of this wave are illustrated for the case of both whistler waves and bi-ion waves where, for the latter, the requisite condition is met near the cross-over frequencies. In the case of the whistler oscilliton, which propagates at speeds in excess of one half of the Alfvn speed (based on the electrons), an analytic solution has been constructed through a phase-portrait integral of the system in which the proton and electron dynamics must be placed on the same footing. The relevance of the different wave structures to diverse space environments is briefly discussed in relation to recently available high-time and spatial resolution data from satellite observations.

  14. Reactions of sulfur-nitrosyl iron complexes of "g=2.03" family with hemoglobin (Hb): kinetics of Hb-NO formation in aqueous solutions.

    PubMed

    Sanina, N A; Syrtsova, L A; Shkondina, N I; Rudneva, T N; Malkova, E S; Bazanov, T A; Kotel'nikov, A I; Aldoshin, S M

    2007-03-01

    NO-donating ability of nitrosyl [Fe-S] complexes, namely, mononuclear dinitrosyl complexes of anionic type [Fe(S2O3)2(NO)2]-(I) and neutral [Fe2(SL1)2(NO)2] with L1=1H-1,2,4-triazole-3-yl (II); tetranitrosyl binuclear neutral complexes [Fe2(SL2)2(NO)4] with L2=5-amino-1,2,4-triazole-3-yl (III); 1-methyl-1H-tetrazole-5-yl (IV); imidazole-2-yl (V) and 1-methyl-imidazole-2-yl (VI) has been studied. In addition, Roussin's "red salt" Na2[Fe2S2(NO)4] x 8H2O (VII) and Na2[Fe(CN)5NO] x H2O (VIII) have been investigated. The method for research has been based on the formation of Hb-NO adduct upon the interaction of hemoglobin with NO generated by complexes I-VIII in aqueous solutions. Kinetics of NO formation was studied by registration of absorption spectra of the reaction systems containing Hb and the complex under study. For determination of HbNO concentration, the experimental absorption spectra were processed during the reaction using standard program MATHCAD to determine the contribution of individual Hb and HbNO spectra in each spectrum. The reaction rate constants were obtained by analyzing kinetic dependence of Hb interaction with NO donors under study. All kinetic dependences for complexes I-VI were shown to be described well in the frame of formalism of pseudo first-order reactions. The effective first-order rate constants for the studied reactions have been determined. As follows from the values of rate constants, the rate of interaction of sulfur-nitrosyl iron complexes (I-VI) with Hb is limited by the stage of NO release in the solution. PMID:17140821

  15. Metabolic Intermediate Complex Formation of Human Cytochrome P450 3A4 by Lapatinib

    PubMed Central

    Takakusa, Hideo; Wahlin, Michelle D.; Zhao, Chunsheng; Hanson, Kelsey L.; New, Lee Sun; Chan, Eric Chun Yong

    2011-01-01

    Lapatinib, an oral breast cancer drug, has recently been reported to be a mechanism-based inactivator of cytochrome P450 (P450) 3A4 and also an idiosyncratic hepatotoxicant. It was suggested that formation of a reactive quinoneimine metabolite was involved in mechanism-based inactivation (MBI) and/or hepatotoxicity. We investigated the mechanism of MBI of P450 3A4 by lapatinib. Liquid chromatography-mass spectrometry analysis of P450 3A4 after incubation with lapatinib did not show any peak corresponding to irreversible modifications. The enzymatic activity inactivated by lapatinib was completely restored by the addition of potassium ferricyanide. These results indicate that the mechanism of MBI by lapatinib is quasi-irreversible and mediated via metabolic intermediate complex (MI complex) formation. This finding was verified by the increase in a signature Soret absorbance at approximately 455 nm. Two amine oxidation products of the metabolism of lapatinib by P450 3A4 were characterized: N-hydroxy lapatinib (M3) and the oxime form of N-dealkylated lapatinib (M2), suggesting that a nitroso or another related intermediate generated from M3 is involved in MI complex formation. In contrast, P450 3A5 was much less susceptible to MBI by lapatinib via MI complex formation than P450 3A4. In addition, P450 3A5 had a significantly lower ability than 3A4 to generate M3, consistent with N-hydroxylation as the initial step in the pathway to MI complex formation. In conclusion, our results demonstrate that the primary mechanism for MBI of P450 3A4 by lapatinib is not irreversible modification by the quinoneimine metabolite, but quasi-irreversible MI complex formation mediated via oxidation of the secondary amine group of lapatinib. PMID:21363997

  16. Gating of single molecule junction conductance by charge transfer complex formation.

    PubMed

    Vezzoli, Andrea; Grace, Iain; Brooke, Carly; Wang, Kun; Lambert, Colin J; Xu, Bingqian; Nichols, Richard J; Higgins, Simon J

    2015-12-01

    The solid-state structures of organic charge transfer (CT) salts are critical in determining their mode of charge transport, and hence their unusual electrical properties, which range from semiconducting through metallic to superconducting. In contrast, using both theory and experiment, we show here that the conductance of metal |single molecule| metal junctions involving aromatic donor moieties (dialkylterthiophene, dialkylbenzene) increase by over an order of magnitude upon formation of charge transfer (CT) complexes with tetracyanoethylene (TCNE). This enhancement occurs because CT complex formation creates a new resonance in the transmission function, close to the metal contact Fermi energy, that is a signal of room-temperature quantum interference. PMID:26510687

  17. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    SciTech Connect

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-13

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  18. Synergistic effect of ATP for RuvA–RuvB–Holliday junction DNA complex formation

    PubMed Central

    Iwasa, Takuma; Han, Yong-Woon; Hiramatsu, Ryo; Yokota, Hiroaki; Nakao, Kimiko; Yokokawa, Ryuji; Ono, Teruo; Harada, Yoshie

    2015-01-01

    The Escherichia coli RuvB hexameric ring motor proteins, together with RuvAs, promote branch migration of Holliday junction DNA. Zero mode waveguides (ZMWs) constitute of nanosized holes and enable the visualization of a single fluorescent molecule under micromolar order of the molecules, which is applicable to characterize the formation of RuvA–RuvB–Holliday junction DNA complex. In this study, we used ZMWs and counted the number of RuvBs binding to RuvA–Holliday junction DNA complex. Our data demonstrated that different nucleotide analogs increased the amount of Cy5-RuvBs binding to RuvA–Holliday junction DNA complex in the following order: no nucleotide, ADP, ATPγS, and mixture of ADP and ATPγS. These results suggest that not only ATP binding to RuvB but also ATP hydrolysis by RuvB facilitates a stable RuvA–RuvB–Holliday junction DNA complex formation. PMID:26658024

  19. Production of unstable proteins through the formation of stable core complexes

    PubMed Central

    Levy, Nicolas; Eiler, Sylvia; Pradeau-Aubreton, Karine; Maillot, Benoit; Stricher, François; Ruff, Marc

    2016-01-01

    Purification of proteins that participate in large transient complexes is impeded by low amounts, heterogeneity, instability and poor solubility. To circumvent these difficulties we set up a methodology that enables the production of stable complexes for structural and functional studies. This procedure is benchmarked and applied to two challenging protein families: the human steroid nuclear receptors (SNR) and the HIV-1 pre-integration complex. In the context of transcriptional regulation studies, we produce and characterize the ligand-binding domains of the glucocorticoid nuclear receptor and the oestrogen receptor beta in complex with a TIF2 (transcriptional intermediary factor 2) domain containing the three SNR-binding motifs. In the context of retroviral integration, we demonstrate the stabilization of the HIV-1 integrase by formation of complexes with partner proteins and DNA. This procedure provides a powerful research tool for structural and functional studies of proteins participating in non-covalent macromolecular complexes. PMID:26983699

  20. Tying synaptonemal complex initiation to the formation and programmed repair of DNA double-strand breaks

    PubMed Central

    Henderson, Kiersten A.; Keeney, Scott

    2004-01-01

    During meiosis, homologous chromosomes recombine and become closely apposed along their lengths within the synaptonemal complex (SC). In part because Spo11 is required both to make the double-strand breaks (DSBs) that initiate recombination and to promote normal SC formation in many organisms, it is clear that these two processes are intimately coupled. The molecular nature of this linkage is not well understood, but it has been proposed that SC formation initiates locally at the sites of ongoing recombination and in particular at the subset of sites that will eventually give rise to crossovers. To test this hypothesis, we examined further the relationship between DSBs and SC formation in Saccharomyces cerevisiae. SCs were monitored in a series of spo11 missense mutants with varying DSB frequencies. Alleles that blocked DSB formation gave SC phenotypes indistinguishable from a deletion mutant, and partial loss-of-function mutations with progressively more severe DSB defects caused corresponding defects in SC formation. These results strongly correlate SC formation with Spo11 catalytic activity per se. Numbers of Zip3 complexes on chromosomes, thought to represent the sites of SC initiation, also declined when Spo11 activity decreased, but in a markedly nonlinear fashion: hypomorphic spo11 alleles caused larger defects in DSB formation than in Zip3 complex formation. This nonlinear response of Zip3 closely paralleled the response of crossover recombination products. The quantitative relationship between Zip3 foci, SC formation, and crossing over strongly implicates crossover-designated recombination intermediates as the sites of SC initiation. PMID:15070750

  1. Multistability and sustained oscillations in a model for protein complex formation

    NASA Astrophysics Data System (ADS)

    Löb, Daniel; Priester, Christopher; Drossel, Barbara

    2016-03-01

    We investigate a model for the formation of protein complexes where each protein can occur at most once in a complex. The reaction rates for association and dissociation of proteins can be chosen independently for each reaction, without imposing detailed balance conditions. We show that this simple model can display multistability and periodic oscillations when it contains at least four different protein species. We prove that a system with three elementary species cannot be multistable.

  2. Acidity and complex formation studies of 3-(adenine-9-yl)-propionic and 3-(thymine-1-yl)-propionic acids in ethanol-water media

    NASA Astrophysics Data System (ADS)

    Hammud, Hassan H.; El Shazly, Shawky; Sonji, Ghassan; Sonji, Nada; Bouhadir, Kamal H.

    2015-05-01

    The ligands 3-(adenine-9-yl)propionic acid (AA) and 3-(thymine-1-yl)propionic acid (TA) were prepared by N9-alkylation of adenine and N1-alkylation of thymine with ethylacrylate in presence of a base catalyst, followed by acid hydrolysis of the formed ethyl esters to give the corresponding propionic acid derivatives. The products were characterized by spectral methods (FTIR, 1H NMR and 13C NMR), which confirm their structures. The dissociation constants of ligands, were potentiometrically determined in 0.3 M KCl at 20-50 °C temperature range. The work was extended to study complexation behavior of AA and TA with various biologically important divalent metal ions (Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Mn2+ and Pb2+) in 50% v/v water-ethanol medium at four different temperatures, keeping ionic strength constant (0.3 M KCl). The order of the stability constants of the formed complexes decreases in the sequence Cu2+ > Pb2+ > Zn2+ > Ni2+ > Co2+ > Mn2+ > Cd2+ for both ligands. The effect of temperature was also studied and the corresponding thermodynamic functions (ΔG, ΔH, ΔS) were derived and discussed. The formation of metal complexes has been found to be spontaneous, and the stability constants were dependant markedly on the basicity of the ligands.

  3. Methionine oxidation of amyloid peptides by peroxovanadium complexes: inhibition of fibril formation through a distinct mechanism.

    PubMed

    He, Lei; Wang, Xuesong; Zhu, Dengsen; Zhao, Cong; Du, Weihong

    2015-12-01

    Fibril formation of amyloid peptides is linked to a number of pathological states. The prion protein (PrP) and amyloid-? (A?) are two remarkable examples that are correlated with prion disorders and Alzheimer's disease, respectively. Metal complexes, such as those formed by platinum and ruthenium compounds, can act as inhibitors against peptide aggregation primarily through metal coordination. This study revealed the inhibitory effect of two peroxovanadium complexes, (NH4)[VO(O2)2(bipy)]4H2O (1) and (NH4)[VO(O2)2(phen)]2H2O (2), on amyloid fibril formation of PrP106-126 and A?1-42via site-specific oxidation of methionine residues, besides direct binding of the complexes with the peptides. Complexes 1 and 2 showed higher anti-amyloidogenic activity on PrP106-126 aggregation than on A?1-42, though their regulation on the cytotoxicity induced by the two peptides could not be differentiated. The action efficacy may be attributed to the different molecular structures of the vanadium complex and the peptide sequence. Results reflected that methionine oxidation may be a crucial action mode in inhibiting amyloid fibril formation. This study offers a possible application value for peroxovanadium complexes against amyloid proteins. PMID:26444976

  4. Nup155 regulates nuclear envelope and nuclear pore complex formation in nematodes and vertebrates

    PubMed Central

    Franz, Cerstin; Askjaer, Peter; Antonin, Wolfram; Iglesias, Carmen Lpez; Haselmann, Uta; Schelder, Malgorzata; de Marco, Ario; Wilm, Matthias; Antony, Claude; Mattaj, Iain W

    2005-01-01

    Nuclear envelope (NE) formation during cell division in multicellular organisms is a central yet poorly understood biological process. We report that the conserved nucleoporin Nup155 has an essential function in NE formation in Caenorhabditis elegans embryos and in Xenopus laevis egg extracts. In vivo depletion of Nup155 led to failure of nuclear lamina formation and defects in chromosome segregation at anaphase. Nup155 depletion inhibited accumulation of nucleoporins at the nuclear periphery, including those recruited to chromatin early in NE formation. Electron microscopy analysis revealed that Nup155 is also required for the formation of a continuous nuclear membrane in vivo and in vitro. Time-course experiments indicated that Nup155 is recruited to chromatin at the time of NE sealing, suggesting that nuclear pore complex assembly has to progress to a relatively late stage before NE membrane assembly occurs. PMID:16193066

  5. Natural organic acids in acidic surface water. acid-base properties, complex formation with aluminum, and their contribution to acidification

    NASA Astrophysics Data System (ADS)

    Lee, Ying-Hua

    In order to assess the natural organic acidity of surface waters a simplified chemical equilibrium model was tested. The application of a potentiometric titration system, allowed the determination of both the concentration and the average proton dissociation constant (pKa) of the moderately weak acidic carboxylic group (COOH)W in streamwaters. The observed weak acidity in the pH range 3.8 to 5.0, could be described by assuming that the predominant acidic sites are comprised of (COOH)W having pKa=4.460.36 (n=84). The concentration of (COOH)W in the studied streamwaters ranged from 31 to 105 M. The (COOH)W content of the DOC in these streamwaters was 7.92.3 meq/g C (n=20) during autumn and 6.31.8 meq/g C (n=10) during summer. The statistical analysis indicated that the total concentration of (COOH)W and of DOC were the principle factors controlling the concentration of non-labile organic Al (Alorg) in these streamwaters. The concentrations of monomeric Al and hydrogen ions were less important. Approximately 8 to 18% of (COOH)W, together with the strong acidic carboxylic groups, may be involved in the formation of Alorg of phthalic-like complexes rather than salicylic-like complexes. The acidic contribution from the dissociation of (COOH)W and Al-organic complexes was estimated.

  6. Communication: Structure, formation, and equilibration of ensembles of Ag-S complexes on an Ag surface

    SciTech Connect

    Russell, Selena M.; Kim, Yousoo; Liu, Da-Jiang; Evans, J. W.; Thiel, P. A.

    2013-02-15

    We have utilized conditions of very low temperature (4.7 K) and very low sulfur coverage to isolate and identify Ag-S complexes that exist on the Ag(111) surface. The experimental conditions are such that the complexes form at temperatures above the temperature of observation. These complexes can be regarded as polymeric chains of varying length, with an Ag4S pyramid at the core of each monomeric unit. Steps may catalyze the formation of the chains and this mechanism may be reflected in the chain length distribution.

  7. The standard enthalpies of combustion and formation of crystalline cobalt tetrakis(4-metoxyphenyl)porphin complex

    NASA Astrophysics Data System (ADS)

    Tarasov, R. P.; Volkov, A. V.; Bazanov, M. I.; Semeikin, A. S.

    2009-05-01

    The energy of combustion of cobalt tetrakis(4-metoxyphenyl)porphin was determined in an isothermic-shell liquid calorimeter with a stationary calorimetric bomb. The standard enthalpies of combustion and formation of the complex were calculated, -? c H o = 27334.06 50.98 kJ/mol and ?f H o = 3062.90 50.97 kJ/mol.

  8. STUDY USING A THREE-DIMENSIONAL SMOG FORMATION MODEL UNDER CONDITIONS OF COMPLEX FLOW

    EPA Science Inventory

    To clarify the photochemical smog formation mechanisms under conditions of complex flow, the SAI Urban Airshed Model was evaluated using a 1981 field observed data base. In the Tokyo Metropolitan Area higher O3 concentrations are usually observed near the shore in the morning. As...

  9. Complex formation equilibria of binary and ternary complexes involving 3,3-bis(1-methylimidazol-2yl)propionic acid and bio-relevant ligands as 1-aminocyclopropane carboxylic acid with reference to plant hormone

    NASA Astrophysics Data System (ADS)

    Shoukry, Mohamed M.; Hassan, Safaa S.

    2014-01-01

    The formation equilibria for the binary complexes of Cu(II) with 1-aminocyclopropane carboxylic acid (ACC) and 3,3-bis(1-methylimidazol-2-yl)propionic acid (BIMP) were investigated. ACC and BIMP form the complexes 1 1 0, 1 2 0 and 1 1 -1. The ternary complexes of Cu(II) with BIMP and biorelevant ligands as some selected amino acids, peptides and DNA constituents are formed in a stepwise mechanism. The stability constants of the complexes formed were determined and their distribution diagrams were evaluated. The kinetics of hydrolysis of glycine methyl ester in presence of [Cu(BIMP)]+ was investigated by pH-stat technique and the mechanism was discussed.

  10. Stability constants for mono- and dioxalato-complexes of Y and the REE, potentially important species in groundwaters and surface freshwaters

    NASA Astrophysics Data System (ADS)

    Schijf, J.; Byrne, R. H.

    2001-04-01

    We present the first measured set of stability constants for mono- and dioxalato-complexes of yttrium and all rare earths except Pm (Y+REE), Ox? n = [MOx n3-2n] [M 3+] -1 [Ox 2-] -n(where [ ] ? concentrations, M ? Y+REE, and Ox 2- ? C 2O 42-). Aqueous solutions of Y+REE were titrated with oxalic acid in the presence of a cation-exchange resin, and Y+REE concentrations in the solution phase were measured by ICP-MS. This method allows investigation of all Y+REE simultaneously under identical conditions and is thus very sensitive to subtle inter-element variations in log Ox? n. Experiments were performed at a single ionic strength ( I = 0.05 M), but at two values of pH. Patterns of log Ox? 1 and log Ox? 2, determined from our experiments, are similar in shape and reminiscent of those for carbonato-complexes. The average ratio of stepwise stability constants K 2/K 1 = Ox? 2/( Ox? 1) 2 is 0.05 0.02 for Y+REE excluding La and Ce. Literature values of Ox? 1(Eu) for 0.03 mol/L ? I ? 1 mol/L were used to derive the relation log Ox? 1(Eu) = log Ox? 10(Eu) - 6.132? I/(1 + 1.47? I) + 0.902 I, where log Ox? 10(Eu) is the stability constant at infinite dilution. Applying this relation to all Y+REE, the following values of log Ox? 10 (at zero ionic strength) were found: 6.66 (Y), 5.87 (La), 5.97 (Ce), 6.25 (Pr), 6.31 (Nd), 6.43 (Sm), 6.52 (Eu), 6.53 (Gd), 6.63 (Tb), 6.74 (Dy), 6.77 (Ho), 6.83 (Er), 6.89 (Tm), 6.95 (Yb), 6.96 (Lu). These values, which are based on direct measurements for each individual Y+REE, agree quite well with published extrapolations that are mostly based on linear free-energy relationships. Total oxalate concentrations of 10 -5-10 -3 M have been reported for soil solutions. Free oxalate ions persist at much lower pH than free carbonate ions and a simple speciation model demonstrates that oxalato-complexes can dominate Y+REE speciation in mildly acidic groundwaters of low-to-moderate alkalinity.

  11. Characterizing Extragalactic Star Formation with GALEX Legacy Photometric Analysis of UV-Bright Stellar Complexes

    NASA Astrophysics Data System (ADS)

    Thilker, David

    At the close of nearly a decade of observing, GALEX has accumulated an unprecedented archive of ultraviolet (UV) images revealing both the scope and intricacy of star formation (SF) in many thousands of galaxies inhabiting the local universe. If the observed hierarchical SF morphology can be quantified systematically, and physically interpreted with multi-wavelength ancillary data and modeling, then the low redshift GALEX legacy will approach completion. However, the GALEX GR6 pipeline database contains a highly incomplete census of young stellar complexes even for very well-studied galaxies. We propose to apply a dedicated photometry algorithm that has been optimized for measuring the properties of irregularly shaped sources in crowded galaxy images containing spatially variant, diffuse intra-clump emission. Structures will be selected in the UV, but we will compile UV-visible-MIR SEDs for each detection utilizing Pan-STARRS1+SDSS and WISE data. These SEDs will then be fit using population-synthesis models to derive estimated stellar mass, age, and extinction. Processing will be completed for the entire diameter-limited GALEX Large Galaxy Atlas (GLGA) sample of 20,000+ galaxies, at a variety of standardized spatial resolutions. Although the precise categorization of the cataloged substructures will depend on galaxy distance, the outcome of our analysis will be a catalog similar to the stellar association surveys of past decades for very nearby galaxies based on resolved stars (e.g. van den Bergh 1964, Hodge 1986, Efremov et al. 1987), except that our investigation will probe a galaxy sample of dramatically larger size using the integrated UV light from such groupings of young stars. Our algorithm is multi-scale in nature and will thus preserve the hierarchical properties of the stellar distribution, by linking sub-clumps to their larger-scale parent feature(s). The resulting database will be a fundamental resource for follow-up multi-wavelength studies probing SF-driven galaxy evolution using both existing NASA databases and operating instruments, in addition to upcoming space telescopes. While a legacy of our project will be the hierarchical photometric database (disseminated via MAST and NED) which supports extragalactic community science, our own goals from the proposed comprehensive measurements address some vital issues: (i) Currently there is controversy regarding the power-law slope of the empirical star formation law (SFL). Is there constant star formation efficiency above the HI-to-H_2 transition gas surface density (implying ~unity slope, see papers by Bigiel et al. and Leroy et al.), or is the SFL relation a stronger function of gas density with a super-linear form (as observed by Kennicutt et al. 2007)? Liu et al. (2011) have shown that the answer may depend critically on whether or not diffuse emission underlying star-forming substructures is removed. Our analysis will allow firm resolution of this issue, as we will also apply our photometry algorithm to Spitzer imaging for a subset of our sample galaxies, thus providing background-subtracted L(UV) and L(IR) measurements for substructures which can then be compared to existing and forthcoming (ALMA) CO imaging. (ii) We will also verify/calibrate our SED-fit based determination of age, extinction, and mass for UV-bright structures via direct comparison to the ground-truth stemming from resolved stellar populations (e.g. in ANGST galaxies) and also high-resolution HST UV-optical star cluster surveys (further out in the Local Volume). (iii) Finally, we will measure the diffuse UV fraction in a few hundred of the nearest galaxies (accounting for variation tied only to spatial resolution), trying to ascertain the characteristic fraction in galaxies of different Hubble type and dust-to-gas ratio. Systematic local variations in diffuse fraction and color will also be quantified as a function of environment.

  12. Formation of complex impact craters - Evidence from Mars and other planets

    NASA Technical Reports Server (NTRS)

    Pike, R. J.

    1980-01-01

    An analysis of the depth vs diameter data of Arthur (1980), is given along with geomorphic data for 73 Martian craters. The implications for the formation of complex impact craters on solid planets is discussed. The analysis integrates detailed morphological observations on planetary craters with geologic data from terrestrial meteorite and explosion craters. The simple to complex transition for impact craters on Mars appears at diameters in the range of 3 to 8 km. Five features appear sequentially with increasing crater size, flat floors, central peaks and shallower depths, scalloped rims, and terraced walls. This order suggests that a shallow depth of excavation and a rebound mechanism have produced the central peaks, not centripetal collapse and deep sliding. Simple craters are relatively uniform in shape from planet to planet, but complex craters vary considerably. Both the average onset diameter for complex impact craters on Mars and the average depth of complex craters vary inversely with gravitational acceleration on four planets.

  13. Structure and kinetics of formation of catechol complexes of ferric soybean lipoxygenase-1

    SciTech Connect

    Nelson, M.J.; Brennan, B.A.; Chase, D.B. |

    1995-11-21

    Ferric soybean lipoxygenase forms stable complexes with 4-substituted catechols. The structure of the complex between the enzyme and 3,4-dihydroxybenzonitrile has been studied by resonance Raman, electron paramagnetic resonance, visible, and X-ray spectroscopies. It is a bidentate iron-catecholate complex with at least one water ligand. The kinetics of formation of complexes between lipoxygenase and 3,4-dihydroxybenzonitrile and 3,4-dihydroxyacetophenone have been studied by stopped-flow spectroscopy. The data are consistent with two kinetically distinct, reversible steps. The pH dependence of the first step suggests that the substrate for the reaction is the catechol monoanion. When these results are combined, plausible mechanisms for the complexation reaction are suggested. 51 refs., 12 figs., 2 tabs.

  14. Effect of entropy-packing fraction relation on the formation of complex metallic materials

    NASA Astrophysics Data System (ADS)

    Tourki Samaei, Arash; Mohammadi, Ehsan

    2015-09-01

    By combining a number of elements to form complex metallic materials without a base element, it was recently shown that one can obtain rather complex structures, including random solute solutions, multi-phased mixtures and amorphous structures with/without nano-precipitations. Compared to conventional metallic materials, these complex ones could show excellent mechanical and physical properties across a wide range of temperatures, therefore being a promising advanced material for high-temperature applications; however, designing these complex materials, at present, still lacks a unified physical approach but relies on the choice of a few metallurgical parameters, such as atomic size mismatch, heat of mixing and valence electron concentration. Here, we identify a physical mechanism through the optimization of the excess configurational entropy of mixing in the control of phase formation in these metallic materials. The theoretical framework herein established is expected to provide a new paradigm in pursuit of complex metallic materials with superior properties.

  15. A new approach to determination of hydration equilibria constants for the case of [Er(EDTA)(H2O)(n)](-) complexes.

    PubMed

    Janicki, Rafał; Mondry, Anna

    2014-12-28

    Two anionic complexes [Er(EDTA)(H2O)2](-) and [Er(EDTA)(H2O)3](-) were obtained in the form of the following compounds: [C(NH2)3]2[Er(EDTA)(H2O)2]ClO4·6H2O () and Na[Er(EDTA)(H2O)3]·5H2O (), respectively. The UV-vis-NIR absorption spectra of both monocrystals were measured at room temperature and at 4.2 K. The influence of the coordination number changes on intensities of the f-f transitions and the crystal field splitting of (2S+1)LJ multiplets are discussed. The weighted sum of molar absorption coefficients of f-f transitions in the spectra of and was used to reproduce the absorption bands of the Er(3+)-EDTA complex in aqueous solution. This approach allowed us to estimate that the complex in solution exists in 95% as the 8-coordinate [Er(EDTA)(H2O)2](-) species and in 5% as the 9-coordinate [Er(EDTA)(H2O)3](-) ones as well as to calculate the conditional hydration equilibrium constant (Kaqua) of the reaction: [Er(EDTA)(H2O)3](-) ↔ [Er(EDTA)(H2O)2](-) + H2O which is rather difficult to determine by using other methods. The Kaqua value was found to be 19 ± 1. PMID:25373563

  16. Recrystallized Impact Glasses of the Onaping Formation and the Sudbury Igneous Complex, Sudbury Structure, Ontario, Canada

    NASA Technical Reports Server (NTRS)

    Dressler, B. O.; Weiser, T.; Brockmeyer, P.

    1996-01-01

    The origin of the Sudbury Structure and of the associated heterolithic breccias of the Onaping Formation and the Sudbury Igneous Complex have been controversial. While an impact origin of the structure has gained wide acceptance over the last 15 years, the origin of the recrystallized Onaping Formation glasses and of the igneous complex is still being debated. Recently the interpretation of the breccias of the Onaping Formation as suevitic fall-back impact breccias has been challenged. The igneous complex is interpreted either as a differentiated impact melt sheet or as a combination of an upper impact melt represented by the granophyre, and a lower, impact-triggered magmatic body consisting of the norite-sublayer formations. The Onaping Formation contains glasses as fluidal and nonfluidal fragments of various shapes and sizes. They are recrystallized, and our research indicates that they are petrographically heterogeneous and span a wide range of chemical compositions. These characteristics are not known from glasses of volcanic deposits. This suggests an origin by shock vitrification, an interpretation consistent with their association with numerous and varied country rock clasts that exhibit microscopic shock metamorphic features. The recrystallized glass fragments represent individual solid-state and liquid-state vitrified rocks or relatively small melt pods. The basal member lies beneath the Gray and Black members of the Onaping Formation and, where not metamorphic, has an igneous matrix. Igneous-textured melt bodies occur in the upper two members and above the Basal Member. A comparison of the chemical compositions of recrystallized glasses and of the matrices of the Basal Member and the melt bodies with the components and the bulk composition of the igneous complex is inconclusive as to the origin of the igneous complex. Basal Member matrix and Melt Bodies, on average, are chemically similar to the granophyre of the Sudbury Igneous Complex, suggesting that they are genetically related. Our chemical results allow interpretation of the entire igneous complex as a differentiated impact melt. However, they are also consistent with the granophyre alone being the impact melt and the nofite and quartz gabbro beneath it representing an impact-triggered magmatic body. This interpretation is preferred, as it is consistent with a number of field observations. A re-evaluation and extension of structural field studies and of geochemical data, as well as a systematic study of the contact relationships of the various igneous phases of the igneous complex, are needed to establish a Sudbury impact model consistent with all data and observations

  17. Ternary complex formation of Eu(III) with o-phthalate in aqueous solutions

    NASA Astrophysics Data System (ADS)

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

    2009-08-01

    Ternary hydroxo complex formation of Eu(III) with o-phthalate was investigated by potentiometry and fluorescence spectrophotometry. Curves of the equilibrium pH versus the amount of NaOH added showed that the pH value starting to form a Eu(III) precipitate was decreased due to the formation of a ternary hydroxo complex, EuOHL(s) (L = phthalate). The formation of EuOHL(s) was qualitatively confirmed by the enhancement of the fluorescence intensity of Eu(III) in the precipitate with the light absorbed by phthalate, and was quantitatively confirmed by the measurement of the amounts of Eu(III), OH - and phthalate included in the precipitate. The solubility product of EuOHL(s) was determined as pKsp0=15.60.4. Characteristic features in the fluorescence spectra and the solubility product of the Eu(III)-phthalate complex were compared with those of the Eu(III)-PDA (PDA = pyridine-2,6-dicarboxylate) complex. The fluorescence intensity of the EuL + complex of L = PDA was about 11 times stronger than that of L = phthalate. The origin of the difference in the fluorescence intensity is discussed based on the intramolecular energy transfer effect from the lowest triplet energy level of the ligand to the resonance energy level of Eu(III).

  18. [Preparation, formation mechanism and preliminary evaluation of oral absorption of a Bicyclol-phospholipid complex].

    PubMed

    Li, Lin; Dong, Wu-Jun; Sheng, Li; Xia, Xue-Jun; Li, Yan; Liu, Yu-Ling

    2014-11-01

    Bicyclol with benzyl alcohol structure, is a poorly water-soluble drug, used for the treatment of chronic hepatitis B. To increase the drug solubility and oral bioavailability, a Bicyclol-phospholipid complex was studied on its preparation, formation mechanism, and the influence on drug physicochemical properties and oral absorption. The complex was prepared by a solvent evaporation method. The optimal formulation was selected by orthogonal experimental design, and a reasonable evaluating method of the complexation rate was established. Various methods, such as differential scanning calorimetry (DSC), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and 31P nuclear magnetic resonance (31P-NMR), were used to explore the phase state and formation mechanism of the complex. The solubility of drug in complex was investigated in water/n-octanol. Preliminary study of its absorption and liver tissue distribution in rats was also carried out. The results showed that Bicyclol and phosphatidylcholine can be complexed entirely in the molar ratio 1 : 2. Bicyclol was dispersed in phospholipids as amorphous state. They were combined by intermolecular hydrogen bond due to charge transfer effect which occurred between the two polarities of the double bond between phosphorus and oxygen (P=O) of phosphatidylcholine and benzalcohol group of Bicyclol. The solubility of the complex compared to the active pharmaceutical ingredient (API) was effectively enhanced 5.75 times in water and 7.72 times in n-octanol, separately. In addition, drug concentrations were also enhanced 43 times in plasma and 13 times in liver with one hour after administering the complex to rats via oral gavage. All of these indicated that Bicyclol with benzalcohol group can interact with phospholipids to form complex, improving drug's physicochemical properties, thus further increasing its absorption and target tissue distribution. This study also provided theoretical reference for the research of other benzalcohol derivatives complexed with phospholipids. PMID:25757289

  19. Enhanced CO2 hydrate formation kinetic under organo-mineral complex environment

    NASA Astrophysics Data System (ADS)

    Kyung, D.; Lee, W.

    2012-12-01

    CO2 hydrate formation under marine sediments can be one of the feasible options to mitigate atmospheric concentration of CO2, main source of global warming. For the better application of CO2 sequestration via hydrate form under ocean, it is indispensable to understand the effects of marine environmental factors on hydrate formation kinetic and equilibrium. In this study, we investigated the effect of organo-mineral complex (i.e., Na-montmorillonite (Na-MMT) and glycine complex) on hydrate formation kinetic both experimentally and computationally. Organo-mineral complex suspension showed much more favorable hydrate formation kinetic (2-6 min) than pure water control (48-80 min). TEM image showed that glycine are well distributed and strongly adsorbed on Na-MMT surface and FT/IR results (i.e., increased frequency of N-H stretch) also proved that amine part of glycine can make strong hydrogen bonding with silicon atoms of Na-MMT. Molecular dynamics (MD) simulation was performed to fully understand the CO2 hydrate nucleation on the organo-mineral complex and its result showed that high concentration of CO2 molecules are located near Na-MMT surface and glycine attached on Na-MMT can attract water molecules to form intermediate hydrate structure. This one plays a key role in complete hydrate formation as nucleation seeds and can significantly enhance the hydrate formation kinetic. This fundamental knowledge could provide idea to select proper CO2 storage site under marine sediments and be applied to in-situ swapping technology to recover CH4 from deep sea gas hydrate deposits and sequester the CO2 to CH4 hydrate layer.

  20. Gating of single molecule junction conductance by charge transfer complex formation

    NASA Astrophysics Data System (ADS)

    Vezzoli, Andrea; Grace, Iain; Brooke, Carly; Wang, Kun; Lambert, Colin J.; Xu, Bingqian; Nichols, Richard J.; Higgins, Simon J.

    2015-11-01

    The solid-state structures of organic charge transfer (CT) salts are critical in determining their mode of charge transport, and hence their unusual electrical properties, which range from semiconducting through metallic to superconducting. In contrast, using both theory and experiment, we show here that the conductance of metal |single molecule| metal junctions involving aromatic donor moieties (dialkylterthiophene, dialkylbenzene) increase by over an order of magnitude upon formation of charge transfer (CT) complexes with tetracyanoethylene (TCNE). This enhancement occurs because CT complex formation creates a new resonance in the transmission function, close to the metal contact Fermi energy, that is a signal of room-temperature quantum interference.The solid-state structures of organic charge transfer (CT) salts are critical in determining their mode of charge transport, and hence their unusual electrical properties, which range from semiconducting through metallic to superconducting. In contrast, using both theory and experiment, we show here that the conductance of metal |single molecule| metal junctions involving aromatic donor moieties (dialkylterthiophene, dialkylbenzene) increase by over an order of magnitude upon formation of charge transfer (CT) complexes with tetracyanoethylene (TCNE). This enhancement occurs because CT complex formation creates a new resonance in the transmission function, close to the metal contact Fermi energy, that is a signal of room-temperature quantum interference. Electronic supplementary information (ESI) available: Synthesis of 1c; experimental details of conductance measurements, formation of charge transfer complexes of 1c and 2 in solution; further details of theoretical methods. See DOI: 10.1039/c5nr04420k

  1. Standard thermodynamic functions of complex formation between Cu2+ and glycine in aqueous solution

    NASA Astrophysics Data System (ADS)

    Gorboletova, G. G.; Metlin, A. A.

    2013-05-01

    Heat effects of the interaction of copper(II) solutions with aminoacetic acid (glycine) are measured by the direct calorimetry at 298.15 K and ionic strengths of 0.5, 1.0, and 1.5 against a background of potassium nitrate. Standard enthalpy values for reactions of the formation of aminoacetic acid copper complexes in aqueous solutions are obtained using an equation with a single individual parameter by extrapolating it to zero ionic strength. The standard thermodynamic characteristics of complex formation in the Cu2+-glycine system are calculated. It is shown that glycine-like coordination is most likely in Cu(II) complexes with L-asparagine, L-glutamine, and L-valine.

  2. Geminin Inhibits a Late Step in the Formation of Human Pre-replicative Complexes*

    PubMed Central

    Wu, Min; Lu, Wenyan; Santos, Ruth E.; Frattini, Mark G.; Kelly, Thomas J.

    2014-01-01

    The initial step in initiation of eukaryotic DNA replication involves the assembly of pre-replicative complexes (pre-RCs) at origins of replication during the G1 phase of the cell cycle. In metazoans initiation is inhibited by the regulatory factor Geminin. We have purified the human pre-RC proteins, studied their interactions in vitro with each other and with origin DNA, and analyzed the effects of HsGeminin on formation of DNA-protein complexes. The formation of an initial complex containing the human origin recognition complex (HsORC), HsCdt1, HsCdc6, and origin DNA is cooperative, involving all possible binary interactions among the components. Maximal association of HsMCM27, a component of the replicative helicase, requires HsORC, HsCdc6, HsCdt1, and ATP, and is driven by interactions of HsCdt1 and HsCdc6 with multiple HsMCM27 subunits. Formation of stable complexes, resistant to high salt, requires ATP hydrolysis. In the absence of HsMCM proteins, HsGeminin inhibits the association of HsCdt1 with DNA or with HsORC-HsCdc6-DNA complexes. However, HsGeminin does not inhibit recruitment of HsMCM27 to DNA to form complexes containing all of the pre-RC proteins. In fact, HsGeminin itself is a component of such complexes, and interacts directly with the HsMcm3 and HsMcm5 subunits of HsMCM27, as well as with HsCdt1. Although HsGeminin does not prevent the initial formation of DNA-protein complexes containing the pre-RC proteins, it strongly inhibits the formation of stable pre-RCs that are resistant to high salt. We suggest that bound HsGeminin prevents transition of the pre-RC to a state that is competent for initiation of DNA replication. PMID:25231993

  3. The significance of ACTH for the process of formation of complex heparin compounds in the blood during immobilization stress

    NASA Technical Reports Server (NTRS)

    Kudryashov, B. A.; Shapiro, F. B.; Lomovskaya, F. B.; Lyapina, L. A.

    1979-01-01

    Adrenocorticotropin (ACTH) was administered to rats at different times following adrenalectomy. Adrenocorticotropin caused a significant increase in the formation of heparin complexes even in the absence of stress factor. When ACTH secretion is blocked, immobilization stress is not accompanied by an increase in the process of complex formation. The effect of ACTH on the formation of heparin complexes was mediated through its stimulation of the adrenal cortex.

  4. Lethal synergism between organic and inorganic wood preservatives via formation of an unusual lipophilic ternary complex

    SciTech Connect

    Sheng, Zhi-Guo; Li, Yan; Fan, Rui-Mei; Chao, Xi-Juan; Zhu, Ben-Zhan; Linus Pauling Institute, Oregon State University, Corvallis, OR 97331

    2013-02-01

    We have shown previously that exposing bacteria to wood preservatives pentachlorophenol (PCP) and copper-containing compounds together causes synergistic toxicity. However, it is not clear whether these findings also hold true in mammalian cells; and if so, what is the underlying molecular mechanism? Here we show that PCP and a model copper complex bis-(1,10-phenanthroline) cupric (Cu(OP){sub 2}), could also induce synergistic cytotoxicity in human liver cells. By the single crystal X-ray diffraction and atomic absorption spectroscopy assay, the synergism was found to be mainly due to the formation of a lipophilic ternary complex with unusual structural and composition characteristics and subsequent enhanced cellular copper uptake, which markedly promoted cellular reactive oxygen species (ROS) production, leading to apoptosis by decreasing mitochondrial membrane potential, increasing pro-apoptotic protein expression, releasing cytochrome c from mitochondria and activating caspase-3, and -9. Analogous results were observed with other polychlorinated phenols (PCPs) and Cu(OP){sub 2}. Synergistic cytotoxicity could be induced by PCP/Cu(OP){sub 2} via formation of an unusual lipophilic complex in HepG2 cells. The formation of ternary complexes with similar lipophilic character could be of relevance as a general mechanism of toxicity, which should be taken into consideration especially when evaluating the toxicity of environmental pollutants found at currently-considered non- or sub-toxic concentrations. -- Highlights: ► The combination of PCP/Cu(OP){sub 2} induces synergistic cytotoxicity in HepG2 cells. ► The synergism is mainly due to forming a lipophilic ternary complex between them. ► The formation of lipophilic ternary complex enhances cellular copper uptake. ► PCP/Cu(OP){sub 2} stimulates the cellular ROS production. ► The ROS promoted by PCP/Cu(OP){sub 2} induces mitochondria-dependent apoptosis.

  5. Notable effects of metal salts on UV-vis absorption spectra of ?-, ?-, ?-, and ?-tocopheroxyl radicals in acetonitrile solution. The complex formation between tocopheroxyls and metal cations.

    PubMed

    Mukai, Kazuo; Kohno, Yutaro; Ouchi, Aya; Nagaoka, Shin-ichi

    2012-08-01

    The measurements of the UV-vis absorption spectra of ?-, ?-, ?-, and ?-tocopheroxyl (?-, ?-, ?-, and ?-Toc()) radicals were performed by reacting aroxyl (ArO()) radical with ?-, ?-, ?-, and ?-tocopherol (?-, ?-, ?-, and ?-TocH), respectively, in acetonitrile solution including three kinds of alkali and alkaline earth metal salts (LiClO(4), NaClO(4), and Mg(ClO(4))(2)) (MX or MX(2)), using stopped-flow spectrophotometry. The maximum wavelengths (?(max)) of the absorption spectra of the ?-, ?-, ?-, and ?-Toc() located at 425-428 nm without metal salts increased with increasing concentrations of metal salts (0-0.500 M) in acetonitrile and approached some constant values, suggesting (Toc()M(+) (or M(2+))) complex formations. Similarly, the values of the apparent molar extinction coefficient (?(max)) increased drastically with increasing concentrations of metal salts in acetonitrile and approached some constant values. The result suggests that the formations of Toc() dimers were suppressed by the metal ion complex formations of Toc() radicals. The stability constants (K) were determined for Li(+), Na(+), and Mg(2+) complexes of ?-, ?-, ?-, and ?-Toc(). The K values increased in the order of NaClO(4) < LiClO(4) < Mg(ClO(4))(2), being independent of the kinds of Toc() radicals. Furthermore, the K values increased in the order of ?- < ?- < ?- < ?-Toc() radicals for each metal salt. The alkali and alkaline earth metal salts having a smaller ionic radius of the cation and a larger charge of the cation gave a larger shift of the ?(max) value, a larger ?(max) value, and a larger K value. The result of the DFT molecular orbital calculations indicated that the ?-, ?-, ?-, and ?-Toc() radicals were stabilized by the (1:1) complex formation with metal cations (Li(+), Na(+), and Mg(2+)). Stabilization energy (E(S)) due to the complex formation increased in the order of Na(+) < Li(+) < Mg(2+) complexes, being independent of the kinds of Toc() radicals. The calculated result also indicated that the metal cations coordinate to the O atom at the sixth position of ?-, ?-, ?-, and ?-Toc() radicals. PMID:22775471

  6. Improved complexation of paraquat derivatives by the formation of crown ether-based cryptands.

    PubMed

    Zhang, Mingming; Zhu, Kelong; Huang, Feihe

    2010-11-21

    Self-assembly allows the construction of advanced molecular or supramolecular systems from small building blocks. Host-guest recognition, for its self-selectivity, environmental responsiveness and convenient application to complex molecular devices, plays a significant role in self-assembled systems. During this process, the association constant between the host and guest is an important standard to identify the properties of the systems. In order to prepare mechanically interlocked structures and large supramolecular systems efficiently from small molecules based on a host-guest recognition motif, it is necessary to increase host-guest association constants. Crown ether-based cryptands have been designed and prepared to improve the binding of paraquat derivatives. This feature article aims to describe the design and syntheses of crown ether-based cryptand hosts for paraquat derivatives and the application of the cryptand/paraquat recognition motif in the fabrication of threaded structures, molecular switches and supramolecular polymers. PMID:20830438

  7. Complex formation with nucleic acids and aptamers alters the antigenic properties of platelet factor 4.

    PubMed

    Jaax, Miriam E; Krauel, Krystin; Marschall, Thomas; Brandt, Sven; Gansler, Julia; Frll, Birgitt; Appel, Bettina; Fischer, Silvia; Block, Stephan; Helm, Christiane A; Mller, Sabine; Preissner, Klaus T; Greinacher, Andreas

    2013-07-11

    The tight electrostatic binding of the chemokine platelet factor 4 (PF4) to polyanions induces heparin-induced thrombocytopenia, a prothrombotic adverse drug reaction caused by immunoglobulin G directed against PF4/polyanion complexes. This study demonstrates that nucleic acids, including aptamers, also bind to PF4 and enhance PF4 binding to platelets. Systematic assessment of RNA and DNA constructs, as well as 4 aptamers of different lengths and secondary structures, revealed that increasing length and double-stranded segments of nucleic acids augment complex formation with PF4, while single nucleotides or single-stranded polyA or polyC constructs do not. Aptamers were shown by circular dichroism spectroscopy to induce structural changes in PF4 that resemble those induced by heparin. Moreover, heparin-induced anti-human-PF4/heparin antibodies cross-reacted with human PF4/nucleic acid and PF4/aptamer complexes, as shown by an enzyme immunoassay and a functional platelet activation assay. Finally, administration of PF4/44mer-DNA protein C aptamer complexes in mice induced anti-PF4/aptamer antibodies, which cross-reacted with murine PF4/heparin complexes. These data indicate that the formation of anti-PF4/heparin antibodies in postoperative patients may be augmented by PF4/nucleic acid complexes. Moreover, administration of therapeutic aptamers has the potential to induce anti-PF4/polyanion antibodies and a prothrombotic diathesis. PMID:23673861

  8. Complex formation with nucleic acids and aptamers alters the antigenic properties of platelet factor 4

    PubMed Central

    Jaax, Miriam E.; Krauel, Krystin; Marschall, Thomas; Brandt, Sven; Gansler, Julia; Frll, Birgitt; Appel, Bettina; Fischer, Silvia; Block, Stephan; Helm, Christiane A.; Mller, Sabine; Preissner, Klaus T.

    2013-01-01

    The tight electrostatic binding of the chemokine platelet factor 4 (PF4) to polyanions induces heparin-induced thrombocytopenia, a prothrombotic adverse drug reaction caused by immunoglobulin G directed against PF4/polyanion complexes. This study demonstrates that nucleic acids, including aptamers, also bind to PF4 and enhance PF4 binding to platelets. Systematic assessment of RNA and DNA constructs, as well as 4 aptamers of different lengths and secondary structures, revealed that increasing length and double-stranded segments of nucleic acids augment complex formation with PF4, while single nucleotides or single-stranded polyA or polyC constructs do not. Aptamers were shown by circular dichroism spectroscopy to induce structural changes in PF4 that resemble those induced by heparin. Moreover, heparin-induced anti-humanPF4/heparin antibodies cross-reacted with human PF4/nucleic acid and PF4/aptamer complexes, as shown by an enzyme immunoassay and a functional platelet activation assay. Finally, administration of PF4/44merDNA protein C aptamer complexes in mice induced antiPF4/aptamer antibodies, which cross-reacted with murine PF4/heparin complexes. These data indicate that the formation of anti-PF4/heparin antibodies in postoperative patients may be augmented by PF4/nucleic acid complexes. Moreover, administration of therapeutic aptamers has the potential to induce anti-PF4/polyanion antibodies and a prothrombotic diathesis. PMID:23673861

  9. PHOSPHOLIPIDS ARE NEEDED FOR PROPER FORMATION, STABILITY AND FUNCTION OF THE PHOTOACTIVATED RHODOPSIN-TRANSDUCIN COMPLEX

    PubMed Central

    Jastrzebska, Beata; Goc, Anna; Golczak, Marcin; Palczewski, Krzysztof

    2009-01-01

    Heterotrimeric G proteins become activated after they form a catalytically active complex with activated G protein-coupled receptors (GPCRs) and GTP replaces GDP on the G protein α subunit. This transient coupling can be stabilized by nucleotide depletion, resulting in an empty-nucleotide G-protein-GPCR complex. Efficient and reproducible formation of conformationally homogenous GPCR-Gt complexes is a prerequisite for structural studies. Herein, we report isolation conditions that enhance the stability, and preserve activity and proper stoichiometry of productive complexes between the purified prototypical GPCR, rhodopsin (Rho), and the rod cell-specific G protein, transducin (Gt). Binding of purified Gt to photoactivated Rho (Rho*) in n-dodecyl-β-maltoside (DDM) examined by gel filtration chromatography was generally modest and purified complexes provided heterogeneous ratios of protein components, most likely because of excess detergent. Rho*-Gt complex stability and activity was greatly increased by addition of phospholipids such as DOPC, DOPE and DOPS, and asolectin to detergent-containing solutions of these proteins. In contrast, native Rho*-Gt complexes purified directly from light-exposed bovine ROS membranes by sucrose gradient centrifugation exhibited improved stability and the expected 2:1 stoichiometry between Rho* and Gt. The above results strongly indicate a lipid requirement for stable complex formation wherein the likely oligomeric structure of Rho provides a superior platform for coupling to Gt, and phospholipids likely form a matrix to which Gt can anchor through its myristoyl and farnesyl groups. Our findings also demonstrate that the choice of detergent and purification method is critical for obtaining highly purified, stable, and active complexes with appropriate stoichiometry between GPCRs and G proteins needed for structural studies. PMID:19413332

  10. Functional insight into the role of Orc6 in septin complex filament formation in Drosophila.

    PubMed

    Akhmetova, Katarina; Balasov, Maxim; Huijbregts, Richard P H; Chesnokov, Igor

    2015-01-01

    Septins belong to a family of polymerizing GTP-binding proteins that are important for cytokinesis and other processes that involve spatial organization of the cell cortex. We reconstituted a recombinant Drosophila septin complex and compared activities of the wild-type and several mutant septin complex variants both in vitro and in vivo. We show that Drosophila septin complex functions depend on the intact GTP-binding and/or hydrolysis domains of Pnut, Sep1, and Sep2. The presence of the functional C-terminal domain of septins is required for the integrity of the complex. Drosophila Orc6 protein, the smallest subunit of the origin recognition complex (ORC), directly binds to septin complex and facilitates septin filament formation. Orc6 forms dimers through the interactions of its N-terminal, TFIIB-like domains. This ability of the protein suggests a direct bridging role for Orc6 in stimulating septin polymerization in Drosophila. Studies reported here provide a functional dissection of a Drosophila septin complex and highlight the basic conserved and divergent features among metazoan septin complexes. PMID:25355953

  11. Complex coacervates obtained from peptide leucine and gum arabic: formation and characterization.

    PubMed

    Gulão, Eliana da S; de Souza, Clitor J F; Andrade, Cristina T; Garcia-Rojas, Edwin E

    2016-03-01

    In this study, interactions between polypeptide-leucine (0.2% w/w) and gum arabic (0.03, 0.06, 0.09, 0.12, and 0.15% w/w) were examined at concentrations of NaCl (0, 0.01, 0.25, 0.3, 0.5mol/l) and at different pH values (from 1.0 to 12.0). Formation of insoluble complex coacervates was highest at pH 4.0. At pH 2.0, which is the pKa of the gum Arabic, the dissociation of precipitate occurred. The pHØ2 positively shifted with the addition of higher concentrations of salt. Samples containing 0.2% PL and 0.03% GA and no salt had higher turbidity and increased formation of precipitates showing greater turbidity and particle sizes. The Fourier transform infrared spectroscopy confirms the complex coacervate formation of leucine and gum arabic, and rheological measurements suggest the elastic behavior of 0.2% PL and 0.03% GA complex. Overall, the study suggests that complex coacervates of PLs could be one feasible ways of incorporating amino acids in food products. PMID:26471607

  12. The influence of amylose-LPC complex formation on the susceptibility of wheat starch to amylase.

    PubMed

    Ahmadi-Abhari, S; Woortman, A J J; Oudhuis, A A C M; Hamer, R J; Loos, K

    2013-09-12

    This study was aimed to assess the role of lysophosphatidylcholine (LPC) in the development of slowly digestible starch (SDS). The influence of LPC, on the enzymatic degradation of diluted 9% wheat starch suspensions (w/w) was investigated, using an in vitro digestion method. Wheat starch suspensions containing 0.5-5% LPC (based on starch) were heated in a Rapid Visco Analyser (RVA) till 95 C and subjected to enzyme hydrolysis by porcine pancreatic ?-amylase at 37 C for several digestion periods. In vitro digestion measurements demonstrated that complexing starch with 5% LPC leads to a 22% decrease in rate of reducing sugar compared to the reference while the samples containing 0.5% LPC showed an equal digestibility comparable to the control. A clear decrease in the formation of reducing sugars was observed in presence of 2-5% LPC, since the results after 15 min digestion imply the formation of SDS due to the formation of amylose-LPC inclusion complexes. The DSC measurements proved the presence of amylose-LPC inclusion complexes even after 240 min digestion demonstrating the low susceptibility of amylose-V complexes to amylase. PMID:23911468

  13. Regulated Clearance of Histone Deacetylase 3 Protects Independent Formation of Nuclear Receptor Corepressor Complexes*

    PubMed Central

    Guo, Chun; Gow, Chien-Hung; Li, Yali; Gardner, Amanda; Khan, Sohaib; Zhang, Jinsong

    2012-01-01

    An important step in transcriptional regulation by corepressors N-CoR and SMRT is the formation of a stable and active histone deacetylase 3 (HDAC3)-containing complex. Although N-CoR and SMRT are thought to bind HDAC3 competitively, multiple studies have shown that they do not interfere with the function of each other. How this functional independence is sustained under the competitive interaction is unclear. Here, we show that the coupling of corepressor expression with HDAC3 degradation allows cells to maintain a stable level of uncomplexed HDAC3, thereby preventing mutual interference in the assembly of N-CoR and SMRT complexes. The free uncomplexed HDAC3 is highly unstable. Unexpectedly, the rate of HDAC3 degradation is inversely correlated with the expression level of corepressors. Our results indicate that reducing one corepressor accelerates HDAC3 clearance, thus preventing an increase in complex formation between HDAC3 and the other corepressor. In addition, this study also indicates that the formation of a stable and active HDAC3-corepressor complex is a stepwise process in which the C terminus of HDAC3 plays a critical role at late steps of the assembly process. PMID:22337871

  14. Reversible Formation and Transmetalation of Schiff-Base Complexes in Subcomponent Self-Assembly Reactions.

    PubMed

    Lewing, Dennis; Koppetz, Hannah; Hahn, F Ekkehardt

    2015-08-01

    Dinuclear complexes [Zn2(NS,NS)2] 3 and [Ni2(NS,NS)2] 6 bearing Schiff-base ligands featuring two NS donor groups were obtained in subcomponent self-assembly reactions using nickel or zinc as template metals. Several transmetalation reactions starting from 3 or 6 yielded the complexes [Pd2(NS,NS)2] 4 and [Co2(NS,NS)2] 5, and their molecular structures were determined by X-ray diffraction. Starting from the mononuclear complex [Ni(NS/NOH)2] 9 featuring a coordinated NS Schiff base and a free NOH Schiff base, completely reversible thermodynamically controlled imine bond formation was observed leading to complex [Ni2(NS,NS)2] 6 and the free Schiff -base ligand NOH,NOH 10. PMID:26161894

  15. QSPR ensemble modelling of the 1:1 and 1:2 complexation of Co?, Ni?, and Cu? with organic ligands: relationships between stability constants.

    PubMed

    Solov'ev, Vitaly; Varnek, Alexandre; Tsivadze, Aslan

    2014-05-01

    Quantitative structure-property relationship (QSPR) modeling of stability constants for the metal:ligand ratio 1:1 (logK) and 1:2 (log?2) complexes of 3 transition metal ions with diverse organic ligands in aqueous solution was performed using ensemble multiple linear regression analysis and substructural molecular fragment descriptors. The modeling was performed on the sets containing 396 and 132 (Co(2+)), 613 and 233 (Ni(2+)), 883 and 257 (Cu(2+)) logK and log? 2 values, respectively. The models have been validated in external fivefold cross-validations procedure as well as on the external test set containing new ligands recently reported in the literature. Predicted logK and log? 2 values were calculated as arithmetic means of several hundred individual models (consensus models) using their applicability domains in averaging. The root mean squared error of predictions varies from 0.94 to 1.2 (logK) and from 1.2 to 1.4 (log?2) which is close to observed experimental systematic errors. Linear correlations between experimental logK values for pair of metal ions were evaluated. For all metal ions and ligands forming both 1:1 and 1:2 complexes the following ratio is observed: log?2/logK = 1.8 0.1, n = 492. PMID:24737030

  16. Complex pattern formation of marine gradient bacteria explained by a simple computer model.

    PubMed

    Thar, Roland; Khl, Michael

    2005-05-01

    We report on the formation of conspicuous patterns by the sulfide-oxidizing bacterium Thiovulum majus and a recently described vibrioid bacterium. These microaerophilic bacteria form mucus veils on top of sulfidic marine sediment exhibiting regular spaced bacterial patterns (honeycombs, interwoven bands, or inverse honeycombs). A simple qualitative computer model, based on chemotaxis towards oxygen and the ability of the bacteria to induce water advection when attached, can explain the formation of the observed patterns. Our study shows that complex bacterial patterns in nature can be explained in terms of chemotaxis and resource optimisation without involvement of cell-cell signalling or social behavior amongst bacteria. PMID:15869964

  17. Formation of multiple focal spots using a high NA lens with a complex spiral phase mask

    NASA Astrophysics Data System (ADS)

    Lalithambigai, K.; Anbarasan, P. M.; Rajesh, K. B.

    2014-07-01

    The formation of a transversally polarized beam by transmitting a tightly focused double-ring-shaped azimuthally polarized beam through a complex spiral phase mask and high numerical aperture lens is presented based on vector diffraction theory. The generation of transversally polarized focal spot segment splitting and multiple focal spots is illustrated numerically. Moreover, we found that a properly designed complex spiral phase mask can move the focal spots along the optical axis in the z direction. Therefore, one can achieve a focal segment of two, three or multiple completely transversely polarized focal spots, which finds applications in optical trapping and in material processing technologies.

  18. Multinuclear complex formation between Ca(II) and gluconate ions in hyperalkaline solutions.

    PubMed

    Pallagi, Attila; Bajnczi, va G; Canton, Sophie E; Bolin, Trudy; Peintler, Gbor; Kutus, Bence; Kele, Zoltn; Plink, Istvn; Sipos, Pl

    2014-06-17

    Alkaline solutions containing polyhydroxy carboxylates and Ca(II) are typical in cementitious radioactive waste repositories. Gluconate (Gluc(-)) is a structural and functional representative of these sugar carboxylates. In the current study, the structure and equilibria of complexes forming in such strongly alkaline solutions containing Ca(2+) and gluconate have been studied. It was found that Gluc(-) significantly increases the solubility of portlandite (Ca(OH)2(s)) under these conditions and Ca(2+) complexes of unexpectedly high stability are formed. The mononuclear (CaGluc(+) and [CaGlucOH](0)) complexes were found to be minor species, and predominant multinuclear complexes were identified. The formation of the neutral [Ca2Gluc(OH)3](0) (log ?213 = 8.03) and [Ca3Gluc2(OH)4](0) (log ?324 = 12.39) has been proven via H2/Pt-electrode potentiometric measurements and was confirmed via XAS, (1)H NMR, ESI-MS, conductometry, and freezing-point depression experiments. The binding sites of Gluc(-) were identified from multinuclear NMR measurements. Besides the carboxylate group, the O atoms on the second and third carbon atoms were proved to be the most probable sites for Ca(2+) binding. The suggested structure of the trinuclear complex was deduced from ab initio calculations. These observations are of relevance in the thermodynamic modeling of radioactive waste repositories, where the predominance of the binuclear Ca(2+) complex, which is a precursor of various high-stability ternary complexes with actinides, is demonstrated. PMID:24865662

  19. Formation of very stable and selective Cu(II) complexes with a non-macrocyclic ligand: can basicity rival pre-organization?

    PubMed

    Abada, Sabah; Lecointre, Alexandre; Elhabiri, Mourad; Charbonnire, Loc J

    2010-10-14

    The synthesis of ligand L based on a 2,6-bis[(N,N-bis(methylene phosphonic acid)aminomethyl] pyridine scaffold is described. Potentiometry combined with UV-Vis absorption spectrophotometric titrations were used to determine the protonation constants of the ligand and the stability constants of its corresponding Cu(II), Ni(II), Zn(II) and Ga(III) cations (0.1 M NaClO(4), 25.0 C). The physico-chemical approach revealed very large stability constants for Cu(II) complexation (logK(CuL) = 22.71(7)) reflected in a very high pCu(II) value of ? 15.5 (pH = 7.4, [L](tot) = 10(-5) M, [Cu](tot) = 10(-6) M), close to those measured for the strong methylphosphonate functionalized cyclen chelators. Based on a literature survey, a correlation is proposed between the pK values of branched polyamine ligands and their stability constants for Cu(II) complexation, allowing for an estimation of the latter on the basis of the protonation constants of L. Ligand L was also shown to be very selective towards Cu(II) compared to the other cations studied (?logK > 4). UV-Vis spectroscopy and kinetic measurements indicated that the formation of the cupric complexes with L is very fast, which, in combination with all other properties, makes it an excellent non-cyclic target for Cu(II) radiopharmaceutical within the frame of (64)Cu positron emission tomography imaging and radiotherapy. PMID:20725674

  20. Formation of geometrically complex lipid nanotube-vesicle networks of higher-order topologies.

    PubMed

    Karlsson, Mattias; Sott, Kristin; Davidson, Maximillian; Cans, Ann-Sofie; Linderholm, Pontus; Chiu, Daniel; Orwar, Owe

    2002-09-01

    We present a microelectrofusion method for construction of fluid-state lipid bilayer networks of high geometrical complexity up to fully connected networks with genus = 3 topology. Within networks, self-organizing branching nanotube architectures could be produced where intersections spontaneously arrange themselves into three-way junctions with an angle of 120 degrees between each nanotube. Formation of branching nanotube networks appears to follow a minimum-bending energy algorithm that solves for pathway minimization. It is also demonstrated that materials can be injected into specific containers within a network by nanotube-mediated transport of satellite vesicles having defined contents. Using a combination of microelectrofusion, spontaneous nanotube pattern formation, and satellite-vesicle injection, complex networks of containers and nanotubes can be produced for a range of applications in, for example, nanofluidics and artificial cell design. In addition, this electrofusion method allows integration of biological cells into lipid nanotube-vesicle networks. PMID:12185244

  1. Green synthesis of ZnO nanoparticles via complex formation by using Curcuma longa extract

    NASA Astrophysics Data System (ADS)

    Fatimah, Is; Yudha, Septian P.; Mutiara, Nur Afisa Lintang

    2016-02-01

    Synthesis of ZnO nanoparticles(NPs) were conducted via Zn(II) complex formation by using Curcuma longa extract as template. Curcuma longa extract has the ability to form zinc ions complex with curcumin as ligating agent. Study on synthesis was conducted by monitoring thermal degradation of the material. Successful formation of zinc oxide nanoparticles was confirmed by employing x-ray diffraction, surface area analysis and transmission electron microscopy(TEM) studies. From the XRD analysis it is denoted that ZnO in hexagonal wurtzite phase was formed and particle size was varied as varied temperature. The data are also confirmed by TEM analysis which shows the particle sie at the range 20-80nm. The NPs exhibited excelent photocatalytic activity for methylene blue degradation and also significant antibacterial activity for Eschericia coli. The activity in methylene blue degradation was also confirmed from fast chemical oxygen demand (COD) reduction.

  2. Formation of complexes between PAMAM-NH2 G4 dendrimer and L-?-tryptophan and L-?-tyrosine in water

    NASA Astrophysics Data System (ADS)

    Buczkowski, Adam; Urbaniak, Pawel; Belica, Sylwia; Sekowski, Szymon; Bryszewska, Maria; Palecz, Bartlomiej

    2014-07-01

    Interactions between electromagnetic radiation and the side substituents of aromatic amino acids are widely used in the biochemical studies on proteins and their interactions with ligand molecules. That is why the aim of our study was to characterize the formation of complexes between PAMAM-NH2 G4 dendrimer and L-?-tryptophan and L-?-tyrosine in water. The number of L-?-tryptophan and L-?-tyrosine molecules attached to the macromolecule of PAMAM-NH2 G4 dendrimer and the formation constants of the supramolecular complexes formed have been determined. The macromolecule of PAMAM-NH2 G4 can reversibly attach about 25 L-?-tryptophan molecules with equilibrium constant K equal to 130 30 and 24 6 L-?-tyrosine molecules. This characterization was deduced on the basis of the solubility measurements of the amino acids in aqueous dendrimer solutions, the 1H NMR and 2D-NOESY measurements of the dendrimer solutions with the amino acids, the equilibrium dialysis and the circular dichroism measurements of the dendrimer aqueous solutions with L-?-tryptophan. Our date confirmed the interactions of L-?-tryptophan and L-?-tyrosine with the dendrimer in aqueous solution and indicated a reversible character of the formed complexes.

  3. Electron Bihole Complex Formation in Neutralization of Ne{sup +} on LiF(001)

    SciTech Connect

    Khemliche, H.; Villette, J.; Borisov, A. G.; Momeni, A.; Roncin, P.

    2001-06-18

    Neutralization of low keV Ne{sup +} ions at a LiF(001) surface is studied in a grazing incidence geometry. The combination of energy loss and electron spectroscopy in coincidence reveals two neutralization channels of comparable importance. Besides the Auger process, the Ne{sup +} neutralization can proceed via peculiar target excitation, corresponding to the formation of an electron bihole complex termed trion.

  4. The LINC complex component Sun4 plays a crucial role in sperm head formation and fertility

    PubMed Central

    Pasch, Elisabeth; Link, Jana; Beck, Carolin; Scheuerle, Stefanie; Alsheimer, Manfred

    2015-01-01

    ABSTRACT LINC complexes are evolutionarily conserved nuclear envelope bridges, physically connecting the nucleus to the peripheral cytoskeleton. They are pivotal for dynamic cellular and developmental processes, like nuclear migration, anchoring and positioning, meiotic chromosome movements and maintenance of cell polarity and nuclear shape. Active nuclear reshaping is a hallmark of mammalian sperm development and, by transducing cytoskeletal forces to the nuclear envelope, LINC complexes could be vital for sperm head formation as well. We here analyzed in detail the behavior and function of Sun4, a bona fide testis-specific LINC component. We demonstrate that Sun4 is solely expressed in spermatids and there localizes to the posterior nuclear envelope, likely interacting with Sun3/Nesprin1 LINC components. Our study revealed that Sun4 deficiency severely impacts the nucleocytoplasmic junction, leads to mislocalization of other LINC components and interferes with the formation of the microtubule manchette, which finally culminates in a globozoospermia-like phenotype. Together, our study provides direct evidence for a critical role of LINC complexes in mammalian sperm head formation and male fertility. PMID:26621829

  5. The cytoprotective effect of nitrite is based on the formation of dinitrosyl iron complexes.

    PubMed

    Dungel, Peter; Perlinger, Martin; Weidinger, Adelheid; Redl, Heinz; Kozlov, Andrey V

    2015-12-01

    Nitrite protects various organs from ischemia-reperfusion injury by ameliorating mitochondrial dysfunction. Here we provide evidence that this protection is due to the inhibition of iron-mediated oxidative reactions caused by the release of iron ions upon hypoxia. We show in a model of isolated rat liver mitochondria that upon hypoxia, mitochondria reduce nitrite to nitric oxide (NO) in amounts sufficient to inactivate redox-active iron ions by formation of inactive dinitrosyl iron complexes (DNIC). The scavenging of iron ions in turn prevents the oxidative modification of the outer mitochondrial membrane and the release of cytochrome c during reoxygenation. This action of nitrite protects mitochondrial function. The formation of DNIC with nitrite-derived NO could also be confirmed in an ischemia-reperfusion model in liver tissue. Our data suggest that the formation of DNIC is a key mechanism of nitrite-mediated cytoprotection. PMID:26415027

  6. Display format and highlight validity effects on search performance using complex visual displays

    NASA Technical Reports Server (NTRS)

    Donner, Kimberly A.; Mckay, Tim; O'Brien, Kevin M.; Rudisill, Marianne

    1991-01-01

    Display format and highlight validity were shown to affect visual display search performance; however, these studies were conducted on small, artificial displays of alphanumeric stimuli. A study manipulating these variables was conducted using realistic, complex Space Shuttle information displays. A 2x2x3 within-subjects analysis of variance found that search times were faster for items in reformatted displays than for current displays. The significant format by highlight validity interaction showed that there was little difference in response time to both current and reformatted displays when the highlight validity was applied; however, under the non or invalid highlight conditions, search times were faster with reformatted displays. Benefits of highlighting and reformatting displays to enhance search and the necessity to consider highlight validity and format characteristics in tandem for predicting search performance are discussed.

  7. Involvement of DPP-IV Catalytic Residues in Enzyme-Saxagliptin Complex Formation

    SciTech Connect

    Metzler,W.; Yanchunas, J.; Weigelt, C.; Kish, K.; Klei, H.; Xie, D.; Zhang, Y.; Corbett, M.; Tamura, J.; et al

    2008-01-01

    The inhibition of DPP-IV by saxagliptin has been proposed to occur through formation of a covalent but reversible complex. To evaluate further the mechanism of inhibition, we determined the X-ray crystal structure of the DPP-IV:saxagliptin complex. This structure reveals covalent attachment between S630 and the inhibitor nitrile carbon (C-O distance <1.3 Angstroms). To investigate whether this serine addition is assisted by the catalytic His-Asp dyad, we generated two mutants of DPP-IV, S630A and H740Q, and assayed them for ability to bind inhibitor. DPP-IVH740Q bound saxagliptin with an {approx}1000-fold reduction in affinity relative to DPP-IVWT, while DPP-IVS630A showed no evidence for binding inhibitor. An analog of saxagliptin lacking the nitrile group showed unchanged binding properties to the both mutant proteins, highlighting the essential role S630 and H740 play in covalent bond formation between S630 and saxagliptin. Further supporting mechanism-based inhibition by saxagliptin, NMR spectra of enzyme-saxagliptin complexes revealed the presence of three downfield resonances with low fractionation factors characteristic of short and strong hydrogen bonds (SSHB). Comparison of the NMR spectra of various wild-type and mutant DPP-IV:ligand complexes enabled assignment of a resonance at {approx}14 ppm to H740. Two additional DPP-IV mutants, Y547F and Y547Q, generated to probe potential stabilization of the enzyme-inhibitor complex by this residue, did not show any differences in inhibitor binding either by ITC or NMR. Together with the previously published enzymatic data, the structural and binding data presented here strongly support a histidine-assisted covalent bond formation between S630 hydroxyl oxygen and the nitrile group of saxagliptin.

  8. Formylglycinamide Ribonucleotide Amidotransferase from Thermotoga maritima: Structural Insights into Complex Formation

    SciTech Connect

    Morar, Mariya; Hoskins, Aaron A.; Stubbe, JoAnne; Ealick, Steven E.

    2008-10-02

    In the fourth step of the purine biosynthetic pathway, formyl glycinamide ribonucleotide (FGAR) amidotransferase, also known as PurL, catalyzes the conversion of FGAR, ATP, and glutamine to formyl glycinamidine ribonucleotide (FGAM), ADP, P{sub i}, and glutamate. Two forms of PurL have been characterized, large and small. Large PurL, present in most Gram-negative bacteria and eukaryotes, consists of a single polypeptide chain and contains three major domains: the N-terminal domain, the FGAM synthetase domain, and the glutaminase domain, with a putative ammonia channel located between the active sites of the latter two. Small PurL, present in Gram-positive bacteria and archaea, is structurally homologous to the FGAM synthetase domain of large PurL, and forms a complex with two additional gene products, PurQ and PurS. The structure of the PurS dimer is homologous with the N-terminal domain of large PurL, while PurQ, whose structure has not been reported, contains the glutaminase activity. In Bacillus subtilis, the formation of the PurLQS complex is dependent on glutamine and ADP and has been demonstrated by size-exclusion chromatography. In this work, a structure of the PurLQS complex from Thermotoga maritima is described revealing a 2:1:1 stoichiometry of PurS:Q:L, respectively. The conformational changes observed in TmPurL upon complex formation elucidate the mechanism of metabolite-mediated recruitment of PurQ and PurS. The flexibility of the PurS dimer is proposed to play a role in the activation of the complex and the formation of the ammonia channel. A potential path for the ammonia channel is identified.

  9. Predicting permeability from the characteristic relaxation time and intrinsic formation factor of complex conductivity spectra

    NASA Astrophysics Data System (ADS)

    Revil, A.; Binley, A.; Mejus, L.; Kessouri, P.

    2015-08-01

    Low-frequency quadrature conductivity spectra of siliclastic materials exhibit typically a characteristic relaxation time, which either corresponds to the peak frequency of the phase or the quadrature conductivity or a typical corner frequency, at which the quadrature conductivity starts to decrease rapidly toward lower frequencies. This characteristic relaxation time can be combined with the (intrinsic) formation factor and a diffusion coefficient to predict the permeability to flow of porous materials at saturation. The intrinsic formation factor can either be determined at several salinities using an electrical conductivity model or at a single salinity using a relationship between the surface and quadrature conductivities. The diffusion coefficient entering into the relationship between the permeability, the characteristic relaxation time, and the formation factor takes only two distinct values for isothermal conditions. For pure silica, the diffusion coefficient of cations, like sodium or potassium, in the Stern layer is equal to the diffusion coefficient of these ions in the bulk pore water, indicating weak sorption of these couterions. For clayey materials and clean sands and sandstones whose surface have been exposed to alumina (possibly iron), the diffusion coefficient of the cations in the Stern layer appears to be 350 times smaller than the diffusion coefficient of the same cations in the pore water. These values are consistent with the values of the ionic mobilities used to determine the amplitude of the low and high-frequency quadrature conductivities and surface conductivity. The database used to test the model comprises a total of 202 samples. Our analysis reveals that permeability prediction with the proposed model is usually within an order of magnitude from the measured value above 0.1 mD. We also discuss the relationship between the different time constants that have been considered in previous works as characteristic relaxation time, including the mean relaxation time obtained from a Debye decomposition of the spectra and the Cole-Cole time constant.

  10. Chelate effect and thermodynamics of metal complex formation in solution: a quantum chemical study.

    PubMed

    Vallet, Valrie; Wahlgren, Ulf; Grenthe, Ingmar

    2003-12-01

    The accuracy of quantum chemical predictions of structures and thermodynamic data for metal complexes depends both on the quantum chemical methods and the chemical models used. A thermodynamic analogue of the Eigen-Wilkins mechanism for ligand substitution reactions (Model A) turns out to be sufficiently simple to catch the essential chemistry of complex formation reactions and allows quantum chemical calculations at the ab initio level of thermodynamic quantities both in gas phase and solution; the latter by using the conductor-like polarizable continuum (CPCM) model. Model A describes the complex formation as a two-step reaction: 1. [M(H2O)x](aq) + L(aq) <==>[M(H2O)x], L(aq); 2. [M(H2O)x], L(aq) <==>[M(H2O)(x-1)L],(H2O)(aq). The first step, the formation of an outer-sphere complex is described using the Fuoss equation and the second, the intramolecular exchange between an entering ligand from the second and water in the first coordination shell, using quantum chemical methods. The thermodynamic quantities for this model were compared to those for the reaction: [M(H2O)x](aq) + L(aq) <==>[M(H2O)(x-1)L](aq) + (H2O)(aq) (Model B), as calculated for each reactant and product separately. The models were tested using complex formation between Zn(2+) and ammonia, methylamine, and ethylenediamine, and complex formation and chelate ring closure reactions in binary and ternary UO(2)(2+)-oxalate systems. The results show that the Gibbs energy of reaction for Model A are not strongly dependent on the number of water ligands and the structure of the second coordination sphere; it provides a much more precise estimate of the thermodynamics of complex formation reactions in solution than that obtained from Model B. The agreement between the experimental and calculated data for the formation of Zn(NH(3))(2+)(aq) and Zn(NH(3))(2)(2+)(aq) is better than 8 kJ/mol for the former, as compared to 30 kJ/mol or larger, for the latter. The Gibbs energy of reaction obtained for the UO(2)(2+) oxalate systems using model B differs between 80 and 130 kJ/mol from the experimental results, whereas the agreement with Model A is better. The errors in the quantum chemical estimates of the entropy and enthalpy of reaction are somewhat larger than those for the Gibbs energy, but still in fair agreement with experiments; adding water molecules in the second coordination sphere improves the agreement significantly. Reasons for the different performance of the two models are discussed. The quantum chemical data were used to discuss the microscopic basis of experimental enthalpy and entropy data, to determine the enthalpy and entropy contributions in chelate ring closure reactions and to discuss the origin of the so-called "chelate effect". Contrary to many earlier suggestions, this is not even in the gas phase, a result of changes in translation entropy contributions. There is no simple explanation of the high stability of chelate complexes; it is a result of both enthalpy and entropy contributions that vary from one system to the other. PMID:14640672

  11. Aggregate formation by ERp57-deficient MHC class I peptide-loading complexes.

    PubMed

    Stepensky, David; Bangia, Naveen; Cresswell, Peter

    2007-11-01

    The endoplasmic reticulum (ER)-resident proteins TAP, tapasin and ERp57 are the core components of the major histocompatibility complex (MHC) class I peptide-loading complex and play an important role in peptide loading by MHC class I-beta(2)microglobulin dimers. ERp57 and tapasin form a stable disulfide-linked heterodimer within the peptide-loading complex. We demonstrate that ERp57-deficient loading complexes, obtained by expression in a tapasin-negative cell line of a tapasin mutant (C95A) that is not able to form a disulfide bond with ERp57, are prone to aggregation. We studied the assembly, stability and aggregation of the core loading complex using cell lines stably expressing fluorescently tagged tapasin (wild type or C95A mutant) and TAP1. Part of the loading complexes containing the tagged C95A tapasin and TAP1 were sequestered in the ER, without change of their ER transmembrane topology, and were surrounded by a mesh of filaments at the cytosolic side, resulting in formation of protein aggregates with characteristic morphology. Protein aggregates were associated with changes in ER protein turnover but did not affect the cell viability and did not induce the unfolded protein response. Fluorescence resonance energy transfer analysis of the aggregate-free ER fraction revealed that lack of ERp57 did not affect the stoichiometry or stability of tapasin-TAP1 interactions in the assembled 'soluble' core loading complexes. We conclude that the presence of ERp57 is important for the stability of core loading complexes, and that in its absence, the core loading complexes may form stable aggregates within the ER. PMID:17822402

  12. Modifications of the acyl-d-alanyl-d-alanine terminus affecting complex-formation with vancomycin

    PubMed Central

    Nieto, M.; Perkins, H. R.

    1971-01-01

    Vancomycin forms complexes with peptides terminating in d-alanyl-d-alanine that are analogous to the biosynthetic precursors of bacterial mucopeptides. The specificity of complex-formation has been studied by means of many synthetic peptides, prepared by both solid-phase and conventional methods. The following conclusions can be drawn: (a) three amide linkages are required to form a stable complex; (b) the terminal carboxyl group must be free; (c) the carboxyl terminal and subterminal residues must be either glycine or of the d-configuration; (d) the size of the side chain in these residues greatly influences the affinity for vancomycin, a methyl group being the optimum in each case; (e) the nature of the side chain in the third and fourth residues has a smaller effect on complex-formation, but an l-configuration was somewhat better than a d-configuration in the third position. In addition to acyl-d-alanyl-d-alanine, other peptides that occur in bacterial cell walls will combine with vancomycin, although less strongly, e.g. acyl-d-alanyl-d-?-amino acid (where the terminal d-residue may form the cross-link in mucopeptide structure) and acyl-l-alanyl-d-glutamylglycine (a sequence found in the mucopeptide of Micrococcus lysodeikticus and related organisms). These results throw some light on the specificity of the uptake of vancomycin by living bacteria. PMID:5124386

  13. The SWI/SNF chromatin remodeling complex regulates germinal center formation by repressing Blimp-1 expression.

    PubMed

    Choi, Jinwook; Jeon, Shin; Choi, Seungjin; Park, Kyungsoo; Seong, Rho Hyun

    2015-02-17

    Germinal center (GC) reaction is crucial in adaptive immune responses. The formation of GC is coordinated by the expression of specific genes including Blimp-1 and Bcl-6. Although gene expression is critically influenced by the status of chromatin structure, little is known about the role of chromatin remodeling factors for regulation of GC formation. Here, we show that the SWI/SNF chromatin remodeling complex is required for GC reactions. Mice lacking Srg3/mBaf155, a core component of the SWI/SNF complex, showed impaired differentiation of GC B and follicular helper T cells in response to T cell-dependent antigen challenge. The SWI/SNF complex regulates chromatin structure at the Blimp-1 locus and represses its expression by interacting cooperatively with Bcl-6 and corepressors. The defect in GC reactions in mice lacking Srg3 was due to the derepression of Blimp-1 as supported by genetic studies with Blimp-1-ablated mice. Hence, our study identifies the SWI/SNF complex as a key mediator in GC reactions by modulating Bcl-6-dependent Blimp-1 repression. PMID:25646472

  14. The SWI/SNF chromatin remodeling complex regulates germinal center formation by repressing Blimp-1 expression

    PubMed Central

    Choi, Jinwook; Jeon, Shin; Choi, Seungjin; Park, Kyungsoo; Seong, Rho Hyun

    2015-01-01

    Germinal center (GC) reaction is crucial in adaptive immune responses. The formation of GC is coordinated by the expression of specific genes including Blimp-1 and Bcl-6. Although gene expression is critically influenced by the status of chromatin structure, little is known about the role of chromatin remodeling factors for regulation of GC formation. Here, we show that the SWI/SNF chromatin remodeling complex is required for GC reactions. Mice lacking Srg3/mBaf155, a core component of the SWI/SNF complex, showed impaired differentiation of GC B and follicular helper T cells in response to T cell-dependent antigen challenge. The SWI/SNF complex regulates chromatin structure at the Blimp-1 locus and represses its expression by interacting cooperatively with Bcl-6 and corepressors. The defect in GC reactions in mice lacking Srg3 was due to the derepression of Blimp-1 as supported by genetic studies with Blimp-1–ablated mice. Hence, our study identifies the SWI/SNF complex as a key mediator in GC reactions by modulating Bcl-6–dependent Blimp-1 repression. PMID:25646472

  15. Monitoring complex formation in the blood-coagulation cascade using aptamer-coated SAW sensors.

    PubMed

    Gronewold, T M A; Glass, S; Quandt, E; Famulok, M

    2005-04-15

    Specific binding of the anticoagulants heparin and antithrombin III to the blood clotting cascade factor human thrombin was recorded as a function of time with a Love-wave biosensor array consisting of five sensor elements. Two of the sensor elements were used as references. Three sensor elements were coated with RNA or DNA aptamers for specific binding of human thrombin. The affinity between the aptamers and thrombin, measured using the biosensor, was within the same range as the value of K(D) measured by filter binding experiments. Consecutive binding of the thrombin inhibitors heparin, antithrombin III or the heparin-antithrombin III complex to the immobilized thrombin molecules, and binding of a ternary complex of heparin, anithrombin III, and thrombin to aptamers was evaluated. The experiments showed attenuation of binding to thrombin due to heparin-antithrombin III complex formation. Binding of heparin activated the formation of the inhibitory complex of antithrombin III with thrombin about 2.7-fold. Binding of the DNA aptamer to exosite II appeared to inhibit heparin binding to exosite I. PMID:15741074

  16. Lowstand transgressive upper Cretaceous (Coniacian) gravelly deltaic complexes of the Cardium formation, West Central Alberta, Canada

    SciTech Connect

    Thomas, D.V.

    1996-12-31

    A detailed facies and sequence stratigraphic analysis is used to demonstrate the reservoir compartmentalization of gravelly deltaic complexes deposited on a ramp margin in the Western Canadian Sedimentary Basin. Gravelly deltas of the Carrot Creek Member of the Cardium Formation in the Cyn Pem Field area of West Central Alberta occur along well defined backslapping shoreline trends that represent high frequency lowstand to transgressive systems tracts that followed the second order sea level fall ({approximately}90 Ma) of the Turonian. The Cyn Pem Cardium D pool is used to illustrate the detailed sedimentologly and stratigraphy of a gravelly deltaic complex. The pool consists of two distinct coarse-grained delta lobes oriented along a northwest-trending shoreline. Up to 21 meters of gravelly stream mouth bar and distributary channel facles were deposited unconformably on distal marine highstand deposits of the Raven River Member (Turonian) of the Cardium Formation. Production data and facies analysis indicates excellent communication along high permeability (>l Darcy) Gilbert-type deltaic foresets oriented parallel to strike and moderate to poor communication in a depositional dip direction. Poorly sorted gravelly distributary channels dissect the deltaic ioresets. A complex history of high frequency lowstand and transgressive erosion resulted in substantial paleotopographic relief that both bounds and compartmentalizes these gravelly deltaic complexes.

  17. Lowstand transgressive upper Cretaceous (Coniacian) gravelly deltaic complexes of the Cardium formation, West Central Alberta, Canada

    SciTech Connect

    Thomas, D.V. )

    1996-01-01

    A detailed facies and sequence stratigraphic analysis is used to demonstrate the reservoir compartmentalization of gravelly deltaic complexes deposited on a ramp margin in the Western Canadian Sedimentary Basin. Gravelly deltas of the Carrot Creek Member of the Cardium Formation in the Cyn Pem Field area of West Central Alberta occur along well defined backslapping shoreline trends that represent high frequency lowstand to transgressive systems tracts that followed the second order sea level fall ([approximately]90 Ma) of the Turonian. The Cyn Pem Cardium D pool is used to illustrate the detailed sedimentologly and stratigraphy of a gravelly deltaic complex. The pool consists of two distinct coarse-grained delta lobes oriented along a northwest-trending shoreline. Up to 21 meters of gravelly stream mouth bar and distributary channel facles were deposited unconformably on distal marine highstand deposits of the Raven River Member (Turonian) of the Cardium Formation. Production data and facies analysis indicates excellent communication along high permeability (>l Darcy) Gilbert-type deltaic foresets oriented parallel to strike and moderate to poor communication in a depositional dip direction. Poorly sorted gravelly distributary channels dissect the deltaic ioresets. A complex history of high frequency lowstand and transgressive erosion resulted in substantial paleotopographic relief that both bounds and compartmentalizes these gravelly deltaic complexes.

  18. Perfluoroalkyl Cobalt(III) Fluoride and Bis(perfluoroalkyl) Complexes: Catalytic Fluorination and Selective Difluorocarbene Formation.

    PubMed

    Leclerc, Matthew C; Bayne, Julia M; Lee, Graham M; Gorelsky, Serge I; Vasiliu, Monica; Korobkov, Ilia; Harrison, Daniel J; Dixon, David A; Baker, R Tom

    2015-12-30

    Four perfluoroalkyl cobalt(III) fluoride complexes have been synthesized and characterized by elemental analysis, multinuclear NMR spectroscopy, X-ray crystallography, and powder X-ray diffraction. The remarkable cobalt fluoride (19)F NMR chemical shifts (-716 to -759 ppm) were studied computationally, and the contributing paramagnetic and diamagnetic factors were extracted. Additionally, the complexes were shown to be active in the catalytic fluorination of p-toluoyl chloride. Furthermore, two examples of cobalt(III) bis(perfluoroalkyl)complexes were synthesized and their reactivity studied. Interestingly, abstraction of a fluoride ion from these complexes led to selective formation of cobalt difluorocarbene complexes derived from the trifluoromethyl ligand. These electrophilic difluorocarbenes were shown to undergo insertion into the remaining perfluoroalkyl fragment, demonstrating the elongation of a perfluoroalkyl chain arising from a difluorocarbene insertion on a cobalt metal center. The reactions of both the fluoride and bis(perfluoroalkyl) complexes provide insight into the potential catalytic applications of these model systems to form small fluorinated molecules as well as fluoropolymers. PMID:26674217

  19. Actomyosin-dependent formation of the mechanosensitive talin-vinculin complex reinforces actin anchoring

    NASA Astrophysics Data System (ADS)

    Ciobanasu, Corina; Faivre, Bruno; Le Clainche, Christophe

    2014-01-01

    The force generated by the actomyosin cytoskeleton controls focal adhesion dynamics during cell migration. This process is thought to involve the mechanical unfolding of talin to expose cryptic vinculin-binding sites. However, the ability of the actomyosin cytoskeleton to directly control the formation of a talin-vinculin complex and the resulting activity of the complex are not known. Here we develop a microscopy assay with pure proteins in which the self-assembly of actomyosin cables controls the association of vinculin to a talin-micropatterned surface in a reversible manner. Quantifications indicate that talin refolding is limited by vinculin dissociation and modulated by the actomyosin network stability. Finally, we show that the activation of vinculin by stretched talin induces a positive feedback that reinforces the actin-talin-vinculin association. This in vitro reconstitution reveals the mechanism by which a key molecular switch senses and controls the connection between adhesion complexes and the actomyosin cytoskeleton.

  20. Mechanistic study of intertypic nucleoprotein complex formation and its inhibitory effect toward influenza A virus.

    PubMed

    Narkpuk, Jaraspim; Jaru-Ampornpan, Peera; Subali, Theressa; Bertulfo, Fatima Carla T; Wongthida, Phonphimon; Jongkaewwattana, Anan

    2015-11-01

    Co-infection of influenza A and B viruses (IAV and IBV) results in marked decreases in IAV replication. Multiple mechanisms have been proposed for this phenomenon. Recently, we reported that IBV nucleoprotein (BNP) alone can suppress IAV replication and proposed an inhibition model in which BNP binds IAV nucleoprotein (ANP) and disrupts IAV polymerase complexes. Here, using mutagenesis and co-immunoprecipitation, we determined the protein motifs mediating the intertypic ANP-BNP complex and showed that it specifically interferes with ANP?s interaction with the PB2 subunit of the IAV polymerase but not with the other subunit PB1. We further demonstrated that BNP only suppresses growth of IAVs but not other RNA viruses. However, different IAV strains display varied sensitivity toward the BNP?s inhibitory effect. Together, our data provide mechanistic insights into intertypic nucleoprotein complex formation and highlight the role of BNP as a potential broad-spectrum anti-IAV agent. PMID:26218215

  1. Mssbauer study of peroxynitrito complex formation with FeIII-chelates

    NASA Astrophysics Data System (ADS)

    Homonnay, Zoltan; Buszlai, Peter; Ndor, Judit; Sharma, Virender K.; Kuzmann, Erno; Vrtes, Attila

    2012-03-01

    The reaction of the ?-oxo-diiron(III)-L complex (L = EDTA, ethylene diamine tetraacetate, HEDTA, hydroxyethyl ethylene diamine triacetate, and CyDTA, cyclohexane diamine tetraacetate) with peroxynitrite in alkaline solution was studied by Mssbauer spectroscopy using rapid-freezing technique. These complexes yield an (L)FeIII( ? 2-O2)^{3-} complex ion when they react with hydrogen peroxide and the formation of the peroxide adduct results in a deep purple coloration of the solution. The same color appears when the reaction occurs with peroxinitrite. Although spectrophotometry indicated some difference between the molar extinction coefficients of the peroxo and the peroxinitrito adducts, the Mssbauer parameters proved to be the same within experimental error. It is concluded that the peroxynitrite ion decomposes when reacting with FeIII(L) and the peroxo adduct forms.

  2. Successive ratio subtraction coupled with constant multiplication spectrophotometric method for determination of hydroquinone in complex mixture with its degradation products, tretinoin and methyl paraben.

    PubMed

    Elghobashy, Mohamed R; Bebawy, Lories I; Shokry, Rafeek F; Abbas, Samah S

    2016-03-15

    A sensitive and selective stability-indicating successive ratio subtraction coupled with constant multiplication (SRS-CM) spectrophotometric method was studied and developed for the spectrum resolution of five component mixture without prior separation. The components were hydroquinone in combination with tretinoin, the polymer formed from hydroquinone alkali degradation, 1,4 benzoquinone and the preservative methyl paraben. The proposed method was used for their determination in their pure form and in pharmaceutical formulation. The zero order absorption spectra of hydroquinone, tretinoin, 1,4 benzoquinone and methyl paraben were determined at 293, 357.5, 245 and 255.2nm, respectively. The calibration curves were linear over the concentration ranges of 4.00-46.00, 1.00-7.00, 0.60-5.20, and 1.00-7.00?gmL(-1) for hydroquinone, tretinoin, 1,4 benzoquinone and methyl paraben, respectively. The pharmaceutical formulation was subjected to mild alkali condition and measured by this method resulting in the polymerization of hydroquinone and the formation of toxic 1,4 benzoquinone. The proposed method was validated according to ICH guidelines. The results obtained were statistically analyzed and compared with those obtained by applying the reported method. PMID:26745510

  3. Successive ratio subtraction coupled with constant multiplication spectrophotometric method for determination of hydroquinone in complex mixture with its degradation products, tretinoin and methyl paraben

    NASA Astrophysics Data System (ADS)

    Elghobashy, Mohamed R.; Bebawy, Lories I.; Shokry, Rafeek F.; Abbas, Samah S.

    2016-03-01

    A sensitive and selective stability-indicating successive ratio subtraction coupled with constant multiplication (SRS-CM) spectrophotometric method was studied and developed for the spectrum resolution of five component mixture without prior separation. The components were hydroquinone in combination with tretinoin, the polymer formed from hydroquinone alkali degradation, 1,4 benzoquinone and the preservative methyl paraben. The proposed method was used for their determination in their pure form and in pharmaceutical formulation. The zero order absorption spectra of hydroquinone, tretinoin, 1,4 benzoquinone and methyl paraben were determined at 293, 357.5, 245 and 255.2 nm, respectively. The calibration curves were linear over the concentration ranges of 4.00-46.00, 1.00-7.00, 0.60-5.20, and 1.00-7.00 μg mL- 1 for hydroquinone, tretinoin, 1,4 benzoquinone and methyl paraben, respectively. The pharmaceutical formulation was subjected to mild alkali condition and measured by this method resulting in the polymerization of hydroquinone and the formation of toxic 1,4 benzoquinone. The proposed method was validated according to ICH guidelines. The results obtained were statistically analyzed and compared with those obtained by applying the reported method.

  4. Complex formation between excited-state saturated amines and water in n-hexane solution

    SciTech Connect

    Halpern, A.M.; Ruggles, C.J.; Zhang, X.K.

    1987-06-10

    Fluorescence spectra and decay curves of dilute solutions (<3 x 10/sup -4/ M) of triethylamine (TEA), tri-n-propylamine (TPA), and 1,4-diazabicyclo(2.2.2)octane (DABCO) in H/sub 2/O- and D/sub 2/O-saturated n-hexane reveal the presence of a complex formed between the electronically excited amine and water. The decay curves, measured between 273 and 323 K (and at 280 and 360 nm; 300 and 400 nm for DABCO), conform to the standard monomer-excimer photokinetic scheme and are analyzed accordingly. These results indicate that the binding energy of the excited TEA-H/sub 2/O complex (B*) is ca. 7.8 kcal/mol, which is larger than that of the ground-state TEA hydrate. B* for the TPA and DABCO-H/sub 2/O complexes is estimated to be ca. 10 and 8.8 kcal/mol, respectively. Stationary-state measurements are consistent with these assignments. The activation energy for the diffusion of water in n-hexane (assumed to be monomeric) appears to be very small (<1 kcal/mol). The decay constants of the three complexes studied are ca. 3.4 x 10/sup 7/ s/sup -1/ for amine-H/sub 2/O and 2.9 x 10/sup 7/ s/sup -1/ for the amine-D/sub 2/O systems. Intrinsic fluorescence quantum efficiencies of the amine-H/sub 2/O complexes are 0.17, 0.23, and 0.28 for TEA, TPA, and DABCO, respectively, at 303 K. A Foerster cycle analysis of the dry and H/sub 2/O-saturated fluorescence spectra of TEA, when taking the ground-state hydrate into account indicates that the repulsion energy of the post-fluorescence (TEA-H/sub 2/O) complex is ca. 10 kcal/mol.

  5. cAMP prevents TNF-induced apoptosis through inhibiting DISC complex formation in rat hepatocytes

    SciTech Connect

    Bhattacharjee, Rajesh; Xiang, Wenpei; Family Planning Research Institute, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, People's Republic of China ; Wang, Yinna; Zhang, Xiaoying

    2012-06-22

    Highlights: Black-Right-Pointing-Pointer cAMP blocks cell death induced by TNF and actinomycin D in cultured hepatocytes. Black-Right-Pointing-Pointer cAMP blocks NF-{kappa}B activation induced by TNF and actinomycin D. Black-Right-Pointing-Pointer cAMP blocks DISC formation following TNF and actinomycin D exposure. Black-Right-Pointing-Pointer cAMP blocks TNF signaling at a proximal step. -- Abstract: Tumor necrosis factor {alpha} (TNF) is a pleiotropic proinflammatory cytokine that plays a role in immunity and the control of cell proliferation, cell differentiation, and apoptosis. The pleiotropic nature of TNF is due to the formation of different signaling complexes upon the binding of TNF to its receptor, TNF receptor type 1 (TNFR1). TNF induces apoptosis in various mammalian cells when the cells are co-treated with a transcription inhibitor like actinomycin D (ActD). When TNFR1 is activated, it recruits an adaptor protein, TNF receptor-associated protein with death domain (TRADD), through its cytoplasmic death effector domain (DED). TRADD, in turn, recruits other signaling proteins, including TNF receptor-associated protein 2 (TRAF2) and receptor-associated protein kinase (RIPK) 1, to form a complex. Subsequently, this complex combines with FADD and procaspase-8, converts into a death-inducing signaling complex (DISC) to induce apoptosis. Cyclic AMP (cAMP) is a second messenger that regulates various cellular processes such as cell proliferation, gene expression, and apoptosis. cAMP analogues are reported to act as anti-apoptotic agents in various cell types, including hepatocytes. We found that a cAMP analogue, dibutyryl cAMP (db-cAMP), inhibits TNF + ActD-induced apoptosis in rat hepatocytes. The protein kinase A (PKA) inhibitor KT-5720 reverses this inhibitory effect of cAMP on apoptosis. Cytoprotection by cAMP involves down-regulation of various apoptotic signal regulators like TRADD and FADD and inhibition of caspase-8 and caspase-3 cleavage. We also found that cAMP exerts its affect at the proximal level of TNF signaling by inhibiting the formation of the DISC complex upon the binding of TNF to TNFR1. In conclusion, our study shows that cAMP prevents TNF + ActD-induced apoptosis in rat hepatocytes by inhibiting DISC complex formation.

  6. Experimental investigation on lane formation in complex plasmas under microgravity conditions

    NASA Astrophysics Data System (ADS)

    Du, C.-R.; Stterlin, K. R.; Jiang, K.; Rth, C.; Ivlev, A. V.; Khrapak, S.; Schwabe, M.; Thomas, H. M.; Fortov, V. E.; Lipaev, A. M.; Molotkov, V. I.; Petrov, O. F.; Malentschenko, Y.; Yurtschichin, F.; Lonchakov, Y.; Morfill, G. E.

    2012-07-01

    A series of experiments dedicated to probing the phenomenon of lane formation in binary complex plasmas over a broad range of parameters has been performed with the PK-3 Plus laboratory on board the International Space Station (ISS) under microgravity conditions. In the experiments, bunches of small particles were driven through a background of big particles. We show that the dynamics of lane formation varies considerably with the density of the background and the size ratio between small and big particles. For consecutive injections of small particles a memory effect of the previous penetration was discovered for the first time. This memory effect was investigated quantitatively with respect to the structure formation and the penetration speed. We show that the memory effect in lane formation is linear. In addition, we studied the crossover from lane formation to phase separation driven by the nonadditive interactions between small and big particles. We found that during this transition the small penetrating particles effectively cage the background particles.

  7. Structural Complexities Influencing Biostratigraphic Interpretations of the Permian Nansen Formation type-section, Ellesmere Island, Canada

    NASA Astrophysics Data System (ADS)

    Hill, M.; Guest, B.

    2011-12-01

    The Carboniferous to Permian aged Nansen Formation is a cyclic carbonate shelf deposit and potential hydrocarbon reservoir. This formation is the thickest, most widespread carbonate sequence in the Sverdrup Basin. Deformed during the Eurekan Orogeny, the Nansen Fm. is topographically prominent and responsible for the rugged topography on Axel Heiburg and Ellesmere Island. The type-section for the Nansen Fm. is located on the north side of Hare Fiord, along Girty Creek. At this location there is an estimated stratigraphic thickness of 2 km. Due to easier access most of the stratigraphic work has been completed on nearby glacially exposed sections that traverse parallel to Girty Creek along glacial margins. Extensive biostratigraphy was completed on a glacier section to the west, however, in a glacier section to the east of Girty Creek, structural complexities appear to be repeating sections of the formation. Here, the Nansen formation is bounded by two regional reverse faults. This has produced duplex structures, with clearly exposed stacked horses, footwall synclines, and truncations. By projecting the structures observed along the eastern glacier section to the western glacier section that was used for biostratigraphic studies, it is clear that these structures would affect biostratigraphic interpretations. It was previously noted by biostratigraphers that thrust faults appear to be repeating sections of the Nansen formation. However by correlating all observed faults with the biostratigraphy, we can determine the extent to which the faulting has affected the interpretations, and whether all faults or stratigraphic repetitions are accounted for.

  8. Complex formation of heterocyclic amines with porphyrins: its use in detection and prevention.

    PubMed

    Hayatsu, H

    1995-01-01

    Porphyrins can suppress mutagenicity of heterocyclic amines. We have shown using the Ames Salmonella test that the mutagenicity of heterocyclic amines is efficiently inhibited by addition of hemin, the red blood porphyrin, in the assay mixture. In this suppression, hemin acts in two ways; inhibition of metabolic activation and suppression of the mutagenicity in the metabolically activated heterocyclic amines. In both of these actions, a complex formation between the porphyrin molecule and the planar molecules of heterocyclic amines seems to play a role. Complex formation and its use in detecting heterocyclic amines in various samples can be seen in the case for copper phthalocyanine, a blue pigment with a porphyrin-like structure. Cellulose bearing copper phthalocyanine trisulfonate as ligand was found to be a selective adsorbent for polycyclic compounds. This adsorbent, named blue cotton/blue rayon, adsorbs polycyclics in aqueous media by forming complexes on the ligand molecules, and releases the adsorbed compounds in organic solvents, such as in methanol plus a small amount of ammonia. The ease in manipulation and its high efficiency have made the blue cotton/blue rayon technique a means now widely used in detecting heterocyclic amines and other polycyclic mutagens in crude samples such as food, urine, and even river water. Chlorophyll, a green plant porphyrin, is another example. Chlorophyll and its stable form, chlorophyllin, have been shown to be inhibitory against the mutagenicity of heterocyclic amines. We have prepared Sepharose-supported chlorophyllin and have shown that heterocyclic amines are adsorbable to this ligand in a reversible fashion. Complex formation between chlorophyllin and heterocyclic amines is also suggested from spectrophotometric studies. A preliminary in vivo study has shown that chlorophyllin is effective in diminishing the cooked beef-derived urinary mutagenicity in humans. PMID:8844808

  9. Role of phospholipids in respiratory cytochrome bc(1) complex catalysis and supercomplex formation.

    PubMed

    Wenz, Tina; Hielscher, Ruth; Hellwig, Petra; Schgger, Hermann; Richers, Sebastian; Hunte, Carola

    2009-06-01

    Specific protein-lipid interactions have been identified in X-ray structures of membrane proteins. The role of specifically bound lipid molecules in protein function remains elusive. In the current study, we investigated how phospholipids influence catalytic, spectral and electrochemical properties of the yeast respiratory cytochrome bc(1) complex and how disruption of a specific cardiolipin binding site in cytochrome c(1) alters respiratory supercomplex formation in mitochondrial membranes. Purified yeast cytochrome bc(1) complex was treated with phospholipase A(2). The lipid-depleted enzyme was stable but nearly catalytically inactive. The absorption maxima of the reduced b-hemes were blue-shifted. The midpoint potentials of the b-hemes of the delipidated complex were shifted from -52 to -82 mV (heme b(L)) and from +113 to -2 mV (heme b(H)). These alterations could be reversed by reconstitution of the delipidated enzyme with a mixture of asolectin and cardiolipin, whereas addition of the single components could not reverse the alterations. We further analyzed the role of a specific cardiolipin binding site (CL(i)) in supercomplex formation by site-directed mutagenesis and BN-PAGE. The results suggested that cardiolipin stabilizes respiratory supercomplex formation by neutralizing the charges of lysine residues in the vicinity of the presumed interaction domain between cytochrome bc(1) complex and cytochrome c oxidase. Overall, the study supports the idea, that enzyme-bound phospholipids can play an important role in the regulation of protein function and protein-protein interaction. PMID:19254687

  10. Molybdenum Hydride and Dihydride Complexes Bearing Diphosphine Ligands with a Pendant Amine: Formation of Complexes With Bound Amines

    SciTech Connect

    Zhang, Shaoguang; Bullock, R. Morris

    2015-07-06

    CpMo(CO)(PNP)H complexes (PNP = (R2PCH2)2NMe, R = Et or Ph) were synthesized by displacement of two CO ligands of CpMo(CO)3H by the PNP ligand; these complexes were characterized by IR and variable temperature 1H and 31P NMR spectroscopy. CpMo(CO)(PNP)H complexes are formed as mixture of cis and trans-isomers. Both cis-CpMo(CO)(PEtNMePEt)H and trans-CpMo(CO)(PPhNMePPh)H were analyzed by single crystal X-ray diffraction. Electrochemical oxidation of CpMo(CO)(PEtNMePEt)H and CpMo(CO)(PPhNMePPh)H in CH3CN are both irreversible at slow scan rates and quasi-reversible at higher scan rates, with E1/2 = -0.36 V (vs. Cp2Fe+/0) for CpMo(CO)(PEtNMePEt)H and E1/2 = -0.18 V for CpMo(CO)(PPhNMePPh)H. Hydride abstraction from CpMo(CO)(PNP)H with [Ph3C]+[A]- (A = B(C6F5)4 or BArF4; [ArF = 3,5-bis(trifluoromethyl)phenyl]) afforded “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes that feature the amine bound to the metal. Displacement of the κ3 Mo-N bond by CD3CN gives [CpMo(CO)(PNP)(CD3CN)]+. The kinetics of this reaction were studied by NMR spectroscopy, providing the activation parameters ΔH‡ = 22.1 kcal/mol, ΔS‡ = 1.89 cal/(mol·K), Ea = 22.7 kcal/mol. Protonation of CpMo(CO)(PEtNMePEt)H affords [CpMo(CO)(κ2-PEtNMePEt)(H)2]+ as a Mo dihydride complex, which loses H2 to generate [CpMo(CO)(κ3-PEtNMePEt)]+ at room temperature. CpMo(CO)(dppp)H (dppp = 1,2-bis(diphenylphosphino)propane) was studied as a Mo diphosphine analogue without a pendant amine, and the product of protonation of this complex gives [CpMo(CO)(dppp)(H)2]+. Our results show that the pendant amine has a strong driving force to form stable “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes, and also promotes hydrogen elimination from [CpMo(CO)(PNP)(H)2]+ complexes by formation of Mo-N dative bond. We thank the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences for support. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy. We thank Monte Helm, Elliott Hulley and Deanna Miller for help on the crystallography, and Ming Fang for assistance on the electrochemical experiments.

  11. In vivo dynamics of chromatin-associated complex formation in mammalian nucleotide excision repair

    PubMed Central

    Mon, Martijn J.; Bernas, Tytus; Dinant, Christoffel; Goedvree, Feliks A.; Manders, Erik M. M.; Volker, Marcel; Houtsmuller, Adriaan B.; Hoeijmakers, Jan H. J.; Vermeulen, Wim; van Driel, Roel

    2004-01-01

    Chromatin is the substrate for many processes in the cell nucleus, including transcription, replication, and various DNA repair systems, all of which require the formation of multiprotein machineries on the chromatin fiber. We have analyzed the kinetics of in vivo assembly of the protein complex that is responsible for nucleotide excision repair (NER) in mammalian cells. Assembly is initiated by UV irradiation of a small area of the cell nucleus, after which the accumulation of GFP-tagged NER proteins in the DNA-damaged area is measured, reflecting the establishment of the dual-incision complex. The dynamic behavior of two NER proteins, ERCC1-XPF and TFIIH, was studied in detail. Results show that the repair complex is assembled with a rate of ?30 complexes per second and is not diffusion limited. Furthermore, we provide in vivo evidence that not only binding of TFIIH, but also its helicase activity, is required for the recruitment of ERCC1-XPF. These studies give quantitative insight into the de novo assembly of a chromatin-associated protein complex in living cells. PMID:15520397

  12. Structural and Thermodynamic Characterization of Cadherin?-Catenin?-Catenin Complex Formation*

    PubMed Central

    Pokutta, Sabine; Choi, Hee-Jung; Ahlsen, Goran; Hansen, Scott D.; Weis, William I.

    2014-01-01

    The classical cadherin?-catenin?-catenin complex mediates homophilic cell-cell adhesion and mechanically couples the actin cytoskeletons of adjacent cells. Although ?-catenin binds to ?-catenin and to F-actin, ?-catenin significantly weakens the affinity of ?-catenin for F-actin. Moreover, ?-catenin self-associates into homodimers that block ?-catenin binding. We investigated quantitatively and structurally ?E- and ?N-catenin dimer formation, their interaction with ?-catenin and the cadherin?-catenin complex, and the effect of the ?-catenin actin-binding domain on ?-catenin association. The two ?-catenin variants differ in their self-association properties: at physiological temperatures, ?E-catenin homodimerizes 10 more weakly than does ?N-catenin but is kinetically trapped in its oligomeric state. Both ?E- and ?N-catenin bind to ?-catenin with a Kd of 20 nm, and this affinity is increased by an order of magnitude when cadherin is bound to ?-catenin. We describe the crystal structure of a complex representing the full ?-catenin?N-catenin interface. A three-dimensional model of the cadherin?-catenin?-catenin complex based on these new structural data suggests mechanisms for the enhanced stability of the ternary complex. The C-terminal actin-binding domain of ?-catenin has no influence on the interactions with ?-catenin, arguing against models in which ?-catenin weakens actin binding by stabilizing inhibitory intramolecular interactions between the actin-binding domain and the rest of ?-catenin. PMID:24692547

  13. Formation mechanism and biological activity of novel thiolated human-like collagen iron complex.

    PubMed

    Zhu, Chenhui; Liu, Lingyun; Deng, Jianjun; Ma, Xiaoxuan; Hui, Junfeng; Fan, Daidi

    2016-03-01

    To develop an iron supplement that is effectively absorbed and utilized, thiolated human-like collagen was created to improve the iron binding capacity of human-like collagen. A thiolated human-like collagen-iron complex was prepared in a phosphate buffer, and one mole of thiolated human-like collagen-iron possessed approximately 28.83 moles of iron. The characteristics of thiolated human-like collagen-iron were investigated by ultraviolet-visible absorption spectroscopy, Fourier transform infrared spectroscopy, circular dichroism, and differential scanning calorimetry. The results showed that the thiolated human-like collagen-iron complex retained the secondary structure of human-like collagen and had greater thermodynamic stability than human-like collagen, although interactions between iron ions and human-like collagen occurred during the formation of the complex. In addition, to evaluate the bioavailability of thiolated human-like collagen-iron, an in vitro Caco-2 cell model and an in vivo iron deficiency anemia mouse model were employed. The data demonstrated that the thiolated human-like collagen-iron complex exhibited greater bioavailability and was more easily utilized than FeSO4, ferric ammonium citrate, or ferrous glycinate. These results indicated that the thiolated human-like collagen-iron complex is a potential iron supplement in the biomedical field. PMID:26847914

  14. Reinvestigation of the formation of a mononuclear Fe(III) hydroperoxido complex using high pressure kinetics.

    PubMed

    Nebe, Thomas; Beitat, Alexander; Wrtele, Christian; Dcker-Benfer, Carlos; van Eldik, Rudi; McKenzie, Christine J; Schindler, Siegfried

    2010-09-01

    Previous stopped flow kinetic experiments suggested an interchange associative mechanism for the ligand substitution reaction, [Fe(bztpen)(OMe)](2+) + H(2)O(2)--> {[Fe(bztpen)(OMe)(HOOH)](2+)}(++)--> [Fe(bztpen)(OOH)](2+) + MeOH (bztpen = N-benzyl-N, N',N'tris(2-methylpyridyl)-ethylenediamine). Thus a seven-coordinate transition state containing both the leaving methoxide and the incoming hydrogen peroxide ligands was proposed. On the basis of high pressure kinetic data we can now conclude that this is not the case since the rate of the reaction is independent of pressure for the formation of the purple low spin transient hydroperoxido complex, [Fe(bztpen)(OOH)](2+). [Fe(bztpen)(OOH)](2+) has so far proved to be too short-lived for solid state isolation. As part of our ongoing pursuit of this elusive species we have structurally characterised the nitrosyl and acetate iron(II) complexes, [Fe(bztpen)(NO)](OTf)(2) and [Fe(bztpen)(OAc)](BPh(4)), as well as the air stable Co(II) complexes [Co(bztpen)Cl)]BF(4), [Co(metpen)Cl]SbF(6) and [Co(bztpen)(OAc)]BPh(4). We did not realise our aim of accessing stable Co(III) hydroperoxido or peroxido complexes by reaction of the cobalt complexes with H(2)O(2). PMID:20648392

  15. Spectrophotometric and AAS determination of ramipril and enalapril through ternary complex formation.

    PubMed

    Ayad, Magda M; Shalaby, Abdalla A; Abdellatef, Hisham E; Hosny, Mervat M

    2002-04-15

    Two sensitive, spectrophotometric and atomic absorption spectrometric procedures are developed for the determination of two antihypertensive agents (enalapril maleate and ramipril). The spectrophotometric procedures for the two cited drugs are based on ternary complex formation. The first ternary complex (copper(II), eosin, and enalapril) was estimated by two methods; the first depends on its extraction with chloroform measuring at 533.4 nm. Beer's law was obeyed in concentration range from 56 to 112 microg ml(-1). The second method for the same complex depends on its direct measurement after addition of methylcellulose as surfactant at the pH value 5 at 558.8 nm. The concentration range is from 19 to 32 microg ml(-1). The second ternary complex (iron(III), thiocyanate, and ramipril) was extracted with methylene chloride, measuring at 436.6 nm, with a concentration range 60-132 microg ml(-1). The direct atomic absorption spectrometric method through the quantitative determination of copper or iron content of the complex was also investigated for the purpose of enhancing the sensitivity of the determination. The spectrophotometric and atomic absorption spectrometric procedures hold their accuracy and precision well when applied to the determination of ramipril and enalapril dosage forms. PMID:11929674

  16. Revised nomenclature and stratigraphic relationships of the Fredericksburg Complex and Quantico Formation of the Virginia Piedmont

    USGS Publications Warehouse

    Pavlides, Louis

    1980-01-01

    The Fredericksburg Complex, in part a migmatitic terrane in northeast Virginia, is subdivided on the basis of lithology, as well as aeromagnetic and aeroradiometric data, into two metamorphic suites. These suites are separated by the northeast-trending Spotsylvania lineament, a rectilinear geophysical feature that is probably the trace of an old fault zone. East of the lineament, the Po River Metamorphic Suite, of Proterozoic Z and (or) early Paleozoic age, consists dominantly of biotite gneiss, generally augen gneiss, and lesser amounts of hornblende gneiss and mica schist. West of the Spotsylvania lineament is the Ta River Metamorphic Suite, composed mostly of amphibolite and amphibole gneiss. However, to the southwest, along its strike belt, the Ta River contains abundant biotite gneiss and mica schist. Both the Ta River and Po River contain abundant foliated granitoid and pegmatoid bodies as concordant tabular masses and as crosscutting dikes; these rocks are considered part of the Ta River and Po River Metamorphic Suites. The amphibolitic Holly Corner Gneiss is interpreted to be a western allochthonous equivalent of the Ta River. Both the Ta River and Holly Corner are considered to be coeval, eastern, distal facies of the Lower Cambrian(?) Chopawamsic Formation. The Paleozoic Falls Run Granite Gneiss intrudes the Ta River Metamorphic Suite and the Holly Corner Gneiss; locally the Falls Run is interpreted to have been transported westward with the Holly Corner after intrusion. The Quantico Formation, in the core of the Quantico-Columbia synclinorium, rests with angular unconformity along its northwest and southeast limbs, respectively, on the Chopawamsic Formation and the Ta River Metamorphic Suite. The Quantico Formation is assigned the same Late Ordovician age and similar stratigraphic position as the Arvonia Slate of the Arvonia syncline. The youngest rocks of the area are the granitoid and pegmatoid bodies of the Falmouth Intrusive Suite. They consist of several generations of chiefly dikes and sills that are intrusive into the Fredericksburg Complex and into the Quantico Formation. Granitoid rocks also form small plutons. The Falmouth is isotopically dated as Carboniferous in age. Some of the metavolcanic rocks of the Evington Group and part of the amphibolite gneiss and amphibolite of the Hatcher Complex, named by W. B. Brown in 1969, are probably coeval with the Chopawamsic Formation and hence equivalents of the Ta River Metamorphic Suite and the Holly Corner Gneiss. The biotitic gneiss and granitoid rocks east of the Spotsylvania lineament in the Dillwyn area are considered to be coeval with the Po River Metamorphic Suite.

  17. Varicella-zoster virus infection triggers formation of an interleukin-1? (IL-1?)-processing inflammasome complex.

    PubMed

    Nour, Adel M; Reichelt, Mike; Ku, Chia-Chi; Ho, Min-Yin; Heineman, Thomas C; Arvin, Ann M

    2011-05-20

    Innate cellular immunity is the immediate host response against pathogens, and activation of innate immunity also modulates the induction of adaptive immunity. The nucleotide-binding oligomerization domain (NOD)-like receptors (NLRs) are a family of intracellular receptors that recognize conserved patterns associated with intracellular pathogens, but information about their role in the host defense against DNA viruses is limited. Here we report that varicella-zoster virus (VZV), an alphaherpesvirus that is the causative agent of varicella and herpes zoster, induces formation of the NLRP3 inflammasome and the associated processing of the proinflammatory cytokine IL-1? by activated caspase-1 in infected cells. NLRP3 inflammasome formation was induced in VZV-infected human THP-1 cells, which are a transformed monocyte cell line, primary lung fibroblasts, and melanoma cells. Absent in melanoma gene-2 (AIM2) is an interferon-inducible protein that can form an alternative inflammasome complex with caspase-1 in virus-infected cells. Experiments in VZV-infected melanoma cells showed that NLRP3 protein recruits the adaptor protein ASC and caspase-1 to form an NLRP3 inflammasome complex independent of AIM2 protein and in the absence of free radical reactive oxygen species release. NLRP3 was also expressed extensively in infected skin xenografts in the severe combined immunodeficiency mouse model of VZV pathogenesis in vivo. We conclude that NLRP3 inflammasome formation is an innate cellular response to infection with this common pathogenic human herpesvirus. PMID:21385879

  18. Carbon Dioxide Influence on the Thermal Formation of Complex Organic Molecules in Interstellar Ice Analogs

    NASA Astrophysics Data System (ADS)

    Vinogradoff, V.; Duvernay, F.; Fray, N.; Bouilloud, M.; Chiavassa, T.; Cottin, H.

    2015-08-01

    Interstellar ices are submitted to energetic processes (thermal, UV, and cosmic-ray radiations) producing complex organic molecules. Laboratory experiments aim to reproduce the evolution of interstellar ices to better understand the chemical changes leading to the reaction, formation, and desorption of molecules. In this context, the thermal evolution of an interstellar ice analogue composed of water, carbon dioxide, ammonia, and formaldehyde is investigated. The ice evolution during the warming has been monitored by IR spectroscopy. The formation of hexamethylenetetramine (HMT) and polymethylenimine (PMI) are observed in the organic refractory residue left after ice sublimation. A better understanding of this result is realized with the study of another ice mixture containing methylenimine (a precursor of HMT) with carbon dioxide and ammonia. It appears that carbamic acid, a reaction product of carbon dioxide and ammonia, plays the role of catalyst, allowing the reactions toward HMT and PMI formation. This is the first time that such complex organic molecules (HMT, PMI) are produced from the warming (without VUV photolysis or irradiation with energetic particles) of abundant molecules observed in interstellar ices (H2O, NH3, CO2, H2CO). This result strengthens the importance of thermal reactions in the ices’ evolution. HMT and PMI, likely components of interstellar ices, should be searched for in the pristine objects of our solar system, such as comets and carbonaceous chondrites.

  19. Water, ammonia, methanol and complex molecules in the earliest phases of star formation

    NASA Astrophysics Data System (ADS)

    Caselli, Paola

    2015-08-01

    Herschel and ground based observations toward the contracting pre-stellar cloud core L1544 in the Taurus Molecular Cloud Complex have provided constraints on the distribution of water and organic molecules just before the formation of a Solar-type star and its potential planetary system. In this talk I shall present Herschel WISH observations of the ground state transitions of ortho-H2O and ortho-NH3 as well as IRAM 30m maps of methanol and deuterated methanol toward L1544. Together with recent observations of complex organic molecules toward the same source, and new ALMA data, conclusions can be drawn on the importance of surface processes and cosmic rays in the chemical evolution during the initial stages of star formation. D and 15N fractionations in this object as well as in other objects in early stages of evolution and in different environments, will also be presented and links to later stages in the star formation process and to our Solar System attempted.

  20. Inhibition of 2-amino-3-methylimidazo[4,5-f]quinoline (IQ)-DNA binding by chlorophyllin: studies of enzyme inhibition and molecular complex formation.

    PubMed

    Dashwood, R; Guo, D

    1992-07-01

    Chlorophyllin (CHL), a copper/sodium salt of chlorophyll used in the treatment of geriatric patients, is an anti-mutagen that has been demonstrated to inhibit carcinogen--DNA binding in vivo. To study the mechanism of inhibition, the microsomal metabolism of 2-amino-3-methylimidazo[4,5-f]quinoline (IQ) and the kinetics of IQ--DNA binding were investigated in the presence and absence of CHL. In time-course studies, CHL produced greater than 80% inhibition of IQ--DNA binding and blocked the metabolism of IQ, such that 80% of the initial dose of carcinogen was recovered unmetabolized from the incubations after 1 h. Kinetic constants were determined for the in vitro DNA binding reaction, with the reaction rate measured as 'pmol IQ bound/mg DNA/min/mg microsomal protein'. Without altering V(max), the Km of the IQ--DNA binding reaction was increased by CHL, and the replot of Km/V(max) versus CHL concentration yielded a straight line with an inhibitor constant of 58.3 microM CHL. Spectrophotometric studies provided evidence in vitro for the formation of a non-covalent complex between CHL and IQ. The CHL--IQ complex had a stoichiometric ratio of 2:1 (mole ratio method) and an apparent dissociation constant from the Benesi-Hilderbrand plot of 1.41 x 10(-4)M at pH 7.4. These results are discussed in the context of a CHL inhibitory mechanism involving enzyme inhibition and molecular complex formation. PMID:1638677

  1. SOHLH2 is essential for synaptonemal complex formation during spermatogenesis in early postnatal mouse testes.

    PubMed

    Park, Miree; Lee, Youngeun; Jang, Hoon; Lee, Ok-Hee; Park, Sung-Won; Kim, Jae-Hwan; Hong, Kwonho; Song, Hyuk; Park, Se-Pill; Park, Yun-Yong; Ko, Jung Jae; Choi, Youngsok

    2016-01-01

    Spermatogenesis- and oogenesis-specific helix-loop-helix transcription factor 2 (SOHLH2) is exclusively expressed in germ cells of the gonads. Previous studies show that SOHLH2 is critical for spermatogenesis in mouse. However, the regulatory mechanism of SOHLH2 during early spermatogenesis is poorly understood. In the present study, we analyzed the gene expression profile of the Sohlh2-deficient testis and examined the role of SOHLH2 during spermatogenesis. We found 513 genes increased in abundance, while 492 genes decreased in abundance in 14-day-old Sohlh2-deficient mouse testes compared to wildtype mice. Gene ontology analysis revealed that Sohlh2 disruption effects the relative abundance of various meiotic genes during early spermatogenesis, including Spo11, Dmc1, Msh4, Prdm9, Sycp1, Sycp2, Sycp3, Hormad1, and Hormad2. Western blot analysis and immunostaining showed that SYCP3, a component of synaptonemal complex, was significantly less abundant in Sohlh2-deficient spermatocytes. We observed a lack of synaptonemal complex formation during meiosis in Sohlh2-deficient spermatocytes. Furthermore, we found that SOHLH2 interacted with two E-boxes on the mouse Sycp1 promoter and Sycp1 promoter activity increased with ectopically expressed SOHLH2. Taken together, our data suggest that SOHLH2 is critical for the formation of synaptonemal complexes via its regulation of Sycp1 expression during mouse spermatogonial differentiation. PMID:26869299

  2. Gas phase uranyl activation: formation of a uranium nitrosyl complex from uranyl azide.

    PubMed

    Gong, Yu; de Jong, Wibe A; Gibson, John K

    2015-05-13

    Activation of the oxo bond of uranyl, UO2(2+), was achieved by collision induced dissociation (CID) of UO2(N3)Cl2(-) in a quadrupole ion trap mass spectrometer. The gas phase complex UO2(N3)Cl2(-) was produced by electrospray ionization of solutions of UO2Cl2 and NaN3. CID of UO2(N3)Cl2(-) resulted in the loss of N2 to form UO(NO)Cl2(-), in which the "inert" uranyl oxo bond has been activated. Formation of UO2Cl2(-) via N3 loss was also observed. Density functional theory computations predict that the UO(NO)Cl2(-) complex has nonplanar Cs symmetry and a singlet ground state. Analysis of the bonding of the UO(NO)Cl2(-) complex shows that the side-on bonded NO moiety can be considered as NO(3-), suggesting a formal oxidation state of U(VI). Activation of the uranyl oxo bond in UO2(N3)Cl2(-) to form UO(NO)Cl2(-) and N2 was computed to be endothermic by 169 kJ/mol, which is energetically more favorable than formation of NUOCl2(-) and UO2Cl2(-). The observation of UO2Cl2(-) during CID is most likely due to the absence of an energy barrier for neutral ligand loss. PMID:25906363

  3. Gas Phase Uranyl Activation: Formation of a Uranium Nitrosyl Complex from Uranyl Azide

    SciTech Connect

    Gong, Yu; De Jong, Wibe A.; Gibson, John K.

    2015-05-13

    Activation of the oxo bond of uranyl, UO22+, was achieved by collision induced dissociation (CID) of UO2(N3)Cl2– in a quadrupole ion trap mass spectrometer. The gas phase complex UO2(N3)Cl2– was produced by electrospray ionization of solutions of UO2Cl2 and NaN3. CID of UO2(N3)Cl2– resulted in the loss of N2 to form UO(NO)Cl2–, in which the “inert” uranyl oxo bond has been activated. Formation of UO2Cl2– via N3 loss was also observed. Density functional theory computations predict that the UO(NO)Cl2– complex has nonplanar Cs symmetry and a singlet ground state. Analysis of the bonding of the UO(NO)Cl2– complex shows that the side-on bonded NO moiety can be considered as NO3–, suggesting a formal oxidation state of U(VI). Activation of the uranyl oxo bond in UO2(N3)Cl2– to form UO(NO)Cl2– and N2 was computed to be endothermic by 169 kJ/mol, which is energetically more favorable than formation of NUOCl2– and UO2Cl2–. The observation of UO2Cl2– during CID is most likely due to the absence of an energy barrier for neutral ligand loss.

  4. Complex conductivity response to microbial growth and biofilm formation on phenanthrene spiked medium

    NASA Astrophysics Data System (ADS)

    Albrecht, Remy; Gourry, Jean Christophe; Simonnot, Marie-Odile; Leyval, Corinne

    2011-11-01

    Several laboratory studies have recently demonstrated the utility of geophysical methods for the investigation of microbial-induced changes over contaminated sites. However, it remains difficult to distinguish the effects due to the new physical properties imparted by microbial processes, to bacterial growth, or to the development of bacterial biofilm. We chose to study the influence of biofilm formation on geophysical response using complex conductivity measurements (0.1-1000 Hz) in phenanthrene-contaminated media. Biotic assays were conducted with two phenanthrene (PHE) degrading bacterial strains: Burkholderia sp (NAH1), which produced biofilm and Stenophomonas maltophilia (MATE10), which did not, and an abiotic control. Results showed that bacterial densities for NAH1 and MATE10 strains continuously increased at the same rate during the experiment. However, the complex conductivity signature showed noticeable differences between the two bacteria, with a phase shift of 50 mrad at 4 Hz for NAH1, which produced biofilm. Biofilm volume was quantified by Scanning Confocal Laser Microscopy (SCLM). Significant correlations were established between phase shift decrease and biofilm volume for NAH1 assays. Results suggest that complex conductivity measurements, specifically phase shift, can be a useful indicator of biofilm formation inside the overall signal of microbial activity on contaminated sites.

  5. SOHLH2 is essential for synaptonemal complex formation during spermatogenesis in early postnatal mouse testes

    PubMed Central

    Park, Miree; Lee, Youngeun; Jang, Hoon; Lee, Ok-Hee; Park, Sung-Won; Kim, Jae-Hwan; Hong, Kwonho; Song, Hyuk; Park, Se-Pill; Park, Yun-Yong; Ko, Jung Jae; Choi, Youngsok

    2016-01-01

    Spermatogenesis- and oogenesis-specific helix-loop-helix transcription factor 2 (SOHLH2) is exclusively expressed in germ cells of the gonads. Previous studies show that SOHLH2 is critical for spermatogenesis in mouse. However, the regulatory mechanism of SOHLH2 during early spermatogenesis is poorly understood. In the present study, we analyzed the gene expression profile of the Sohlh2-deficient testis and examined the role of SOHLH2 during spermatogenesis. We found 513 genes increased in abundance, while 492 genes decreased in abundance in 14-day-old Sohlh2-deficient mouse testes compared to wildtype mice. Gene ontology analysis revealed that Sohlh2 disruption effects the relative abundance of various meiotic genes during early spermatogenesis, including Spo11, Dmc1, Msh4, Prdm9, Sycp1, Sycp2, Sycp3, Hormad1, and Hormad2. Western blot analysis and immunostaining showed that SYCP3, a component of synaptonemal complex, was significantly less abundant in Sohlh2-deficient spermatocytes. We observed a lack of synaptonemal complex formation during meiosis in Sohlh2-deficient spermatocytes. Furthermore, we found that SOHLH2 interacted with two E-boxes on the mouse Sycp1 promoter and Sycp1 promoter activity increased with ectopically expressed SOHLH2. Taken together, our data suggest that SOHLH2 is critical for the formation of synaptonemal complexes via its regulation of Sycp1 expression during mouse spermatogonial differentiation. PMID:26869299

  6. Coordination Modes in the Formation of Ternary Complexes of Am(III), Cm(III) and Eu(III) with EDTA and NTA: TRLFS, 13C NMR, EXAFS, and Thermodynamics of the complexation.

    SciTech Connect

    Mathur,J.; Thakur, P.; Dodge, C.; Francis, A.; Choppin, G.

    2006-01-01

    The formation and the structure of the ternary complexes of trivalent Am, Cm, and Eu with mixtures of EDTA+NTA (ethylenediamine tetraacetate and nitrilotriacetate) have been studied by time-resolved laser fluorescence spectroscopy, {sup 13}C NMR, extended X-ray absorption fine structure, and two-phase metal ion equilibrium distribution at 6.60 m (NaClO{sub 4}) and a hydrogen ion concentration value (pcH) between 3.60 and 11.50. In the ternary complexes, EDTA binds via four carboxylates and two nitrogens, while the binding of the NTA varies with the hydrogen ion concentration, pcH, and the concentration ratios of the metal ion and the ligand. When the concentration ratios of the metal to ligand is low (1:1:1-1:1:2), two ternary complexes, M(EDTA)(NTAH){sup 3-} and M(EDTA)(NTA){sup 4-}, are formed at pcH ca. 9.00 in which NTA binds via three carboxylates, via two carboxylates and one nitrogen, or via two carboxylates and a H{sub 2}O. At higher ratios (1:1:20 and 1:10:10) and pcH's of ca. 9.00 and 11.50, one ternary complex, M(EDTA)(NTA){sup 4-}, is formed in which NTA binds via three carboxylates and not via nitrogen. The two-phase equilibrium distribution studies at tracer concentrations of Am, Cm, and Eu have also confirmed the formation of the ternary complex M(EDTA)(NTA){sup 4-} at temperatures between 0 and 60 {sup o}C. The stability constants (log{beta}{sub 111}) for these metal ions increase with increasing temperature. The endothermic enthalpy and positive entropy indicated a significant effect of cation dehydration in the formation of the ternary complexes at high ionic strength.

  7. Chiral symmetry breaking in complex chemical systems during formation of life on earth

    NASA Astrophysics Data System (ADS)

    Konstantinova, A. F.; Konstantinov, K. K.

    2015-09-01

    The chiral symmetry in complex chemical systems containing many amino acids and characterized by many similar chemical reactions (a situation corresponding to the formation of life on Earth) is considered. It is shown that effective averaging over similar reaction channels may lead to very weak effective enantioselectivity, which does not allow for chiral symmetry breaking in most known models. A class of models with simple and catalytic synthesis of one amino acid, the formation of peptides with a length reaching three, and the precipitation of one insoluble pair of materials is analyzed. It is proven that chiral symmetry breaking may occur in one possible version from an insoluble pair of materials even in the complete absence of catalytic synthesis of amino acid. It is shown that the presence of weakly enantioselective catalytic synthesis in a model significantly increases the number of possible versions in which chiral symmetry breaks.

  8. Two quorum sensing systems control biofilm formation and virulence in members of the Burkholderia cepacia complex

    PubMed Central

    Suppiger, Angela; Schmid, Nadine; Aguilar, Claudio; Pessi, Gabriella; Eberl, Leo

    2013-01-01

    The Burkholderia cepacia complex (Bcc) consists of 17 closely related species that are problematic opportunistic bacterial pathogens for cystic fibrosis patients and immunocompromised individuals. These bacteria are capable of utilizing two different chemical languages: N-acyl homoserine lactones (AHLs) and cis-2-unsaturated fatty acids. Here we summarize the current knowledge of the underlying molecular architectures of these communication systems, showing how they are interlinked and discussing how they regulate overlapping as well as specific sets of genes. A particular focus is laid on the role of these signaling systems in the formation of biofilms, which are believed to be highly important for chronic infections. We review genes that have been implicated in the sessile lifestyle of this group of bacteria. The new emerging role of the intracellular second messenger cyclic dimeric guanosine monophosphate (c-di-GMP) as a downstream regulator of the fatty acid signaling cascade and as a key factor in biofilm formation is also discussed. PMID:23799665

  9. Struvite crystal growth inhibition by trisodium citrate and the formation of chemical complexes in growth solution

    NASA Astrophysics Data System (ADS)

    Prywer, Jolanta; Mielniczek-Brzóska, Ewa; Olszynski, Marcin

    2015-05-01

    Effect of trisodium citrate on the crystallization of struvite was studied. To evaluate such an effect an experiment of struvite growth from artificial urine was performed. The investigations are related to infectious urinary stones formation. The crystallization process was induced by the addition of aqueous ammonia solution to mimic the bacterial activity. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to struvite formation and decreases the growth efficiency of struvite. The inhibitory effect of trisodium citrate on the nucleation and growth of struvite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is related with the fact that trisodium citrate binds NH4 + and Mg2+ ions in the range of pH from 7 to 9.5 characteristic for struvite precipitation. The most important is the MgCit- complex whose concentration strongly depends on an increase in pH rather than on an increase in citrate concentrations.

  10. Cord formation in BACTEC(TM) medium aids rapid identification of Mycobacterium tuberculosis complex.

    PubMed

    O'Hara, G A; Abdullah, S; Creer, D D; Elsaghier, A F

    2015-06-01

    Mycobacterium tuberculosis complex (MTC) organisms form serpentine cords in fluid culture medium. Reporting of a presumptive identification of MTC based on cording allows rapid identification of patients with tuberculosis. A total of 612 positive mycobacterial cultures from 316 patients over 3 years (2008-2010) were evaluated for the presence of cord formation. Cording was identified in 426 (69.6%) specimens, while the reference laboratory confirmed M. tuberculosis in 424 specimens (69.3%). Sensitivity of the test in our laboratory was 99.1% (95%CI 97.4-99.7) and specificity was 96.8% (95%CI 92.8-98.7). Presumptive identification of M. tuberculosis by the presence of cording formation is both sensitive and specific. PMID:25946364

  11. A new mechanism for the control of phenoloxidase activity: inhibition and complex formation with quinone isomerase.

    PubMed

    Sugumaran, M; Nellaiappan, K; Valivittan, K

    2000-07-15

    Insect phenoloxidases participate in three physiologically important processes, viz., cuticular hardening (sclerotization), defense reactions (immune reaction), and wound healing. Arrest or even delay of any of these processes compromises the survival of insects. Since the products of phenoloxidase action, viz., quinones, are cytotoxic, uncontrolled phenoloxidase action is deleterious to the insects. Therefore, the activity of this important enzyme has to be finely controlled. A novel inhibition of insect phenoloxidases, which serves as a new regulatory mechanism for control of its activity, is described. The activity of phenoloxidases isolated from both Sarcophaga bullata and Manduca sexta is drastically inhibited by quinone isomerase (isolated from Calliphora), an enzyme that utilizes the phenoloxidase-generated 4-alkylquinones. In turn, phenoloxidase reciprocated the inhibition of isomerase. By forming a complex and controlling each other's activity, these two enzymes seem to regulate the levels of endogenously quinones. In support of this contention, an endogenous complex consisting of phenoloxidase, quinone isomerase, and quinone methide isomerase was characterized from the insect, Calliphora. This sclerotinogenic complex was isolated and purified by borate extraction of the larval cuticle, ammonium sulfate precipitation, and Sepharose 6B column chromatography. The complex exhibited a molecular mass of about 620-680 kDa, as judged by size-exclusion chromatography on Sepharose 6B and HPLC and did not even enter 3% polyacrylamide gel during electrophoresis. The phenoloxidase activity of the complex exhibited a wide substrate specificity. Incubation of the complex with N-acetyldopamine rapidly generated N-acetylnorepinephrine, dehydro-N-acetyldopamine, and its dimers. In addition, transient accumulation of N-acetyldopamine quinone was also observed. These results confirm the presence of phenoloxidase, quinone isomerase, and quinone methide isomerase in the complex. Attempts to dissociate the complex with even trace amounts of SDS ended in the total loss of quinone isomerase activity. The complex does not seems to be made up of stoichiometric amounts of individual enzymes as the ratio of phenoloxidase to quinone isomerase varied from preparation to preparation. It is proposed that the complex formation between sequential enzymes of sclerotinogenic pathway is advantageous for the organism to effectively channel various reactive intermediates during cuticular hardening. PMID:10898942

  12. CLOPPA-IPPP analysis of cooperative effects in hydrogen-bonded molecular complexes. Application to intermolecular 2hJ(N,C) spin-spin coupling constants in linear (CNH)n complexes.

    PubMed

    Giribet, Claudia G; Aza, Martn C Ruiz de

    2008-05-01

    The cooperative effects on NMR indirect nuclear coupling constants are analyzed by means of the IPPP-CLOPPA approach (where CLOPPA is the Contributions from Localized Orbitals within the Polarization Propagator Approach and IPPP is the Inner Projections of the Polarization Propagator). The decomposition of the J coupling allows one to classify these effects as those due to changes in the geometric structure and those that directly involve the transmission mechanisms. This latter contribution admits a further classification, taking into account its electronic origin. As an example, the cooperative effects on intermolecular 2hJ(N,C) couplings of the linear complexes (CNH)n (n = 2, 3, 4) are discussed. PMID:18410158

  13. IR dust bubbles: gas, dust and star formation in the S21-S24 complex

    NASA Astrophysics Data System (ADS)

    Cappa, E. C.; Romero, A. G.; Vasquez, J.; Firpo, V.; Dorunea, N.; Rubio, M.; Kobilnicky, C.

    2013-06-01

    Churchwell et al. (2006) identified many IR dust bubbles in the GLIMPSE images at 8 μm. Among these bubbles, S21, S22, S23, and S24 conform a poorly studied complex plenty of small scale bubbles, with IRDCs and signposts of recent star formation, located at about 4.5 kpc. Based on 12CO(2-1), 13CO(2-1), and 13CO(3-2) line observations obtained with the APEX telescope (angular resolution of 20"-30"), LABOCA continuum observations at 870 μm (angular resolution of 18.5") also from APEX, Spitzer-IRAC and -MIPS images in the near and mid IR (3.6 to 24 μm, and Herschel-PACS and -SPIRE images in the far infrared (70-500 μm), we performed an analysis of the characteristics of the gas and dust in this high density complex. This study allowed molecular shells linked to these bubbles to be revealed, and to estimate new distances, excitation conditions, masses, and ambient densities. Cold dust counterparts were revealed by Herschel and LABOCA images, showing the material available for new generations of stars. In addition to the presence of EGOs and methanol masers, a search for young stellar objets in the complex using the available data at several wavelengths in the infrared revealed many active areas of star formation coincident with the densest regions. We compare our results with those for other IR dust bubbles and investigate the possibility that the expansion of the bubbles has triggered the star formation activity.

  14. Mechanisms of chlorophyllin anticarcinogenesis against aflatoxin B1: complex formation with the carcinogen.

    PubMed

    Breinholt, V; Schimerlik, M; Dashwood, R; Bailey, G

    1995-06-01

    Chlorophyllin (CHL), a food-grade derivative of the green plant pigment chlorophyll, has recently been shown in this laboratory to be a potent inhibitor in vivo of hepatic aflatoxin B1 (AFB1)-DNA adduction and hepatocarcinogenesis (Breinholt et al. (1995) Cancer Res. 55, 57-62). We report here that CHL forms a strong noncovalent complex with AFB1 in vitro (dissociation constant (Kd) by Scatchard analysis = 1.4 (+/- 0.4) microM based on copper chlorin content), which may contribute to its anticarcinogenic activity. Kd values for the related porphyrins chlorine e6, protoporphyrin IX, and zinc protoporphyrin IX were also of the same order of magnitude as that of the commercial CHL. Mole ratio analysis provided evidence that all porphyrins examined associate with AFB1 at an approximate one to one stoichiometric ratio. Energy minimization computer modeling of the complex indicates a favorable association energy of -20 kcal/mol, independent of oxidation state of the 8,9-double bond of AFB1. AFB1 incubated in vitro with liver microsomes in the presence of added CHL showed comparable levels of inhibition in the production of several phase 1 metabolites, including the postulated procarcinogenic metabolite AFB1 8,9-epoxide. Kinetic analysis of microsome-catalyzed AFB1-DNA adduction suggested a CHL inhibition constant near 10 microM chlorin. In vivo, addition of CHL to concentrated AFB1 solutions followed by gavage administration resulted in dose-dependent inhibition of hepatic AFB1-DNA adduction, whereas the same dosages of AFB1 and CHL incorporated into a single bolus of trout diet for gavage provided less protection at all CHL doses.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7548730

  15. Spontaneous formation of complex and ordered structures on oxygen-plasma-treated elastomeric polydimethylsiloxane

    NASA Astrophysics Data System (ADS)

    Chua, Diana B. H.; Ng, H. T.; Li, Sam F. Y.

    2000-02-01

    In this letter, we describe the spontaneous formation of complex and ordered structures on polydimethylsiloxane when subjected to oxygen plasma treatment. Periodicity of wavy structures from submicrometer to micrometer length scales could be generated reproducibly and quantitatively accounted for. The origin of these patterns could be related to the relief of compressive stress by buckling of the silica-like thin film that was formed as a result of the plasma exposures. Atomic force microscope has been used to characterize the varied trends of the modifications. The present approach could be extended to the fabrication of intricate ordered patterns on polymeric surfaces with integrated relief structures obtained by soft lithography and micromolding.

  16. Formation of charge-transfer-complex in organic:metal oxides systems

    NASA Astrophysics Data System (ADS)

    Wu, S. P.; Kang, Y.; Liu, T. L.; Jin, Z. H.; Jiang, N.; Lu, Z. H.

    2013-04-01

    It is found that composite systems consisting of 4,4'-bis(carbazol-9-yl)biphenyl (CBP) and molybdenum trioxide (MoO3) form an IR absorption band around 847 nm. It is also found that the vibrational modes of the CBP, as measured by Fourier Transform Infrared Spectroscopy, are quenched upon the formation of charge-transfer-complex (CTC) between CBP and MoO3. By examining several sets of organic:metal oxides systems, we discovered that the IR absorption band of the CTCs follow two distinct mechanisms depending on the nature and location of the HOMOs in the organic molecules.

  17. Preferential formation of the different hydrogen bonds and their effects in tetrahydrofuran and tetrahydropyran microhydrated complexes.

    PubMed

    Vallejos, Margarita M; Peruchena, Nélida M

    2012-04-26

    The role of cycloether-water (c-w) and water-water (w-w) hydrogen bonds (H-bonds) on the stability of the tetrahydrofuran THF/(H(2)O)(n) and the tetrahydropyran THP/(H(2)O)(n) complexes with n = 1-4 was investigated herein using the density functional and ab initio methods and the atoms in molecules theory. Geometry optimizations for these complexes were carried out with various possible initial guess structures. It was revealed that the major contributions of the mono and dihydrated complexes came from c-w H-bonds. A competition between c-w and w-w H-bonds contribution was observed for trihydrated complexes. For most of tetrahydrated complexes, the inter-water H-bonds provided the greatest contribution, whereas the c-w contributions were small but not negligible. It was confirmed that to produce a hydrophobic hydration of cycloethers, the C-H···O(w) H-bond should be associated with a network of H-bonds that connects both portions of the solute, through the formation of a bifunctional H-bond. A linear correlation is obtained for the sum of electron density at the bond critical points (ρ(b)) with the interaction energy (ΔE) and with the solute-solvent interaction energy (ΔE(s-w)) of the microhydrated complexes. In addition, a new way to estimate the energetic contribution as well as the preferential formation of the different H-bonds based completely on ρ(b) was found. Even more, it allows to differentiate the contribution from c-w interactions in both hydrophilic and hydrophobic contributions, it is therefore a useful tool for studying the hydration of large biomolecules. The analysis of the modifications in the atomic and group properties brought about by successive addition of H(2)O molecules allowed to pinpoint the atoms or molecular groups that undergo the greatest changes in electron population and energetic stabilization. It was identified that the remarkable stabilization of the water oxygen atoms is crucial for the stabilization of the complexes. PMID:22429188

  18. Formation and dynamics of "waterproof" photoluminescent complexes of rare earth ions in crowded environment.

    PubMed

    Ignatova, Tetyana; Blades, Michael; Duque, Juan G; Doorn, Stephen K; Biaggio, Ivan; Rotkin, Slava V

    2014-12-28

    Understanding behavior of rare-earth ions (REI) in crowded environments is crucial for several nano- and bio-technological applications. Evolution of REI photoluminescence (PL) in small compartments inside a silica hydrogel, mimic to a soft matter bio-environment, has been studied and explained within a solvation model. The model uncovered the origin of high PL efficiency to be the formation of REI complexes, surrounded by bile salt (DOC) molecules. Comparative study of these REI-DOC complexes in bulk water solution and those enclosed inside the hydrogel revealed a strong correlation between an up to 5-longer lifetime of REIs and appearance of the DOC ordered phase, further confirmed by dynamics of REI solvation shells, REI diffusion experiments and morphological characterization of microstructure of the hydrogel. PMID:25379879

  19. Galvanic Cells and the Determination of Equilibrium Constants

    ERIC Educational Resources Information Center

    Brosmer, Jonathan L.; Peters, Dennis G.

    2012-01-01

    Readily assembled mini-galvanic cells can be employed to compare their observed voltages with those predicted from the Nernst equation and to determine solubility products for silver halides and overall formation constants for metal-ammonia complexes. Results obtained by students in both an honors-level first-year course in general chemistry and…

  20. Galvanic Cells and the Determination of Equilibrium Constants

    ERIC Educational Resources Information Center

    Brosmer, Jonathan L.; Peters, Dennis G.

    2012-01-01

    Readily assembled mini-galvanic cells can be employed to compare their observed voltages with those predicted from the Nernst equation and to determine solubility products for silver halides and overall formation constants for metal-ammonia complexes. Results obtained by students in both an honors-level first-year course in general chemistry and

  1. Radiation increases the cellular uptake of exosomes through CD29/CD81 complex formation

    SciTech Connect

    Hazawa, Masaharu; Tomiyama, Kenichi; Saotome-Nakamura, Ai; Obara, Chizuka; Yasuda, Takeshi; Gotoh, Takaya; Tanaka, Izumi; Yakumaru, Haruko; Ishihara, Hiroshi; Tajima, Katsushi

    2014-04-18

    Highlights: • Radiation increases cellular uptake of exosomes. • Radiation induces colocalization of CD29 and CD81. • Exosomes selectively bind the CD29/CD81 complex. • Radiation increases the cellular uptake of exosomes through CD29/CD81 complex formation. - Abstract: Exosomes mediate intercellular communication, and mesenchymal stem cells (MSC) or their secreted exosomes affect a number of pathophysiologic states. Clinical applications of MSC and exosomes are increasingly anticipated. Radiation therapy is the main therapeutic tool for a number of various conditions. The cellular uptake mechanisms of exosomes and the effects of radiation on exosome–cell interactions are crucial, but they are not well understood. Here we examined the basic mechanisms and effects of radiation on exosome uptake processes in MSC. Radiation increased the cellular uptake of exosomes. Radiation markedly enhanced the initial cellular attachment to exosomes and induced the colocalization of integrin CD29 and tetraspanin CD81 on the cell surface without affecting their expression levels. Exosomes dominantly bound to the CD29/CD81 complex. Knockdown of CD29 completely inhibited the radiation-induced uptake, and additional or single knockdown of CD81 inhibited basal uptake as well as the increase in radiation-induced uptake. We also examined possible exosome uptake processes affected by radiation. Radiation-induced changes did not involve dynamin2, reactive oxygen species, or their evoked p38 mitogen-activated protein kinase-dependent endocytic or pinocytic pathways. Radiation increased the cellular uptake of exosomes through CD29/CD81 complex formation. These findings provide essential basic insights for potential therapeutic applications of exosomes or MSC in combination with radiation.

  2. Fluids circulations during the formation of the Naxos Metamorphic Core Complex (Greece)

    NASA Astrophysics Data System (ADS)

    Vanderhaeghe, Olivier; Boiron, Marie-Christine; Siebenaller, Luc

    2015-04-01

    The island of Naxos, in the central part of the Cycladic Metamorphic Core Complex (Greece) represents a perfect example to address the evolution of fluid circulations during collapse of an orogenic belt. It displays a complex detachment system characterized by mylonites, cataclasites and high-angle normal faults which geometric relationships reflect rheological layering of the orogenic crust and its evolution during collapse. The chemistry of fluid inclusions determined by microthermometry, RAMAN spectroscopy, LA-ICPMS, and crush-leach combined with C and H isotopic signatures point to three distinct types of fluids, namely (i) a H2O-dominated fluid, (ii) a composite H2O-CO2 fluid, and (iii) a NaCl-rich fluid concentrated in metals. These different types of fluids are interpreted to reflect mixtures to various degrees among fluids generated by (i) condensation of clouds (meteoric aqueous fluid), (ii) dehydration and decarbonatation of metasedimentary rocks during metamorphism (metamorphic aqueous-carbonic fluid), and (iii) crystallization of granitic magmas (magmatic saline fluid with high metal contents). The distribution of fluids with respect to microstructures evidences the close link between deformation and fluid circulations at the mineral scale from intracristalline deformation to fracturing. The orientation of fluid inclusion planes, veins and alteration zones allows to identify the scale and geometry of the reservoir into which fluids are circulating and their evolution during the formation of the Metamorphic Core Complex. These data indicate that the orogenic crust is subdivided in two reservoirs separated by the ductile/fragile transition. Meteoric fluids circulate in the upper crust affected by brittle deformation whereas metamorphic and magmatic fluids circulate in relation to intracristalline ductile deformation affecting the lower crust. The geometry of these reservoirs evolves during the formation of the Naxos Metamorphic Core Complex as the orogenic crust is extended and cooled. In particular, the exhumation of metamorphic rocks and their transfer from the ductile to the fragile reservoir is marked by a transition from a lithostatic to an hydrostatic pressure associated with a drastic decrease of the geothermal gradient from 60-100C/km to 35-60C/km. This implies that fluid circulations during the formation of a Metamorphic Core Complex are intimately related to the rheologic layering of the orogenic crust and its evolution during collapse. Accordingly, the ductile/fragile transition, in addition to represent a fundamental rheologic boundary, also corresponds to a thermal and hydrologic crustal-scale transition zone.

  3. Hormad1 mutation disrupts synaptonemal complex formation, recombination, and chromosome segregation in mammalian meiosis.

    PubMed

    Shin, Yong-Hyun; Choi, Youngsok; Erdin, Serpil Uckac; Yatsenko, Svetlana A; Kloc, Malgorzata; Yang, Fang; Wang, P Jeremy; Meistrich, Marvin L; Rajkovic, Aleksandar

    2010-11-01

    Meiosis is unique to germ cells and essential for reproduction. During the first meiotic division, homologous chromosomes pair, recombine, and form chiasmata. The homologues connect via axial elements and numerous transverse filaments to form the synaptonemal complex. The synaptonemal complex is a critical component for chromosome pairing, segregation, and recombination. We previously identified a novel germ cell-specific HORMA domain encoding gene, Hormad1, a member of the synaptonemal complex and a mammalian counterpart to the yeast meiotic HORMA domain protein Hop1. Hormad1 is essential for mammalian gametogenesis as knockout male and female mice are infertile. Hormad1 deficient (Hormad1(-/) (-)) testes exhibit meiotic arrest in the early pachytene stage, and synaptonemal complexes cannot be visualized by electron microscopy. Hormad1 deficiency does not affect localization of other synaptonemal complex proteins, SYCP2 and SYCP3, but disrupts homologous chromosome pairing. Double stranded break formation and early recombination events are disrupted in Hormad1(-/) (-) testes and ovaries as shown by the drastic decrease in the ?H2AX, DMC1, RAD51, and RPA foci. HORMAD1 co-localizes with ?H2AX to the sex body during pachytene. BRCA1, ATR, and ?H2AX co-localize to the sex body and participate in meiotic sex chromosome inactivation and transcriptional silencing. Hormad1 deficiency abolishes ?H2AX, ATR, and BRCA1 localization to the sex chromosomes and causes transcriptional de-repression on the X chromosome. Unlike testes, Hormad1(-/) (-) ovaries have seemingly normal ovarian folliculogenesis after puberty. However, embryos generated from Hormad1(-/) (-) oocytes are hyper- and hypodiploid at the 2 cell and 8 cell stage, and they arrest at the blastocyst stage. HORMAD1 is therefore a critical component of the synaptonemal complex that affects synapsis, recombination, and meiotic sex chromosome inactivation and transcriptional silencing. PMID:21079677

  4. Zeaxanthin Radical Cation Formation in Minor Light-Harvesting Complexes of Higher Plant Antenna

    SciTech Connect

    Avenson, Thomas H.; Ahn, Tae Kyu; Zigmantas, Donatas; Niyogi, Krishna K.; Li, Zhirong; Ballottari, Matteo; Bassi, Roberto; Fleming, Graham R.

    2008-01-31

    Previous work on intact thylakoid membranes showed that transient formation of a zeaxanthin radical cation was correlated with regulation of photosynthetic light-harvesting via energy-dependent quenching. A molecular mechanism for such quenching was proposed to involve charge transfer within a chlorophyll-zeaxanthin heterodimer. Using near infrared (880-1100 nm) transient absorption spectroscopy, we demonstrate that carotenoid (mainly zeaxanthin) radical cation generation occurs solely in isolated minor light-harvesting complexes that bind zeaxanthin, consistent with the engagement of charge transfer quenching therein. We estimated that less than 0.5percent of the isolated minor complexes undergo charge transfer quenching in vitro, whereas the fraction of minor complexes estimated to be engaged in charge transfer quenching in isolated thylakoids was more than 80 times higher. We conclude that minor complexes which bind zeaxanthin are sites of charge transfer quenching in vivo and that they can assume Non-quenching and Quenching conformations, the equilibrium LHC(N)<--> LHC(Q) of which is modulated by the transthylakoid pH gradient, the PsbS protein, and protein-protein interactions.

  5. Ice Complex formation in arctic East Siberia during the MIS3 Interstadial

    NASA Astrophysics Data System (ADS)

    Wetterich, Sebastian; Tumskoy, Vladimir; Rudaya, Natalia; Andreev, Andrei A.; Opel, Thomas; Meyer, Hanno; Schirrmeister, Lutz; Hls, Matthias

    2014-01-01

    A continuous 15 m long sequence of Ice Complex permafrost (Yedoma) exposed in a thermo-cirque at the southern coast of Bol'shoy Lyakhovsky Island (New Siberian Archipelago, Dmitry Laptev Strait) was studied to reconstruct past landscape and environmental dynamics. The sequence accumulated during the Marine Isotope Stage 3 (MIS3) Interstadial between >49 and 29 ka BP in an ice-wedge polygon. The frozen deposits were cryolithologically described and sampled on a vertical bluff between two ice wedges. According to sedimentological and geochronological data, the section is subdivided into three units which correlate with environmental conditions of the early, middle, and late MIS3 period. Palynological data support this stratification. The stable isotope signature of texture ice in the polygon structure reflects fractionation due to local freeze-thaw processes, while the signature of an approximately 5 m wide and more than 17 m high ice wedge fits very well into the regional stable-water isotope record. Regional climate dynamics during the MIS3 Interstadial and local landscape conditions of the polygonal patterned ground controlled the Ice Complex formation. The sequence presented here completes previously published MIS3 permafrost records in Northeast Siberia. Late Quaternary stadial-interstadial climate variability in arctic West Beringia is preserved at millennial resolution in the Ice Complex. A MIS3 climate optimum was revealed between 48 and 38 ka BP from the Ice Complex on Bol'shoy Lyakhovsky Island.

  6. Coupling of downstream RNA polymerase-promoter interactions with formation of catalytically competent transcription initiation complex

    PubMed Central

    Mekler, Vladimir; Minakhin, Leonid; Borukhov, Sergei; Mustaev, Arkady; Severinov, Konstantin

    2014-01-01

    Bacterial RNA polymerase (RNAP) makes extensive contacts with duplex DNA downstream of the transcription bubble in initiation and elongation complexes. We investigated the role of downstream interactions in formation of catalytically competent transcription initiation complex by measuring initiation activity of stable RNAP complexes with model promoter DNA fragments whose downstream ends extend from +3 to +21 relative to the transcription start site at +1. We found that DNA downstream of position +6 does not play a significant role in transcription initiation when RNAP-promoter interactions upstream of the transcription start site are strong and promoter melting region is AT-rich. Further shortening of downstream DNA dramatically reduces efficiency of transcription initiation. The boundary of minimal downstream DNA duplex needed for efficient transcription initiation shifted further away from the catalytic center upon increasing the GC content of promoter melting region or in the presence of bacterial stringent response regulators DksA and ppGpp. These results indicate that the strength of RNAP-downstream DNA interactions has to reach a certain threshold to retain the catalytically competent conformation of the initiation complex and that establishment of contacts between RNAP and downstream DNA can be coupled with promoter melting. The data further suggest that RNAP interactions with DNA immediately downstream of the transcription bubble are particularly important for initiation of transcription. We hypothesize that these active center-proximal contacts stabilize the DNA template strand in the active center cleft and/or position the RNAP clamp domain to allow RNA synthesis. PMID:25311862

  7. Munc18-1 prevents the formation of ectopic SNARE complexes in living cells.

    PubMed

    Medine, Claire N; Rickman, Colin; Chamberlain, Luke H; Duncan, Rory R

    2007-12-15

    Membrane trafficking in eukaryotic cells must be strictly regulated both temporally and spatially. The assembly at the plasma membrane of the ternary SNARE complex, formed between syntaxin1a, SNAP-25 and VAMP, is essential for efficient exocytotic membrane fusion. These exocytotic SNAREs are known to be highly promiscuous in their interactions with other non-cognate SNAREs. It is therefore an important cellular requirement to traffic exocytotic SNARE proteins through the endoplasmic reticulum and Golgi complex while avoiding ectopic interactions between SNARE proteins. Here, we show that syntaxin1a traffics in an inactive form to the plasma membrane, requiring a closed-form interaction, but not N-terminal binding, with munc18-1. If syntaxin is permitted to interact with SNAP-25, both proteins fail to traffic to the plasma membrane, becoming trapped in intracellular compartments. The munc18-1-syntaxin interactions must form before syntaxin encounters SNAP-25 in the Golgi complex, preventing the formation of intracellular exocytotic SNARE complexes there. Upon delivery to the plasma membrane, most SNARE clusters in resting cells do not produce detectable FRET between t-SNARE proteins. These observations highlight the crucial role that munc18-1 plays in trafficking syntaxin through the secretory pathway. PMID:18057031

  8. Dinitrosyl iron complexes with cysteine. Kinetics studies of the formation and reactions of DNICs in aqueous solution.

    PubMed

    Pereira, José Clayston Melo; Iretskii, Alexei V; Han, Rui-Min; Ford, Peter C

    2015-01-14

    Kinetics studies provide mechanistic insight regarding the formation of dinitrosyl iron complexes (DNICs) now viewed as playing important roles in the mammalian chemical biology of the ubiquitous bioregulator nitric oxide (NO). Reactions in deaerated aqueous solutions containing FeSO4, cysteine (CysSH), and NO demonstrate that both the rates and the outcomes are markedly pH dependent. The dinuclear DNIC Fe2(μ-CysS)2(NO)4, a Roussin's red salt ester (Cys-RSE), is formed at pH 5.0 as well as at lower concentrations of cysteine in neutral pH solutions. The mononuclear DNIC Fe(NO)2(CysS)2(-) (Cys-DNIC) is produced from the same three components at pH 10.0 and at higher cysteine concentrations at neutral pH. The kinetics studies suggest that both Cys-RSE and Cys-DNIC are formed via a common intermediate Fe(NO)(CysS)2(-). Cys-DNIC and Cys-RSE interconvert, and the rates of this process depend on the cysteine concentration and on the pH. Flash photolysis of the Cys-RSE formed from Fe(II)/NO/cysteine mixtures in anaerobic pH 5.0 solution led to reversible NO dissociation and a rapid, second-order back reaction with a rate constant kNO = 6.9 × 10(7) M(-1) s(-1). In contrast, photolysis of the mononuclear-DNIC species Cys-DNIC formed from Fe(II)/NO/cysteine mixtures in anaerobic pH 10.0 solution did not labilize NO but instead apparently led to release of the CysS(•) radical. These studies illustrate the complicated reaction dynamics interconnecting the DNIC species and offer a mechanistic model for the key steps leading to these non-heme iron nitrosyl complexes. PMID:25479566

  9. Computational approaches that predict metabolic intermediate complex formation with CYP3A4 (+b5).

    PubMed

    Jones, David R; Ekins, Sean; Li, Lang; Hall, Stephen D

    2007-09-01

    Some mechanism-based inhibitors cause irreversible inhibition by forming a metabolic intermediate complex (MIC) with cytochrome P450. In the present study, 54 molecules (substrates of CYP3A and amine-containing compounds that are not known substrates of CYP3A) were spectrophotometrically assessed for their propensity to cause MIC formation with recombinant CYP3A4 (+b(5)). Comparisons of common physicochemical properties showed that mean (+/-S.D.) mol. wt. of MIC-forming compounds was significantly greater than mean mol. wt. of non-MIC-forming compounds, 472 (+/-173) versus 307 (+/-137), respectively. Computational pharmacophores, logistic regression, and recursive partitioning (RP) approaches were applied to predict MIC formation from molecular structure and to generate a quantitative structure activity relationship. A pharmacophore built with SKF-525A (2-diethylaminoethyl 2:2-diphenylvalerate hydrochloride), erythromycin, amprenavir, and norverapamil indicated that four hydrophobic features and a hydrogen bond acceptor were important for these MIC-forming compounds. Two different RP methods using either simple descriptors or 2D augmented atom descriptors indicated that hydro-phobic and hydrogen bond acceptor features were required for MIC formation. Both of these RP methods correctly predicted the MIC formation status with CYP3A4 for 10 of 12 literature molecules in an independent test set. Logistic multiple regression and a third classification tree model predicted 11 of 12 molecules correctly. Both models possessed a hydrogen bond acceptor and represent an approach for predicting CYP3A4 MIC formation that can be improved using more data and molecular descriptors. The preliminary pharmacophores provide structural insights that complement those for CYP3A4 inhibitors and substrates. PMID:17537872

  10. Theoretical study of the formation of mercury (Hg2+) complexes in solution using an explicit solvation shell in implicit solvent calculations.

    PubMed

    Afaneh, Akef T; Schreckenbach, Georg; Wang, Feiyue

    2014-09-25

    The structures and harmonic vibrational frequencies of water clusters (H2O)n, n = 1-10, have been computed using the M06-L/, B3LYP/, and CAM-BLYP/cc-pVTZ levels of theories. On the basis of the literature and our results, we use three hexamer structures of the water molecules to calculate an estimated "experimental" average solvation free energy of [Hg(H2O)6](2+). Aqueous formation constants (log K) for Hg(2+) complexes, [Hg(L)m(H2O)n](2-mq), L = Cl(-), HO(-), HS(-), and S(2-), are calculated using a combination of experimental (solvation free energies of ligands and Hg(2+)) and calculated gas- and liquid-phase free energies. A combined approach has been used that involves attaching n explicit water molecules to the Hg(2+) complexes such that the first coordination sphere is complete, then surrounding the resulting (Hg(2+)-Lm)-(OH2)n cluster by a dielectric continuum, and using suitable thermodynamic cycles. This procedure significantly improves the agreement between the calculated log K values and experiment. Thus, for some neutral and anionic Hg(II) complexes, particularly Hg(II) metal ion surrounded with homo- or heteroatoms, augmenting implicit solvent calculations with sufficient explicit water molecules to complete the first coordination sphere is required-and adequate-to account for strong short-range hydrogen bonding interactions between the anion and the solvent. Calculated values for formation constants of Hg(2+) complexes with S(2-) and SH(-) are proposed. Experimental measurements of these log K values have been lacking or controversial. PMID:25076413

  11. Synthesis and charge-transfer complex formations of 1,n-bis(3,6-diethylcarbazol-9-yl)alkanes with three ?-acceptors

    NASA Astrophysics Data System (ADS)

    Asker, Erol; Filiz, Fahrettin

    2013-05-01

    Dimeric 1,n-bis(3,6-diethylcarbazol-9-yl)alkanes (where n = 1-5) were synthesized and their structures were characterized via spectroscopic techniques. Structures of two of the dimers, 1,2-bis(3,6-diethylcarbazol-9-yl)ethane (2b) and 1,4-bis(3,6-diethylcarbazol-9-yl)butane (2d), were investigated by single crystal X-ray crystallographic techniques. The crystal structures of 2b and 2d were solved in the monoclinic space groups C2/c and P21/n, respectively. The methylene chain adopted an anti conformation in 2b and a gauche-anti-gauche conformation in 2d, enabling coplanar orientations of carbazole rings in both structures. The molecular packing in both structures was stabilized by intermolecular ?-? stacking. Charge transfer complexations of 2a-2e with the ?-acceptors p-chloranil, tetracyanoethylene, and tetracyanoquinodimethane in solution were investigated by determining their stoichiometries, molar absorptivities, equilibrium constants, enthalpies, and entropies. All the dimers formed weakly associated complexes with each of the acceptors having equilibrium constants between 1.32-8.94 M-1 in 1,2-dichloroethane. Complexations were driven by the slightly negative formation enthalpies between -2.00 and -4.24 kcal mol-1.

  12. Complex formation between ovalbumin and strong polyanion PSSNa: study of structure and properties.

    PubMed

    Trabelsi, Saber; Aschi, Adel; Othman, Tahar; Gharbi, Abdelhafidh

    2014-09-01

    The mixture system of long-chain polyelectrolyte complexed with a globular protein was investigated based on dynamic light scattering and turbidimetric measurements. We have discussed at different pH values the influence of high salt concentration and mass ratio (protein:PSSNa) on the behavior of the mixture. In dilute concentration regime, the PSSNa chain contracts at pHc by patch binding. We found two critical values of mass ratio: The first corresponds to the maximum shrinking of PSSNa. The second indicates the system that became more stable where the number of proteins attached to the PSSNa chain was constant. The screen of electrostatic interaction shows a high contribution of hydrophobic interaction at large salt concentration to form the coacervates. By building phase diagram, the continuity of pH?1 in over whole range of salt concentrations and the widening of pH window (pH?1-pH?2) were observed. At certain salt concentrations, we can obtain the coexistence of two types of complex particles formed by electrostatic and hydrophobic interactions. PMID:25063122

  13. Paleobiology of a Neoproterozoic tidal flat/lagoonal complex: the Draken Conglomerate Formation, Spitsbergen

    NASA Technical Reports Server (NTRS)

    Knoll, A. H.; Swett, K.; Mark, J.

    1991-01-01

    Carbonates and rare shales of the ca 700-800 Ma old Draken Conglomerate Formation, northeastern Spitsbergen, preserve a record of environmental variation within a Neoproterozoic tidal flat/lagoon complex. Forty-two microfossil taxa have been recognized in Draken rocks, and of these, 39 can be characterized in terms of their paleoenvironmental distributions along a gradient from the supratidal zone to permanently submerged lagoons. Supratidal to subtidal trends include: increasing microbenthic diversity, increasing abundance and diversity of included allochthonous (presumably planktonic) elements, decreasing sheath thickness of mat-building organisms (with significant taphonomic consequences), and an increasing sediment/fossil ratio in fossiliferous rocks. Five principal and several minor biofacies can be distinguished. The paleoecological resolution obtainable in the Draken Conglomerate Formation rivals that achieved for most Phanerozoic fossil deposits. It documents the complexity and diversity of Proterozoic coastal ecosystems and indicates that both environment and taphonomy need to be taken into explicit consideration in attempts to understand evolutionary trends in early fossil record. Three species, Coniunctiophycus majorinum, Myxococcoides distola, and M. chlorelloidea, are described as new; Siphonophycus robustum, Siphonophycus septatum, and Gorgonisphaeridium maximum are proposed as new combinations.

  14. Ammonium chloride complex formation during downstream microwave ammonia plasma treatment of parylene-C

    SciTech Connect

    Pruden, K.G.; Beaudoin, S.P.

    2005-11-15

    In this work, parylene-C is exposed to the effluent from a microwave ammonia plasma with a goal of producing primary amine groups on the parylene-C. These amine groups are desired as sites for the attachment of various biomolecules that will influence the biocompatibility of the parylene-C. Ammonia plasma treatment is an effective approach for creating amine species on polymers. In this work, attenuated total reflectance infrared spectroscopy studies showed that no primary amine groups resulted from this treatment of parylene-C. Instead, reactive nitrogen-bearing radicals from the plasma appear to have been complexed by chlorine in the polymer. The formation of these complexes scavenged nitrogen-bearing radicals from the plasma and prevented the formation of nitrogenous species, such as the desired primary amines, on the parylene-C. These results are consistent with results of ammonia plasma treatment of other chlorinated polymers and suggest that alternative approaches are required to create nitrogen-bearing species on parylene-C.

  15. Probing formation of cargo/importin-? transport complexes in plant cells using a pathogen effector.

    PubMed

    Wirthmueller, Lennart; Roth, Charlotte; Fabro, Georgina; Caillaud, Marie-Ccile; Rallapalli, Ghanasyam; Asai, Shuta; Sklenar, Jan; Jones, Alexandra M E; Wiermer, Marcel; Jones, Jonathan D G; Banfield, Mark J

    2015-01-01

    Importin-?s are essential adapter proteins that recruit cytoplasmic proteins destined for active nuclear import to the nuclear transport machinery. Cargo proteins interact with the importin-? armadillo repeat domain via nuclear localization sequences (NLSs), short amino acids motifs enriched in Lys and Arg residues. Plant genomes typically encode several importin-? paralogs that can have both specific and partially redundant functions. Although some cargos are preferentially imported by a distinct importin-? it remains unknown how this specificity is generated and to what extent cargos compete for binding to nuclear transport receptors. Here we report that the effector protein HaRxL106 from the oomycete pathogen Hyaloperonospora arabidopsidis co-opts the host cell's nuclear import machinery. We use HaRxL106 as a probe to determine redundant and specific functions of importin-? paralogs from Arabidopsis thaliana. A crystal structure of the importin-?3/MOS6 armadillo repeat domain suggests that five of the six Arabidopsis importin-?s expressed in rosette leaves have an almost identical NLS-binding site. Comparison of the importin-? binding affinities of HaRxL106 and other cargos in vitro and in plant cells suggests that relatively small affinity differences in vitro affect the rate of transport complex formation in vivo. Our results suggest that cargo affinity for importin-?, sequence variation at the importin-? NLS-binding sites and tissue-specific expression levels of importin-?s determine formation of cargo/importin-? transport complexes in plant cells. PMID:25284001

  16. Peroxynitrite affects exocytosis and SNARE complex formation and induces tyrosine nitration of synaptic proteins.

    PubMed

    Di Stasi, A M Michela; Mallozzi, Cinzia; Macchia, Gianfranco; Maura, Guido; Petrucci, Tamara C; Minetti, Maurizio

    2002-07-01

    The reactive species peroxynitrite, formed via the near diffusion-limited reaction of nitric oxide and superoxide anion, is a potent oxidant that contributes to tissue damage in neurodegenerative disorders. Peroxynitrite readily nitrates tyrosine residues in proteins, producing a permanent modification that can be immunologically detected. We have previously demonstrated that in the nerve terminal, nitrotyrosine immunoreactivity is primarily associated with synaptophysin. Here we identify two other presynaptic proteins nitrated by peroxynitrite, Munc-18 and SNAP25, both of which are involved in sequential steps leading to vesicle exocytosis. To investigate whether peroxynitrite affects vesicle exocytosis, we used the fluorescent dye FM1-43 to label a recycling population of secretory vesicles within the synaptosomes. Bolus addition of peroxynitrite stimulated exocytosis and glutamate release. Notably, these effects were strongly reduced in the presence of NaHCO(3), indicating that peroxynitrite acts mainly intracellularly. Furthermore, peroxynitrite enhanced the formation of the sodium dodecyl sulfate-resistant SNARE complex in a dose-dependent manner (100-1000 microm) and induced the formation of 3-nitrotyrosine in proteins of SNARE complex. These data suggest that modification(s) of synaptic vesicle proteins induced by peroxynitrite may affect protein-protein interactions in the docking/fusion steps, thus promoting exocytosis, and that, under excessive production of superoxide and nitric oxide, neurons may up-regulate neuronal signaling. PMID:12124443

  17. Studies on the weak interactions and CT complex formations between chloranilic acid, 2,3-dichloro-5,6-dicyano-p-benzoquinone, tetracyanoethylene and papaverine in acetonitrile and their thermodynamic properties, theoretically, spectrophotometrically aided by FTIR

    NASA Astrophysics Data System (ADS)

    Datta, Asim Sagar; (Chattaraj), Seema Bagchi; Chakrabortty, Ashutosh; Lahiri, Sujit Chandra

    2015-07-01

    Spectrophotometric, FTIR and theoretical studies of the charge-transfer complexes between mild narcotic drug papaverine and the acceptors chloranilic acid (Cl-A), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and tetracyanoethylene (TCNE) in acetonitrile, their association constants, thermodynamic (?G0, ?H0 and ?S0) and other related properties had been described. Papaverine was found to form colored charge-transfer complexes with Cl-A, DDQ and TCNE in acetonitrile. The absorption maxima of the complexes were 518.5, 584.0 and 464.0 nm for Cl-A complex, DDQ complex, and TCNE complex respectively. The compositions of the papaverine complexes were determined to be 1:1 from Job's method of continuous variation. Solid complexes formed between papaverine and the acceptors were isolated. Comparison of the FTIR spectra of the solid complexes between papaverine and the acceptors and their constituents showed considerable shift in absorption peaks, changes in intensities of the peaks and formation of the new bands on complexation. However, no attempt has been made to purify the complexes and study the detailed spectra both theoretically and experimentally. The energies h?CT of the charge-transfer complexes were compared with the theoretical values of h?CT of the complexes obtained from HOMO and LUMO of the donor and the acceptors. The reasons for the differences in h?CT values were explained. Density function theory was used for calculation. h?CT (experimental) values of the transition energies of the complexes in acetonitrile differed from h?CT (theoretical) values. IDV value of papaverine was calculated. Charge-transfer complexes were assumed to be partial electrovalent compounds with organic dative ions D+ and A- (in the excited state) and attempts had been made to correlate the energy changes for the formation of the complexes with the energy changes for the formation of electrovalent compounds between M+ and X- ions.

  18. Studies on the weak interactions and CT complex formations between chloranilic acid, 2,3-dichloro-5,6-dicyano-p-benzoquinone, tetracyanoethylene and papaverine in acetonitrile and their thermodynamic properties, theoretically, spectrophotometrically aided by FTIR.

    PubMed

    Datta, Asim Sagar; Chattaraj, Seema Bagchi; Chakrabortty, Ashutosh; Lahiri, Sujit Chandra

    2015-07-01

    Spectrophotometric, FTIR and theoretical studies of the charge-transfer complexes between mild narcotic drug papaverine and the acceptors chloranilic acid (Cl-A), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and tetracyanoethylene (TCNE) in acetonitrile, their association constants, thermodynamic (?G(0), ?H(0) and ?S(0)) and other related properties had been described. Papaverine was found to form colored charge-transfer complexes with Cl-A, DDQ and TCNE in acetonitrile. The absorption maxima of the complexes were 518.5, 584.0 and 464.0 nm for Cl-A complex, DDQ complex, and TCNE complex respectively. The compositions of the papaverine complexes were determined to be 1:1 from Job's method of continuous variation. Solid complexes formed between papaverine and the acceptors were isolated. Comparison of the FTIR spectra of the solid complexes between papaverine and the acceptors and their constituents showed considerable shift in absorption peaks, changes in intensities of the peaks and formation of the new bands on complexation. However, no attempt has been made to purify the complexes and study the detailed spectra both theoretically and experimentally. The energies h?(CT) of the charge-transfer complexes were compared with the theoretical values of h?(CT) of the complexes obtained from HOMO and LUMO of the donor and the acceptors. The reasons for the differences in h?CT values were explained. Density function theory was used for calculation. h?(CT) (experimental) values of the transition energies of the complexes in acetonitrile differed from h?(CT) (theoretical) values. ID(V) value of papaverine was calculated. Charge-transfer complexes were assumed to be partial electrovalent compounds with organic dative ions D(+) and A(-) (in the excited state) and attempts had been made to correlate the energy changes for the formation of the complexes with the energy changes for the formation of electrovalent compounds between M(+) and X(-) ions. PMID:25813169

  19. Frataxin Accelerates [2Fe-2S] Cluster Formation on the Human Fe–S Assembly Complex

    PubMed Central

    Fox, Nicholas G.; Das, Deepika; Chakrabarti, Mrinmoy; Lindahl, Paul A.; Barondeau, David P.

    2015-01-01

    Iron–sulfur (Fe–S) clusters function as protein cofactors for a wide variety of critical cellular reactions. In human mitochondria, a core Fe–S assembly complex [called SDUF and composed of NFS1, ISD11, ISCU2, and frataxin (FXN) proteins] synthesizes Fe–S clusters from iron, cysteine sulfur, and reducing equivalents and then transfers these intact clusters to target proteins. In vitro assays have relied on reducing the complexity of this complicated Fe–S assembly process by using surrogate electron donor molecules and monitoring simplified reactions. Recent studies have concluded that FXN promotes the synthesis of [4Fe-4S] clusters on the mammalian Fe–S assembly complex. Here the kinetics of Fe–S synthesis reactions were determined using different electron donation systems and by monitoring the products with circular dichroism and absorbance spectroscopies. We discovered that common surrogate electron donor molecules intercepted Fe–S cluster intermediates and formed high-molecular weight species (HMWS). The HMWS are associated with iron, sulfide, and thiol-containing proteins and have properties of a heterogeneous solubilized mineral with spectroscopic properties remarkably reminiscent of those of [4Fe-4S] clusters. In contrast, reactions using physiological reagents revealed that FXN accelerates the formation of [2Fe-2S] clusters rather than [4Fe-4S] clusters as previously reported. In the preceding paper [Fox, N. G., et al. (2015) Biochemistry 54, DOI: 10.1021/bi5014485], [2Fe-2S] intermediates on the SDUF complex were shown to readily transfer to uncomplexed ISCU2 or apo acceptor proteins, depending on the reaction conditions. Our results indicate that FXN accelerates a rate-limiting sulfur transfer step in the synthesis of [2Fe-2S] clusters on the human Fe–S assembly complex. PMID:26016518

  20. Nucleoprotein complex formation by the enhancer binding protein nifA.

    PubMed Central

    Wang, X Y; Kolb, A; Cannon, W; Buck, M

    1997-01-01

    The nitrogen fixation protein NifA is a member of the protein family activating transcription by the alternative eubacterial sigmaN (sigma54) RNA polymerase holoenzyme. Binding sites for NifA, upstream activator sequences (UASs), are remotely located. Interaction between holoenzyme bound in a closed promoter complex and NiFA is facilitated by bending of the intervening DNA by integration host factor (IHF). We have examined NifA contact with the Klebsiella pneumoniae nifH promoter UAS in the presence and absence of holoenzyme and IHF. Footprints with UV light were made on 5-BrdU-substituted DNA and DNase I and laser UV footprints on conventional DNA templates. Results establish that the consensus thymidine residues of the UAS motif 5'-TGT are in close proximity to NifA. Reactivity suggests that each UAS thymidine is not structurally equivalent. Titration of NifA binding to the UAS in the presence or absence of the closed promoter complex indicates that the interaction of NifA with the UAS is not strongly co-operative with holoenzyme or IHF, a result supportive of an activation mechanism not reliant upon simple recruitment of factors to the promoter. Laser footprints demonstrated that holoenzyme suppressed reactivity of promoter consensus -14, -15 and -16 T residues, indicating close contact. Binding of holoenzyme resulted in a specific increase in 5-BrdU reactivity at -9 within the holoenzyme binding site, likely reflecting DNA distortion. Enhanced -9 reactivity required sigmaNN-terminal sequences that are necessary for activation. Since T-9 is melted in open complexes the closed complex appears poised for melting. Open promoter complex formation was accompanied by a distinct change in laser footprint signal at -11, consistent with the view that nucleation of strand separation occurs within or close to the -12 promoter element. PMID:9254707

  1. Vacancy formation on C60/Pt (111): unraveling the complex atomistic mechanism

    NASA Astrophysics Data System (ADS)

    Pinardi, Anna L.; Biddau, Giulio; van De Ruit, Kees; Otero-Irurueta, Gonzalo; Gardonio, Sara; Lizzit, Silvano; Schennach, Robert; Flipse, Cees F. J.; Lpez, Mara F.; Mndez, Javier; Prez, Rubn; Martn-Gago, Jos A.

    2014-09-01

    The interaction of fullerenes with transition metal surfaces leads to the development of an atomic network of ordered vacancies on the metal. However, the structure and formation mechanism of this intricate surface reconstruction is not yet understood at an atomic level. We combine scanning tunneling microscopy, high resolution and temperature programmed-x-ray photoelectrons spectroscopy, and density functional theory calculations to show that the vacancy formation in C60/Pt(111) is a complex process in which fullerenes undergo two significant structural rearrangements upon thermal annealing. At first, the molecules are physisorbed on the surface; next, they chemisorb inducing the formation of an adatom-vacancy pair on the side of the fullerene. Finally, this metastable state relaxes when the adatom migrates away and the vacancy moves under the molecule. The evolution from a weakly-bound fullerene to a chemisorbed state with a vacancy underneath could be triggered by residual H atoms on the surface which prevent a strong surface-adsorbate bonding right after deposition. Upon annealing at about 440 K, when all H has desorbed, the C60 interacts with the Pt surface atoms forming the vacancy-adatom pair. This metastable state induces a small charge transfer and precedes the final adsorption structure.

  2. Quantum chemical insights in energy dissipation and carotenoid radical cation formation in light harvesting complexes.

    PubMed

    Wormit, Michael; Dreuw, Andreas

    2007-06-21

    Light harvesting complexes (LHCs) have been identified in all photosynthetic organisms. To understand their function in light harvesting and energy dissipation, detailed knowledge about possible excitation energy transfer (EET) and electron transfer (ET) processes in these pigment proteins is of prime importance. This again requires the study of electronically excited states of the involved pigment molecules, in LHCs of chlorophylls and carotenoids. This paper represents a critical review of recent quantum chemical calculations on EET and ET processes between pigment pairs relevant for the major LHCs of green plants (LHC-II) and of purple bacteria (LH2). The theoretical methodology for a meaningful investigation of such processes is described in detail, and benefits and limitations of standard methods are discussed. The current status of excited state calculations on chlorophylls and carotenoids is outlined. It is focused on the possibility of EET and ET in the context of chlorophyll fluorescence quenching in LHC-II and carotenoid radical cation formation in LH2. In the context of non-photochemical quenching of green plants, it is shown that replacement of the carotenoid violaxanthin by zeaxanthin in its binding pocket of LHC-II can not result in efficient quenching. In LH2, our computational results give strong evidence that the S(1) states of the carotenoids are involved in carotenoid cation formation. By comparison of theoretical findings with recent experimental data, a general mechanism for carotenoid radical cation formation is suggested. PMID:17551615

  3. Formation of complex organic molecules in cold objects: the role of gas-phase reactions

    NASA Astrophysics Data System (ADS)

    Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

    2015-04-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

  4. A Multi-wavelength Study of Star Formation Activity in the S235 Complex

    NASA Astrophysics Data System (ADS)

    Dewangan, L. K.; Ojha, D. K.; Luna, A.; Anandarao, B. G.; Ninan, J. P.; Mallick, K. K.; Mayya, Y. D.

    2016-03-01

    We have carried out an extensive multi-wavelength study to investigate the star formation process in the S235 complex. The S235 complex has a spherelike shell appearance at wavelengths longer than 2 μm and harbors an O9.5V type star approximately at its center. A near-infrared extinction map of the complex traces eight subregions (having AV > 8 mag), and five of them appear to be distributed in an almost regularly spaced manner along the spherelike shell surrounding the ionized emission. This picture is also supported by the integrated 12CO and 13CO intensity maps and by Bolocam 1.1 mm continuum emission. The position–velocity analysis of CO reveals an almost semi-ringlike structure, suggesting an expanding H ii region. We find that the Bolocam clump masses increase as we move away from the location of the ionizing star. This correlation is seen only for those clumps that are distributed near the edges of the shell. Photometric analysis reveals 435 young stellar objects (YSOs), 59% of which are found in clusters. Six subregions (including five located near the edges of the shell) are very well correlated with the dust clumps, CO gas, and YSOs. The average values of Mach numbers derived using NH3 data for three (East 1, East 2, and Central E) out of these six subregions are 2.9, 2.3, and 2.9, indicating these subregions are supersonic. The molecular outflows are detected in these three subregions, further confirming the ongoing star formation activity. Together, all these results are interpreted as observational evidence of positive feedback of a massive star.

  5. Effects of the Preparation Method on the Formation of True Nimodipine SBE-?-CD/HP-?-CD Inclusion Complexes and Their Dissolution Rates Enhancement.

    PubMed

    Semcheddine, Farouk; Guissi, Nida El Islem; Liu, XueYin; Wu, ZuoMin; Wang, Bo

    2015-06-01

    The aims of this study were to enhance the solubility and dissolution rate of nimodipine (ND) by preparing the inclusion complexes of ND with sulfobutylether-b-cyclodextrin (SBE-?-CD) and 2-hydroxypropyl-b-cyclodextrin (HP-?-CD) and to study the effect of the preparation method on the in vitro dissolution profile in different media (0.1 N HCl pH 1.2, phosphate buffer pH 7.4, and distilled water). Thus, the inclusion complexes were prepared by kneading, coprecipitation, and freeze-drying methods. Phase solubility studies were conducted to characterize the complexes in the liquid state. The inclusion complexes in the solid state were investigated with differential scanning calorimetry (DSC), X-ray diffractometry (X-RD), and Fourier transform infrared spectroscopy (FT-IR). Stable complexes of ND/SBE-?-CD and ND/HP-?-CD were formed in distilled water in a 1:1 stoichiometric inclusion complex as indicated by an AL-type diagram. The apparent stability constants (Ks) were 1334.4 and 464.1 M(-1) for ND/SBE-?-CD and ND/HP-?-CD, respectively. The water-solubility of ND was significantly increased in an average of 22- and 8-fold for SBE-?-CD and HP-?-CD, respectively. DSC results showed the formation of true inclusion complexes between the drug and both SBE-?-CD and HP-?-CD prepared by the kneading method. In contrast, crystalline drug was detectable in all other products. The dissolution studies showed that all the products exhibited higher dissolution rate than those of the physical mixtures and ND alone, in all mediums. However, the kneading complexes displayed the maximum dissolution rate in comparison with drug and other complexes, confirming the influence of the preparation method on the physicochemical properties of the products. PMID:25511809

  6. Nucleophilicity and P-C Bond Formation Reactions of a Terminal Phosphanido Iridium Complex.

    PubMed

    Serrano, ngel L; Casado, Miguel A; Ciriano, Miguel A; de Bruin, Bas; Lpez, Jos A; Tejel, Cristina

    2016-01-19

    The diiridium complex [{Ir(ABPN2)(CO)}2(?-CO)] (1; [ABPN2](-) = [(allyl)B(Pz)2(CH2PPh2)](-)) reacts with diphenylphosphane affording [Ir(ABPN2)(CO)(H) (PPh2)] (2), the product of the oxidative addition of the P-H bond to the metal. DFT studies revealed a large contribution of the terminal phosphanido lone pair to the HOMO of 2, indicating nucleophilic character of this ligand, which is evidenced by reactions of 2 with typical electrophiles such as H(+), Me(+), and O2. Products from the reaction of 2 with methyl chloroacetate were found to be either [Ir(ABPN2)(CO)(H)(PPh2CH2CO2Me)][PF6] ([6]PF6) or [Ir(ABPN2)(CO)(Cl)(H)] (7) and the free phosphane (PPh2CH2CO2Me), both involving P-C bond formation, depending on the reaction conditions. New complexes having iridacyclophosphapentenone and iridacyclophosphapentanone moieties result from reactions of 2 with dimethyl acetylenedicarboxylate and dimethyl maleate, respectively, as a consequence of a further incorporation of the carbonyl ligand. In this line, the terminal alkyne methyl propiolate gave a mixture of a similar iridacyclophosphapentanone complex and [Ir(ABPN2){CH?C(CO2Me)-CO}{PPh2-CH?CH(CO2Me)}] (10), which bears the functionalized phosphane PPh2-CH?CH(CO2Me) and an iridacyclobutenone fragment. Related model reactions aimed to confirm mechanistic proposals are also studied. PMID:26695592

  7. Spectrophotometric determination of tizanidine and orphenadrine via ion pair complex formation using eosin Y.

    PubMed

    Walash, Mohamed I; Belal, Fathalla F; Eid, Manal I; Mohamed, Samah Abo El Abass

    2011-01-01

    A simple, sensitive and rapid spectrophotometric method was developed and validated for the determination of two skeletal muscle relaxants namely, tizanidine hydrochloride (I) and orphenadrine citrate (II) in pharmaceutical formulations. The proposed method is based on the formation of a binary complex between the studied drugs and eosin Y in aqueous buffered medium (pH 3.5). Under the optimum conditions, the binary complex showed absorption maxima at 545 nm for tizanidine and 542 nm for orphenadrine. The calibration plots were rectilinear over concentration range of 0.5-8 ?g/mL and 1-12 ?g/mL with limits of detection of 0.1 ?g/mL and 0.3 ?g/mL for tizanidine and orphenadrine respectively. The different experimental parameters affecting the development and stability of the complex were studied and optimized. The method was successfully applied for determination of the studied drugs in their dosage forms; and to the content uniformity test of tizanidine in tablets. PMID:21982341

  8. Substrate-Na{sup +} complex formation: Coupling mechanism for {gamma}-aminobutyrate symporters

    SciTech Connect

    Pallo, Anna; Simon, Agnes; Bencsura, Akos; Heja, Laszlo; Kardos, Julianna

    2009-07-24

    Crystal structures of transmembrane transport proteins belonging to the important families of neurotransmitter-sodium symporters reveal how they transport neurotransmitters across membranes. Substrate-induced structural conformations of gated neurotransmitter-sodium symporters have been in the focus of research, however, a key question concerning the mechanism of Na{sup +} ion coupling remained unanswered. Homology models of human glial transporter subtypes of the major inhibitory neurotransmitter {gamma}-aminobutyric acid were built. In accordance with selectivity data for subtype 2 vs. 3, docking and molecular dynamics calculations suggest similar orthosteric substrate (inhibitor) conformations and binding crevices but distinguishable allosteric Zn{sup 2+} ion binding motifs. Considering the occluded conformational states of glial human {gamma}-aminobutyric acid transporter subtypes, we found major semi-extended and minor ring-like conformations of zwitterionic {gamma}-aminobutyric acid in complex with Na{sup +} ion. The existence of the minor ring-like conformation of {gamma}-aminobutyric acid in complex with Na{sup +} ion may be attributed to the strengthening of the intramolecular H-bond by the electrostatic effect of Na{sup +} ion. Coupling substrate uptake into cells with the thermodynamically favorable Na{sup +} ion movement through substrate-Na{sup +} ion complex formation may be a mechanistic principle featuring transmembrane neurotransmitter-sodium symporter proteins.

  9. STAR FORMATION ACTIVITY IN THE GALACTIC H II COMPLEX S255-S257

    SciTech Connect

    Ojha, D. K.; Ghosh, S. K.; Samal, M. R.; Pandey, A. K.; Sharma, Saurabh; Bhatt, B. C.; Tamura, M.; Mohan, V.; Zinchenko, I.

    2011-09-10

    We present results on the star formation activity of an optically obscured region containing an embedded cluster (S255-IR) and molecular gas between two evolved H II regions, S255 and S257. We have studied the complex using optical and near-infrared (NIR) imaging, optical spectroscopy, and radio continuum mapping at 15 GHz, along with Spitzer-IRAC results. We found that the main exciting sources of the evolved H II regions S255 and S257 and the compact H II regions associated with S255-IR are of O9.5-B3 V nature, consistent with previous observations. Our NIR observations reveal 109 likely young stellar object (YSO) candidates in an area of {approx}4.'9 x 4.'9 centered on S255-IR, which include 69 new YSO candidates. To see the global star formation, we constructed the V - I/V diagram for 51 optically identified IRAC YSOs in an area of {approx}13' x 13' centered on S255-IR. We suggest that these YSOs have an approximate age between 0.1 and 4 Myr, indicating a non-coeval star formation. Using spectral energy distribution models, we constrained physical properties and evolutionary status of 31 and 16 YSO candidates outside and inside the gas ridge, respectively. The models suggest that the sources associated with the gas ridge are younger (mean age {approx}1.2 Myr) than the sources outside the gas ridge (mean age {approx}2.5 Myr). The positions of the young sources inside the gas ridge at the interface of the H II regions S255 and S257 favor a site of induced star formation.

  10. Electrostatic and hydrophobic interactions during complex formation and electron transfer in the ferredoxin/ferredoxin: NADP{sup +} reductase system from Anabaena

    SciTech Connect

    Hurley, J.K.; Tollin, G.; Fillat, M.F.; Gomez-Moreno, C.

    1996-06-19

    Transient kinetics and protein-protein binding measurements over a wide range of ionic strength (I) have been used to characterize the interactions occurring during complex formation and electron transfer (et) between recombinant ferredoxin (Fd) and both native and recombinant ferredoxin: NADP{sup +} reductase (FNR) from the cyanobacterium Anabaena. Between I = 12 mM and I = 100 mM, the dissociation constant (K{sub d}) for the complex formed between oxidized Fd and oxidized native FNR increases from 4.5 to 8.1 {mu}M, whereas K{sub d} for the Fd complex with recombinant FNR increases from 0.3 to 3.3 {mu}M. For both pairs of proteins, the ionic strength dependence of k{sub obs} for the et reaction is biphasic. Electrostatic analysis of the kinetic data above I = 100 mM allows a prediction of the ionic strength dependence of the K{sub d} values, if electrostatic interactions are the only determinant of complex stability. The predicted dependence is dramatically larger than the observed one, indicating that hydrophobic interactions make an important contribution to complex stability. The differences in binding between native and recombinant FNR are ascribed to proteolytic cleavage at the N-terminus, which occurs during preparation of the native enzyme and which removes two positively charged residues, thereby decreasing the electrostatic interactions with Fd. 39 refs., 4 figs., 1 tab.

  11. Sensitive and selective spectrophotometric assay of piroxicam in pure form, capsule and human blood serum samples via ion-pair complex formation.

    PubMed

    Alizadeh, Nina; Keyhanian, Fereshteh

    2014-09-15

    A simple, accurate and highly sensitive spectrophotometric method has been developed for the rapid determination of piroxicam (PX) in pure and pharmaceutical formulations. The proposed method involves formation of stable yellow colored ion-pair complexes of the amino derivative (basic nitrogen) of PX with three sulphonphthalein acid dyes namely; bromocresol green (BCG), bromothymol blue (BTB), bromophenol blue (BPB) in acidic medium. The colored species exhibited absorption maxima at 438, 429 and 432 nm with molar absorptivity values of 9.40010(3), 1.21810(3) and 1.0210(4) L mol(-1) cm(-1) for PX-BCG, PX-BTB and PX-BPB complexes, respectively. The effect of optimum conditions via acidity, reagent concentration, time and solvent were studied. The reactions were extremely rapid at room temperature and the absorbance values remained constant for 48h. Beer's law was obeyed with a good correlation coefficient in the concentration ranges 1-100 ?g mL(-1) for BCG, BTB complexes and 1-95 ?g mL(-1) for BPB complex. The composition ratio of the ion-pair complexes were found to be 1:1 in all cases as established by Job's method. No interference was observed from common additives and excipients which may be present in the pharmaceutical preparations. The proposed method was successfully applied for the determination of PX in capsule and human blood serum samples with good accuracy and precision. PMID:24792197

  12. Sensitive and selective spectrophotometric assay of piroxicam in pure form, capsule and human blood serum samples via ion-pair complex formation

    NASA Astrophysics Data System (ADS)

    Alizadeh, Nina; Keyhanian, Fereshteh

    2014-09-01

    A simple, accurate and highly sensitive spectrophotometric method has been developed for the rapid determination of piroxicam (PX) in pure and pharmaceutical formulations. The proposed method involves formation of stable yellow colored ion-pair complexes of the amino derivative (basic nitrogen) of PX with three sulphonphthalein acid dyes namely; bromocresol green (BCG), bromothymol blue (BTB), bromophenol blue (BPB) in acidic medium. The colored species exhibited absorption maxima at 438, 429 and 432 nm with molar absorptivity values of 9.400 × 103, 1.218 × 103 and 1.02 × 104 L mol-1 cm-1 for PX-BCG, PX-BTB and PX-BPB complexes, respectively. The effect of optimum conditions via acidity, reagent concentration, time and solvent were studied. The reactions were extremely rapid at room temperature and the absorbance values remained constant for 48 h. Beer’s law was obeyed with a good correlation coefficient in the concentration ranges 1-100 μg mL-1 for BCG, BTB complexes and 1-95 μg mL-1 for BPB complex. The composition ratio of the ion-pair complexes were found to be 1:1 in all cases as established by Job’s method. No interference was observed from common additives and excipients which may be present in the pharmaceutical preparations. The proposed method was successfully applied for the determination of PX in capsule and human blood serum samples with good accuracy and precision.

  13. The formation of glycine and other complex organic molecules in exploding ice mantles.

    PubMed

    Rawlings, J M C; Williams, D A; Viti, S; Cecchi-Pestellini, C; Duley, W W

    2014-01-01

    Complex Organic Molecules (COMs), such as propylene (CH3CHCH2) and the isomers of C2H4O2 are detected in cold molecular clouds (such as TMC-1) with high fractional abundances (Marcelino et al., Astrophys. J., 2007, 665, L127). The formation mechanism for these species is the subject of intense speculation, as is the possibility of the formation of simple amino acids such as glycine (NH2CH2COOH). At typical dark cloud densities, normal interstellar gas-phase chemistries are inefficient, whilst surface chemistry is at best ill defined and does not easily reproduce the abundance ratios observed in the gas phase. Whatever mechanism(s) is/are operating, it/they must be both efficient at converting a significant fraction of the available carbon budget into COMs, and capable of efficiently returning the COMs to the gas phase. In our previous studies we proposed a complementary, alternative mechanism, in which medium- and large-sized molecules are formed by three-body gas kinetic reactions in the warm high density gas phase. This environment exists, for a very short period of time, after the total sublimation of grain ice mantles in transient co-desorption events. In order to drive the process, rapid and efficient mantle sublimation is required and we have proposed that ice mantle 'explosions' can be driven by the catastrophic recombination of trapped hydrogen atoms, and other radicals, in the ice. Repeated cycles of freeze-out and explosion can thus lead to a cumulative molecular enrichment of the interstellar medium. Using existing studies we based our chemical network on simple radical addition, subject to enthalpy and valency restrictions. In this work we have extended the chemistry to include the formation pathways of glycine and other large molecular species that are detected in molecular clouds. We find that the mechanism is capable of explaining the observed molecular abundances and complexity in these sources. We find that the proposed mechanism is easily capable of explaining the large abundances of all three isomers of C2H4O2 that are observationally inferred for star-forming regions. However, the model currently does not provide an obvious explanation for the predominance of methyl formate, suggesting that some refinement to our (very simplistic) chemistry is necessary. The model also predicts the production of glycine at a (lower) abundance level, that is consistent with its marginal detection in astrophysical sources. PMID:25302390

  14. Formation of Aqueous MgUO2(CO3)32- Complex and Uranium Anion Exchange Mechanism onto an Exchange Resin

    SciTech Connect

    Dong, Wenming; Brooks, Scott C

    2008-01-01

    The formation of and stability constants for aqueous Mg-UO2-CO3 complexes were determined using an anion exchange method. Magnesium concentration was varied (up to 20 mmol/L) at constant ionic strength (I = 0.101, 0.202, 0.304, 0.406, and 0.509 mol/kg NaNO3), pH = 8.1, total [U(VI)] = 10.4 mol/L under equilibrium with atmospheric CO2. The results indicate that only the MgUO2(CO3)32- complex is formed. The cumulative formation constant extrapolated to zero ionic strength is similar regardless of the activity correction convention used: log = 25.8 b 0.5 using Davies equation and = 25.02 b 0.08 using specific ion interaction theory (SIT). Uranium sorption onto the exchange resin decreased in the presence of Mg putatively due to the formation of MgUO2(CO3)32- that had a lower affinity for the resin than UO2(CO3)34-. Uranium sorption results are consistent with an equivalent anion exchange reaction between NO3- and UO2(CO3)34- species to retain charge neutrality regardless of Mg concentration. No Mg was associated with the anion exchange resin indicating that the MgUO2(CO3)32- complex did not sorb.

  15. Coronavirus Replicase-Reporter Fusions Provide Quantitative Analysis of Replication and Replication Complex Formation

    PubMed Central

    Freeman, Megan Culler; Graham, Rachel L.; Lu, Xiaotao; Peek, Christopher T.

    2014-01-01

    ABSTRACT The replication of coronaviruses occurs in association with multiple virus-induced membrane structures that evolve during the course of infection; however, the dynamics of this process remain poorly understood. Previous studies of coronavirus replication complex organization and protein interactions have utilized protein overexpression studies and immunofluorescence of fixed cells. Additionally, live-imaging studies of coronavirus replicase proteins have used fluorescent reporter molecules fused to replicase proteins, but expressed from nonnative locations, mostly late-transcribed subgenomic mRNAs, in the presence or absence of the native protein. Thus, the timing and targeting of native replicase proteins expressed in real time from native locations in the genome remain unknown. In this study, we tested whether reporter molecules could be expressed from the replicase polyprotein of murine hepatitis virus as fusions with nonstructural protein 2 or 3 and whether such reporters could define the targeting and activity of replicase proteins during infection. We demonstrate that the fusion of green fluorescent protein and firefly luciferase with either nonstructural protein 2 or 3 is tolerated and that these reporter-replicase fusions can be used to quantitate replication complex formation and virus replication. The results show that the replicase gene has flexibility to accommodate a foreign gene addition and can be used directly to study replicase complex formation and evolution during infection as well as to provide highly sensitive and specific markers for protein translation and genome replication. IMPORTANCE Coronaviruses are a family of enveloped, positive-sense RNA viruses that are important agents of disease, including severe acute respiratory syndrome coronavirus and Middle East respiratory syndrome coronavirus. Replication is associated with multiple virus-induced membrane structures that evolve during infection; however, the dynamics of this process remain poorly understood. In this study, we tested whether reporter molecules expressed from native locations within the replicase polyprotein of murine hepatitis virus as fusions with nonstructural proteins could define the expression and targeting of replicase proteins during infection in live cells. We demonstrate that the replicase gene tolerates the introduction of green fluorescent protein or firefly luciferase as fusions with replicase proteins. These viruses allow early quantitation of virus replication as well as real-time measurement of replication complexes. PMID:24623413

  16. Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles.

    PubMed

    Guan, Zong; Namyslo, Jan C; Drafz, Martin H H; Nieger, Martin; Schmidt, Andreas

    2014-01-01

    Deprotonation of indazolium salts at low temperatures gives N-heterocyclic carbenes of indazoles (indazol-3-ylidenes) which can be trapped as rhodium complexes (X-ray analysis). In the absence of Rh, the indazol-3-ylidenes spontaneously dimerize under ring cleavage of one of the N,N-bonds and ring closure to an indazole-indole spiro compound which possesses an exocyclic imine group. The E/Z isomers of the imines can be separated by column chromatography when methanol is used as eluent. We present results of a single crystal X-ray analysis of one of the E-isomers, which equilibrate in solution as well as in the solid state. Heating of the indazole-indole spiro compounds results in the formation of quinazolines by a ring-cleavage/ring-closure sequence (X-ray analysis). Results of DFT calculations are presented. PMID:24778738

  17. Spontaneous formation of complex structures made from elastic membranes in an aluminum-hydroxide-carbonate system

    NASA Astrophysics Data System (ADS)

    Kiehl, Micah; Kaminker, Vitaliy; Pantaleone, James; Nowak, Piotr; Dyonizy, Agnieszka; Maselko, Jerzy

    2015-06-01

    A popular playground for studying chemo-hydrodynamic patterns and instabilities is chemical gardens, also known as silicate gardens. In these systems, complex structures spontaneously form, driven by buoyant forces and either osmotic or mechanical pumps. Here, we report on systems that differ somewhat from classical chemical gardens in that the membranes are much more deformable and soluble. These properties lead to structures that self-construct and evolve in new ways. For example, they exhibit the formation of chemical balloons, a new growth mechanism for tubes, and also the homologous shrinking of these tubes. The stretching mechanism for the membranes is probably different than for other systems by involving membrane "self-healing." Other unusual properties are osmosis that sometimes occurs out of the structure and also small plumes that flow away from the structure, sometimes upwards, and sometimes downwards. Mathematical models are given that explain some of the observed phenomena.

  18. The oyster genome reveals stress adaptation and complexity of shell formation.

    PubMed

    Zhang, Guofan; Fang, Xiaodong; Guo, Ximing; Li, Li; Luo, Ruibang; Xu, Fei; Yang, Pengcheng; Zhang, Linlin; Wang, Xiaotong; Qi, Haigang; Xiong, Zhiqiang; Que, Huayong; Xie, Yinlong; Holland, Peter W H; Paps, Jordi; Zhu, Yabing; Wu, Fucun; Chen, Yuanxin; Wang, Jiafeng; Peng, Chunfang; Meng, Jie; Yang, Lan; Liu, Jun; Wen, Bo; Zhang, Na; Huang, Zhiyong; Zhu, Qihui; Feng, Yue; Mount, Andrew; Hedgecock, Dennis; Xu, Zhe; Liu, Yunjie; Domazet-Lošo, Tomislav; Du, Yishuai; Sun, Xiaoqing; Zhang, Shoudu; Liu, Binghang; Cheng, Peizhou; Jiang, Xuanting; Li, Juan; Fan, Dingding; Wang, Wei; Fu, Wenjing; Wang, Tong; Wang, Bo; Zhang, Jibiao; Peng, Zhiyu; Li, Yingxiang; Li, Na; Wang, Jinpeng; Chen, Maoshan; He, Yan; Tan, Fengji; Song, Xiaorui; Zheng, Qiumei; Huang, Ronglian; Yang, Hailong; Du, Xuedi; Chen, Li; Yang, Mei; Gaffney, Patrick M; Wang, Shan; Luo, Longhai; She, Zhicai; Ming, Yao; Huang, Wen; Zhang, Shu; Huang, Baoyu; Zhang, Yong; Qu, Tao; Ni, Peixiang; Miao, Guoying; Wang, Junyi; Wang, Qiang; Steinberg, Christian E W; Wang, Haiyan; Li, Ning; Qian, Lumin; Zhang, Guojie; Li, Yingrui; Yang, Huanming; Liu, Xiao; Wang, Jian; Yin, Ye; Wang, Jun

    2012-10-01

    The Pacific oyster Crassostrea gigas belongs to one of the most species-rich but genomically poorly explored phyla, the Mollusca. Here we report the sequencing and assembly of the oyster genome using short reads and a fosmid-pooling strategy, along with transcriptomes of development and stress response and the proteome of the shell. The oyster genome is highly polymorphic and rich in repetitive sequences, with some transposable elements still actively shaping variation. Transcriptome studies reveal an extensive set of genes responding to environmental stress. The expansion of genes coding for heat shock protein 70 and inhibitors of apoptosis is probably central to the oyster's adaptation to sessile life in the highly stressful intertidal zone. Our analyses also show that shell formation in molluscs is more complex than currently understood and involves extensive participation of cells and their exosomes. The oyster genome sequence fills a void in our understanding of the Lophotrochozoa. PMID:22992520

  19. Magellan observations of Alpha Regio - Implications for formation of complex ridged terrains on Venus

    NASA Technical Reports Server (NTRS)

    Bindschadler, Duane L.; Decharon, Annette; Beratan, Kathi K.; Smrekear, Suzanne E.; Head, James W.

    1992-01-01

    The deformational features that make up the complex ridged terrain (CRT) of Alpha Regio are characterized, and observations of these features and their interpretations are used to evaluate quantitative models for the formation of Alpha Regio. In particular, two models are considered: a hotspot or mantle plume model and a coldspot or mantle downwelling model. Based on an analysis of the observed morphology of structures, their distribution, superposition and crosscutting relationships, and Magellan altimetry, a sequence of deformational events is suggested, and the observed topography, tectonics, and volcanism are compared with the predictions of the hotspot and coldspot models. It is found that a number of observations are more consistent with the downwelling than a hotspot model. This is particularly true of margin-parallel compressional features near the plains-CRT boundary in much of Alpha Regio.

  20. Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles

    PubMed Central

    Guan, Zong; Namyslo, Jan C; Drafz, Martin H H; Nieger, Martin

    2014-01-01

    Summary Deprotonation of indazolium salts at low temperatures gives N-heterocyclic carbenes of indazoles (indazol-3-ylidenes) which can be trapped as rhodium complexes (X-ray analysis). In the absence of Rh, the indazol-3-ylidenes spontaneously dimerize under ring cleavage of one of the N,N-bonds and ring closure to an indazoleindole spiro compound which possesses an exocyclic imine group. The E/Z isomers of the imines can be separated by column chromatography when methanol is used as eluent. We present results of a single crystal X-ray analysis of one of the E-isomers, which equilibrate in solution as well as in the solid state. Heating of the indazoleindole spiro compounds results in the formation of quinazolines by a ring-cleavage/ring-closure sequence (X-ray analysis). Results of DFT calculations are presented. PMID:24778738

  1. Solvent effects on charge-transfer intensities and heats of formation of chloranil complexes with aromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Bhowmik, Benoy B.; Bhattacharyya, Amar

    The spectrophotometric and thermodynamic properties of the charge-transfer complexes of chloranil with aromatic hydrocarbons such as benzene, toluene, xylenes ( o-, m- and p-) and mesitylene have been studied in n-heptane solvent to make a correlation between the charge-transfer intensities and the heats of formation of the complexes. The results disagree with M ULLIKEN's predictionthe charge-transfer intensities decrease with increase of heats of formation. An attempt has been made to calculate the thermodynamic as well as spectrophotometric properties of these complexes free from the influence of chloranilsolvent interaction and the results thus obtained show a good correlation between the charge-transfer intensities and the heats of formation of the complexes.

  2. Amphiphilic Residues 29-44 of DREAM N-Termini Mediate Calmodulin:DREAM Complex Formation.

    PubMed

    Gonzalez, Walter G; Arango, Andres S; Miksovska, Jaroslava

    2015-07-21

    DREAM (downstream regulatory element antagonist modulator) is a neuronal calcium sensor that has been shown to modulate gene expression as well as to be involved in numerous neuronal processes. In this report, we show that association of calcium-bound calmodulin (CaM) with DREAM is mediated by a short amphipathic amino acid sequence located between residues 29 and 44 on DREAM. The association of CaM with a peptide analogous to DREAM(29-44) or to full-length DREAM protein is calcium-dependent with a dissociation constant of 136 nM or 3.4 ?M, respectively. Thermodynamic and kinetic studies show that the observed decrease in affinity for the native protein is due to electrostatic interactions between the basic N-terminus and an electronegative surface on DREAM. These results are further supported by circular dichroism, binding studies, and molecular dynamics simulations. Additionally, fluorescence anisotropy decay measurements show a rotational correlation time of 10.8 ns for a complex of CaM with a DREAM(29-44) peptide, supporting a wraparound semispherical model with 1:1 stoichiometry. Furthermore, the interaction between an IEDANS-labeled CaM construct with DREAM is best modeled as a heterotetramer that adopts an elongated conformation with a correlation time of 45 ns in the presence of Ca(2+). We also demonstrate that association of CaM with DREAM eliminates the nonspecific interaction of DREAM with the DRE double-stranded DNA sequence of the human prodynorphin gene. This work provides molecular insight into the CaM:DREAM complex and its potential role in modulation of gene expression. PMID:26108881

  3. Validation of a Parcel-Based Reduced-Complexity Model for River Delta Formation (Invited)

    NASA Astrophysics Data System (ADS)

    Liang, M.; Geleynse, N.; Passalacqua, P.; Edmonds, D. A.; Kim, W.; Voller, V. R.; Paola, C.

    2013-12-01

    Reduced-Complexity Models (RCMs) take an intuitive yet quantitative approach to represent processes with the goal of getting maximum return in emergent system-scale behavior with minimum investment in computational complexity. This approach is in contrast to reductionist models that aim at rigorously solving the governing equations of fluid flow and sediment transport. RCMs have had encouraging successes in modeling a variety of geomorphic systems, such as braided rivers, alluvial fans, and river deltas. Despite the fact that these models are not intended to resolve detailed flow structures, questions remain on how to interpret and validate the output of RCMs beyond qualitative behavior-based descriptions. Here we present a validation of the newly developed RCM for river delta formation with channel dynamics (Liang, 2013). The model uses a parcel-based 'weighted-random-walk' method that resolves the formation of river deltas at the scale of channel dynamics (e.g., avulsions and bifurcations). The main focus of this validation work is the flow routing model component. A set of synthetic test cases were designed to compare hydrodynamic results from the RCM and Delft3D, including flow in a straight channel, around a bump, and flow partitioning at a single bifurcation. Output results, such as water surface slope and flow field, are also compared to field observations collected at Wax Lake Delta. Additionally, we investigate channel avulsion cycles and flow path selection in an alluvial fan with differential styles of subsidence and compare model results to laboratory experiments, as a preliminary effort in pairing up numerical and experimental models to understand channel organization at process scale. Strengths and weaknesses of the RCM are discussed and potential candidates for model application identified.

  4. Transcriptional activation through the tetrameric complex formation of E4TF1 subunits.

    PubMed Central

    Sawada, J; Goto, M; Sawa, C; Watanabe, H; Handa, H

    1994-01-01

    Transcription factor E4TF1 is composed of two types of subunit, an ets-related DNA binding protein, E4TF1-60, and its associated proteins with four tandemly repeated Notch-ankyrin motifs, E4TF1-53 and E4TF1-47. To determine the functional domains, we constructed various mutants of the subunits. E4TF1-60 bound to DNA as a monomer. The ets domain and its N-terminal flanking region were necessary to recognize the specific DNA sequence. The 48 amino acids at the E4TF1-60 C-terminus were required for interaction with the other type of subunit. E4TF1-53 and E4TF1-47 share the N-terminal 332 amino acids but differ at the C-termini. They interacted with E4TF1-60 through the N-terminal flanking region to form a heterodimer. E4TF1-53 dimerized with itself, whereas E4TF1-47 did not. The C-terminal region specific for E4TF1-53 was required for the dimerization. Therefore, heterodimers composed of E4TF1-53 and E4TF1-60 were further dimerized, resulting in the formation of a tetrameric complex, which stimulated transcription in vitro. Heterodimers of E4TF1-47 and E4TF1-60 weakly stimulated transcription in vitro. The results indicated that the tetrameric complex formation of E4TF1 subunits was necessary to activate transcription efficiently in vitro. Images PMID:8137823

  5. Probing formation of cargo/importin-α transport complexes in plant cells using a pathogen effector

    PubMed Central

    Wirthmueller, Lennart; Roth, Charlotte; Fabro, Georgina; Caillaud, Marie-Cécile; Rallapalli, Ghanasyam; Asai, Shuta; Sklenar, Jan; Jones, Alexandra M E; Wiermer, Marcel; Jones, Jonathan D G; Banfield, Mark J

    2015-01-01

    Importin-αs are essential adapter proteins that recruit cytoplasmic proteins destined for active nuclear import to the nuclear transport machinery. Cargo proteins interact with the importin-α armadillo repeat domain via nuclear localization sequences (NLSs), short amino acids motifs enriched in Lys and Arg residues. Plant genomes typically encode several importin-α paralogs that can have both specific and partially redundant functions. Although some cargos are preferentially imported by a distinct importin-α it remains unknown how this specificity is generated and to what extent cargos compete for binding to nuclear transport receptors. Here we report that the effector protein HaRxL106 from the oomycete pathogen Hyaloperonospora arabidopsidis co-opts the host cell's nuclear import machinery. We use HaRxL106 as a probe to determine redundant and specific functions of importin-α paralogs from Arabidopsis thaliana. A crystal structure of the importin-α3/MOS6 armadillo repeat domain suggests that five of the six Arabidopsis importin-αs expressed in rosette leaves have an almost identical NLS-binding site. Comparison of the importin-α binding affinities of HaRxL106 and other cargos in vitro and in plant cells suggests that relatively small affinity differences in vitro affect the rate of transport complex formation in vivo. Our results suggest that cargo affinity for importin-α, sequence variation at the importin-α NLS-binding sites and tissue-specific expression levels of importin-αs determine formation of cargo/importin-α transport complexes in plant cells. PMID:25284001

  6. Unraveling the complexities of circadian and sleep interactions with memory formation through invertebrate research

    PubMed Central

    Michel, Maximilian; Lyons, Lisa C.

    2014-01-01

    Across phylogeny, the endogenous biological clock has been recognized as providing adaptive advantages to organisms through coordination of physiological and behavioral processes. Recent research has emphasized the role of circadian modulation of memory in generating peaks and troughs in cognitive performance. The circadian clock along with homeostatic processes also regulates sleep, which itself impacts the formation and consolidation of memory. Thus, the circadian clock, sleep and memory form a triad with ongoing dynamic interactions. With technological advances and the development of a global 24/7 society, understanding the mechanisms underlying these connections becomes pivotal for development of therapeutic treatments for memory disorders and to address issues in cognitive performance arising from non-traditional work schedules. Invertebrate models, such as Drosophila melanogaster and the mollusks Aplysia and Lymnaea, have proven invaluable tools for identification of highly conserved molecular processes in memory. Recent research from invertebrate systems has outlined the influence of sleep and the circadian clock upon synaptic plasticity. In this review, we discuss the effects of the circadian clock and sleep on memory formation in invertebrates drawing attention to the potential of in vivo and in vitro approaches that harness the power of simple invertebrate systems to correlate individual cellular processes with complex behaviors. In conclusion, this review highlights how studies in invertebrates with relatively simple nervous systems can provide mechanistic insights into corresponding behaviors in higher organisms and can be used to outline possible therapeutic options to guide further targeted inquiry. PMID:25136297

  7. Generalized additive models reveal the intrinsic complexity of wood formation dynamics

    PubMed Central

    Cuny, Henri E.; Rathgeber, Cyrille B.K.; Kiess, Tristan Senga; Hartmann, Felix P.; Barbeito, Ignacio; Fournier, Meriem

    2013-01-01

    The intra-annual dynamics of wood formation, which involves the passage of newly produced cells through three successive differentiation phases (division, enlargement, and wall thickening) to reach the final functional mature state, has traditionally been described in conifers as three delayed bell-shaped curves followed by an S-shaped curve. Here the classical view represented by the Gompertz function (GF) approach was challenged using two novel approaches based on parametric generalized linear models (GLMs) and data-driven generalized additive models (GAMs). These three approaches (GFs, GLMs, and GAMs) were used to describe seasonal changes in cell numbers in each of the xylem differentiation phases and to calculate the timing of cell development in three conifer species [Picea abies (L.), Pinus sylvestris L., and Abies alba Mill.]. GAMs outperformed GFs and GLMs in describing intra-annual wood formation dynamics, showing two left-skewed bell-shaped curves for division and enlargement, and a right-skewed bimodal curve for thickening. Cell residence times progressively decreased through the season for enlargement, whilst increasing late but rapidly for thickening. These patterns match changes in cell anatomical features within a tree ring, which allows the separation of earlywood and latewood into two distinct cell populations. A novel statistical approach is presented which renews our understanding of xylogenesis, a dynamic biological process in which the rate of cell production interplays with cell residence times in each developmental phase to create complex seasonal patterns. PMID:23530132

  8. Formation of Large Polysulfide Complexes during the Lithium-Sulfur Battery Discharge

    SciTech Connect

    Wang, Bin; Alhassan, Saeed M.; Pantelides, Sokrates T

    2014-01-01

    Sulfur cathodes have much larger capacities than transition-metal-oxide cathodes used in commercial lithium-ion batteries but suffer from unsatisfactory capacity retention and long-term cyclability. Capacity degradation originates from soluble lithium polysulfides gradually diffusing into the electrolyte. Understanding of the formation and dynamics of soluble polysulfides during the discharging process at the atomic level remains elusive, which limits further development of lithium-sulfur (Li-S) batteries. Here we report first-principles molecular dynamics simulations and density functional calculations, through which the discharging products of Li-S batteries are studied. We find that, in addition to simple Li2Sn (1 n 8) clusters generated from single cyclooctasulfur (S8) rings, large Li-S clusters form by collectively coupling several different rings to minimize the total energy. At high lithium concentration, a Li-S network forms at the sulfur surfaces. The results can explain the formation of the soluble Li-S complex, such as Li2S8, Li2S6, and Li2S4, and the insoluble Li2S2 and Li2S structures. In addition, we show that the presence of oxygen impurities in graphene, particularly oxygen atoms bonded to vacancies and edges, may stabilize the lithium polysulfides that may otherwise diffuse into the electrolyte.

  9. Formation of Large Polysulfide Complexes during the Lithium-Sulfur Battery Discharge

    NASA Astrophysics Data System (ADS)

    Wang, Bin; Alhassan, Saeed M.; Pantelides, Sokrates T.

    2014-09-01

    Sulfur cathodes have much larger capacities than transition-metal-oxide cathodes used in commercial lithium-ion batteries but suffer from unsatisfactory capacity retention and long-term cyclability. Capacity degradation originates from soluble lithium polysulfides gradually diffusing into the electrolyte. Understanding of the formation and dynamics of soluble polysulfides during the discharging process at the atomic level remains elusive, which limits further development of lithium-sulfur (Li-S) batteries. Here we report first-principles molecular dynamics simulations and density functional calculations, through which the discharging products of Li-S batteries are studied. We find that, in addition to simple Li2Sn (1?n ?8) clusters generated from single cyclooctasulfur (S8) rings, large Li-S clusters form by collectively coupling several different rings to minimize the total energy. At high lithium concentration, a Li-S network forms at the sulfur surfaces. The results can explain the formation of the soluble Li-S complex, such as Li2S8, Li2S6, and Li2S4, and the insoluble Li2S2 and Li2S structures. In addition, we show that the presence of oxygen impurities in graphene, particularly oxygen atoms bonded to vacancies and edges, may stabilize the lithium polysulfides that may otherwise diffuse into the electrolyte.

  10. Complex organic molecules during low-mass star formation: Pilot survey results

    SciTech Connect

    berg, Karin I.; Graninger, Dawn; Lauck, Trish

    2014-06-10

    Complex organic molecules (COMs) are known to be abundant toward some low-mass young stellar objects (YSOs), but how these detections relate to typical COM abundance are not yet understood. We aim to constrain the frequency distribution of COMs during low-mass star formation, beginning with this pilot survey of COM lines toward six embedded YSOs using the IRAM 30 m Telescope. The sample was selected from the Spitzer c2d ice sample and covers a range of ice abundances. We detect multiple COMs, including CH{sub 3}CN, toward two of the YSOs, and tentatively toward a third. Abundances with respect to CH{sub 3}OH vary between 0.7% and 10%. This sample is combined with previous COM observations and upper limits to obtain a frequency distributions of CH{sub 3}CN, HCOOCH{sub 3}, CH{sub 3}OCH{sub 3}, and CH{sub 3}CHO. We find that for all molecules more than 50% of the sample have detections or upper limits of 1%-10% with respect to CH{sub 3}OH. Moderate abundances of COMs thus appear common during the early stages of low-mass star formation. A larger sample is required, however, to quantify the COM distributions, as well as to constrain the origins of observed variations across the sample.

  11. Hydrogenation of a rhodium peroxido complex by formate derivatives: mechanistic studies and the catalytic formation of H2O2 from O2.

    PubMed

    Meier, Gregor; Braun, Thomas

    2012-12-01

    Hydrogenation of dioxygen: The rhodium peroxido complex 1, which can be prepared from 2 and dioxygen, can be reduced with dihydrogen sources to yield hydrogen peroxide. In a catalytic experiment, hydrogen peroxide is produced from dioxygen and ammonium formate under ambient conditions in the presence of 1 (see scheme). PMID:23125187

  12. Electrocatalytic Oxidation of Formate by [Ni(P{sup R}?N{sup R'}?)?(CH?CN)]{sup 2+} Complexes

    SciTech Connect

    Galan, Brandon R; Schoffel, Julia; Linehan, John C; Seu, Candace; Appel, Aaron M; Roberts, John A.; Helm, Monte L; Kilgore, Uriah J; Yang, Jenny Y; DuBois, Daniel L; Kubiak, Clifford P

    2011-08-17

    [Ni(P{sup R}?N{sup R?}?)?(CH?CN)]{sup 2+} complexes with R = Ph, R? = 4-MeOPh or R = Cy, R? = Ph , and a mixed-ligand [Ni(P{sup R}?N{sup R?}?)(P{sup R??}?N{sup R?}?)(CH?CN)]{sup 2+} with R = Cy, R? = Ph, R?? = Ph, have been synthesized and characterized by single-crystal X-ray crystallography. These and previously reported complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO?, protons, and electrons, with rates that are first-order in catalyst and formate at formate concentrations below ?0.04 M (34 equiv). At concentrations above ?0.06 M formate (52 equiv), catalytic rates become nearly independent of formate concentration. For the catalysts studied, maximum observed turnover frequencies vary from <1.1 to 15.8 s{sup 1} at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. These catalysts are the only base-metal electrocatalysts as well as the only homogeneous electrocatalysts reported to date for the oxidation of formate. An acetate complex demonstrating an ?-OC(O)CH? binding mode to nickel has also been synthesized and characterized by single-crystal X-ray crystallography. Based on this structure and the electrochemical and spectroscopic data, a mechanistic scheme for electrocatalytic formate oxidation is proposed which involves formate binding followed by a rate-limiting proton and two-electron transfer step accompanied by CO? liberation. The pendant amines have been demonstrated to be essential for electrocatalysis, as no activity toward formate oxidation was observed for the similar [Ni(depe)?]{su p2+} (depe = 1,2-bis(diethylphosphino)ethane) complex.

  13. In Silico Inhibition Studies of Jun-Fos-DNA Complex Formation by Curcumin Derivatives

    PubMed Central

    Kumar, Anil; Bora, Utpal

    2012-01-01

    Activator protein-1 (AP1) is a transcription factor that consists of the Jun and Fos family proteins. It regulates gene expression in response to a variety of stimuli and controls cellular processes including proliferation, transformation, inflammation, and innate immune responses. AP1 binds specifically to 12-O-tetradecanoylphorbol-13-acetate (TPA) responsive element 5?-TGAG/CTCA-3? (AP1 site). It has been found constitutively active in breast, ovarian, cervical, and lung cancers. Numerous studies have shown that inhibition of AP1 could be a promising strategy for cancer therapeutic applications. The present in silico study provides insights into the inhibition of Jun-Fos-DNA complex formation by curcumin derivatives. These derivatives interact with the amino acid residues like Arg155 and Arg158 which play a key role in binding of Jun-Fos complex to DNA (AP1 site). Ala151, Ala275, Leu283, and Ile286 were the residues present at binding site which could contribute to hydrophobic contacts with inhibitor molecules. Curcumin sulphate was predicted to be the most potent inhibitor amongst all the natural curcumin derivatives docked. PMID:25374685

  14. A calorimetric study of the hydrolysis and peroxide complex formation of the uranyl(VI) ion.

    PubMed

    Zanonato, Pier Luigi; Di Bernardo, Plinio; Grenthe, Ingmar

    2014-02-14

    The enthalpies of reaction for the formation of uranyl(vi) hydroxide {[(UO2)2(OH)2](2+), [(UO2)3(OH)4](2+), [(UO2)3(OH)5](+), [(UO2)3(OH)6](aq), [(UO2)3(OH)7](-), [(UO2)3(OH)8](2-), [(UO2)(OH)3](-), [(UO2)(OH)4](2-)} and peroxide complexes {[UO2(O2)(OH)](-) and [(UO2)2(O2)2(OH)](-)} have been determined from calorimetric titrations at 25 °C in a 0.100 M tetramethyl ammonium nitrate ionic medium. The hydroxide data have been used to test the consistency of the extensive thermodynamic database published by the Nuclear Energy Agency (I. Grenthe, J. Fuger, R. J. M. Konings, R. J. Lemire, A. B. Mueller, C. Nguyen-Trung and H. Wanner, Chemical Thermodynamics of Uranium, North-Holland, Amsterdam, 1992 and R. Guillaumont, T. Fanghänel, J. Fuger, I. Grenthe, V. Neck, D. J. Palmer and M. R. Rand, Update on the Chemical Thermodynamics of Uranium, Neptunium, Plutonium, Americium and Technetium, Elsevier, Amsterdam, 2003). A brief discussion is given about a possible structural relationship between the trinuclear complexes [(UO2)3(OH)n](6-n), n = 4-8. PMID:24301256

  15. A reduced-complexity model for river delta formation - Part 1: Modeling deltas with channel dynamics

    NASA Astrophysics Data System (ADS)

    Liang, M.; Voller, V. R.; Paola, C.

    2015-01-01

    In this work we develop a reduced-complexity model (RCM) for river delta formation (referred to as DeltaRCM in the following). It is a rule-based cellular morphodynamic model, in contrast to reductionist models based on detailed computational fluid dynamics. The basic framework of this model (DeltaRCM) consists of stochastic parcel-based cellular routing schemes for water and sediment and a set of phenomenological rules for sediment deposition and erosion. The outputs of the model include a depth-averaged flow field, water surface elevation and bed topography that evolve in time. Results show that DeltaRCM is able (1) to resolve a wide range of channel dynamics - including elongation, bifurcation, avulsion and migration - and (2) to produce a variety of deltas such as alluvial fan deltas and deltas with multiple orders of bifurcations. We also demonstrate a simple stratigraphy recording component which tracks the distribution of coarse and fine materials and the age of the deposits. Essential processes that must be included in reduced-complexity delta models include a depth-averaged flow field that guides sediment transport a nontrivial water surface profile that accounts for backwater effects at least in the main channels, both bedload and suspended sediment transport, and topographic steering of sediment transport.

  16. Electrocatalytic Oxidation of Formate with Nickel Diphosphane Dipeptide Complexes: Effect of Ligands Modified with Amino Acids

    SciTech Connect

    Galan, Brandon R.; Reback, Matthew L.; Jain, Avijita; Appel, Aaron M.; Shaw, Wendy J.

    2013-10-28

    A series of nickel bis-diphosphine complexes with dipeptides appended to the ligands were investigated for the catalytic oxidation of formate. Typical rates of ~7 s-1 were found, similar to the parent complex (~8 s-1), with amino acid size and positioning contributing very little to rate or operating potential. Hydroxyl functionalities did result in lower rates, which were recovered by protecting the hydroxyl group. The results suggest that the overall dielectric introduced by the dipeptides does not play an important role in catalysis, but free hydroxyl groups do influence activity suggesting contributions from intra- or intermolecular interactions. These observations are important in developing a fundamental understanding of the affect that an enzyme-like outer coordination sphere can have upon molecular catalysts. This work was funded by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (BRG, AJ, AMA, WJS), the US DOE Basic Energy Sciences, Physical Bioscience program (MLR). Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  17. MOZ increases p53 acetylation and premature senescence through its complex formation with PML.

    PubMed

    Rokudai, Susumu; Laptenko, Oleg; Arnal, Suzzette M; Taya, Yoichi; Kitabayashi, Issay; Prives, Carol

    2013-03-01

    Monocytic leukemia zinc finger (MOZ)/KAT6A is a MOZ, Ybf2/Sas3, Sas2, Tip60 (MYST)-type histone acetyltransferase that functions as a coactivator for acute myeloid leukemia 1 protein (AML1)- and Ets family transcription factor PU.1-dependent transcription. We previously reported that MOZ directly interacts with p53 and is essential for p53-dependent selective regulation of p21 expression. We show here that MOZ is an acetyltransferase of p53 at K120 and K382 and colocalizes with p53 in promyelocytic leukemia (PML) nuclear bodies following cellular stress. The MOZ-PML-p53 interaction enhances MOZ-mediated acetylation of p53, and this ternary complex enhances p53-dependent p21 expression. Moreover, we identified an Akt/protein kinase B recognition sequence in the PML-binding domain of MOZ protein. Akt-mediated phosphorylation of MOZ at T369 has a negative effect on complex formation between PML and MOZ. As a result of PML-mediated suppression of Akt, the increased PML-MOZ interaction enhances p21 expression and induces p53-dependent premature senescence upon forced PML expression. Our research demonstrates that MOZ controls p53 acetylation and transcriptional activity via association with PML. PMID:23431171

  18. Formation of the ternary inclusion complex of limaprost with ?- and ?-cyclodextrins in aqueous solution.

    PubMed

    Inoue, Yasuo; Sekiya, Noboru; Yamamoto, Masanobu; Iohara, Daisuke; Hirayama, Fumitoshi; Uekama, Kaneto

    2015-01-01

    The inclusion mode of Limaprost in the presence of ?- and ?-cyclodextrins (CDs) was investigated to gain insight into the stabilization mechanism of Limaprost-alfadex upon the addition of ?-CD in the solid state. The inclusion sites of ?- and ?-CDs were studied by NMR spectroscopic and kinetic methods. With the addition of ?- and ?-CDs, displacements in (13)C chemical shifts of prostaglandin F2? (PGF2?) were observed in the ?-chain and the five-membered ring, respectively, of the drug. Similar shift changes were observed with the addition of both ?- and ?-CDs. In two-dimensional (2D) (1)H-NMR spectra, intermolecular correlation peaks were observed between protons of PGF2? and protons of both ?- and ?-CDs, suggesting that PGF2? interacts with ?- and ?-CDs to form a ternary complex by including the ?-chain with the former CD and the five-membered ring with the latter. In kinetic studies in aqueous solution, Limaprost was degraded to 17S,20-dimethyl-trans-?(2)-PGA1 (11-deoxy-?(10)) and 17S,20-dimethyl-trans-?(2)-8-iso-PGE1 (8-iso). The addition of ?-CD promoted the dehydration to 11-deoxy-?(10), while ?-CD promoted the isomerization to 8-iso, under these conditions. In the presence of both ?- and ?-CDs, dehydration and isomerization were also accelerated, supporting the formation of the ternary Limaprost/?-CD/?-CD complex. PMID:25948325

  19. Efficient Super Energy Transfer Collisions Through Reactive-Complex Formation: H + SO2

    NASA Astrophysics Data System (ADS)

    Smith, Jonathan M.; Wilhelm, Michael J.; Ma, Jianqiang; Dai, HAI-LUNG

    2015-06-01

    Translational-to-vibrational energy transfer (ET) from a hyperthermal H atom to ambient SO2 was characterized using time-resolved Fourier transform infrared emission spectroscopy. Vibrational excitation of SO2, following collisions with H atoms containing 59 kcal/mol of kinetic energy, generated from the 193 nm photolysis of HBr, is detected in two distinct energy distributions: one with excitation predominantly at the fundamental vibrational levels is attributable to classical impulsive collisions, while the other, accounting for 80% of the excited SO2 with vibrational energy as high as 14,000 wn, is proposed to arise from the formation of a transient reactive-complex during the collision. The cross-section for this super ET collision is determined to be 0.530.05 2, or roughly 2% of all hard sphere collisions. This observation reveals that in collisions between a hyperthermal atom and an ambient molecule, for which a reactive-complex exists on the potential energy surface, a large quantity of translational energy can be transferred to the molecule with high efficiency.

  20. UXT-V1 protects cells against TNF-induced apoptosis through modulating complex II formation

    PubMed Central

    Huang, Yuefeng; Chen, Liang; Zhou, Yi; Liu, Heng; Yang, Jueqing; Liu, Zhenggang; Wang, Chen

    2011-01-01

    Proteins that directly regulate tumor necrosis factor (TNF) signaling have critical roles in determining cell death and survival. Previously we characterized ubiquitously expressed transcript (UXT)-V2 as a novel transcriptional cofactor to regulate nuclear factor-?B in the nucleus. Here we report that another splicing isoform of UXT, UXT-V1, localizes in cytoplasm and regulates TNF-induced apoptosis. UXT-V1 knockdown cells are hypersensitive to TNF-induced apoptosis. We demonstrated that UXT-V1 is a new component of TNF receptor signaling complex. We found that UXT-V1 binds to TNF receptor-associated factor 2 and prevents TNF receptorassociated death domain protein from recruiting Fas-associated protein with death domain. More importantly, UXT-V1 is a short-half-life protein, the degradation of which facilitates the formation of the apoptotic receptor complex II in response to TNF treatment. This study demonstrates that UXT-V1 is a novel regulator of TNF-induced apoptosis and sheds new light on the underlying molecular mechanism of this process. PMID:21307340

  1. Formation and unimolecular dissociation of Al3+(DMSO)n complexes

    NASA Astrophysics Data System (ADS)

    El-Nahas, Ahmed M.; Xiao, Chuanyun; Hagelberg, Frank

    2004-09-01

    Density functional theory (DFT) calculations at the B3LYP/6-31+G(d) level have been performed to follow up the formation and dissociation of Al3+(DMSO)n complexes (n = 1-3) in the gas phase. Different exit channels are examined and transition states for unimolecular dissociation processes have been located. These channels include loss of neutral (DMSO, CH3, and CH4) as well as charged (DMSO+, (CH3)2S+, CH3+, and DMSOH+) fragments. The minimum number (nmin) of DMSO ligands needed to stabilize Al3+ is 2. Loss of the neutral species is energetically unfavorable and release of DMSO needs high coordination number. On the other hand, charge-separation processes (loss of DMSO+, CH3+, and (CH3)2S+) are thermodynamically feasible. The loss of a methyl cation is thermodynamically the most favorable process for n = 2, while the loss of the dimethyl thioether cation is the preferred one for n = 3. Nevertheless, the presence of sizable kinetic energy barriers (40-89 kcal/mol) hinders such transformation and yields metastable Al3+(DMSO)2,3 complexes. Therefore, DMSO di- and triligated Al trications form kinetically metastable species and could be observed in the gas phase. Comparison with the available experimental data is presented and could motivate further studies.

  2. Selfconsistent Formation of complex layered mantle flow with a Rough Core-Mantle Boundary

    NASA Astrophysics Data System (ADS)

    Hansen, Ulrich; Stein, Claudia

    2015-04-01

    Thermal boundary layers play a key role for the dynamics of the Earth's mantle. They mark the transition between the core and the mantle and, at least locally and transiently, the transition between the upper and the lower mantle at a depth of 670 km. There is much evidence that these boundary layers do not resemble the picture of a simple thermal boundary layer, as known from thermal convection at high Rayleigh numbers. Especially the core-mantle boundary (CMB) seems to be of complex structure, possible induced by compositionally dense material. Present models of mantle convection, aiming at simulating the complex structure and dynamics of the CMB require several ad hoc assumptions. Especially the density excess and the mass of compositionally distinct material need to be assumed. Both conditions are critical for the dynamics but hardly constrained. We have developed models where the internal boundary as well as a thermochemical CMB develop selfconsistently without the named ad hoc assumptions. As a starting condition we assume that a chemically stratified mantle, as resulting from fractional crystallization in an early magma ocean, is heated by the hot core. Double diffusive convection in material with strongly variable viscosity leads then to layering and, in a later state to the formation of a rough lower thermochemical boundary layer, displaying compositionally distinct piles.

  3. Functionalized organotin-chalcogenide complexes that exhibit defect heterocubane scaffolds: formation, synthesis, and characterization.

    PubMed

    Euner, Jens P; Barth, Beatrix E K; Leusmann, Eliza; You, Zhiliang; Rinn, Niklas; Dehnen, Stefanie

    2013-10-01

    The synthesis of new functionalized organotin-chalcogenide complexes was achieved by systematic optimization of the reaction conditions. The structures of compounds [(R(1,?2) Sn)3 S4 Cl] (1, 2), [((R(2) Sn)2 SnS4 )2 (?-S)2 ] (3), [(R(1,?2) Sn)3 Se4 ][SnCl3 ] (4, 5), and [Li(thf)n ][(R(3) Sn)(HR(3) Sn)2 Se4 Cl] (6), in which R(1) =CMe2 CH2 C(O)Me, R(2) =CMe2 CH2 C(NNH2 )Me, and R(3) =CH2 CH2 COO, are based on defect heterocubane scaffolds, as shown by X-ray diffraction, (119) Sn?NMR spectroscopy, and ESI mass spectrometry analyses. Compounds 4, 5, and 6 constitute the first examples of defect heterocubane-type metal-chalcogenide complexes that are comprised of selenide ligands. Comprehensive DFT calculations prompted us to search for the formal intermediates [(R(1) SnCl2 )2 (?-S)] (7) and [(R(1) SnCl)2 (?-S)2 ] (8), which were isolated and helped to understand the stepwise formation of compounds 1-6. PMID:23963989

  4. Labeled EF-Tus for rapid kinetic studies of pretranslocation complex formation.

    PubMed

    Liu, Wei; Kavaliauskas, Darius; Schrader, Jared M; Poruri, Kiran; Birkedal, Victoria; Goldman, Emanuel; Jakubowski, Hieronim; Mandecki, Wlodek; Uhlenbeck, Olke C; Knudsen, Charlotte R; Goldman, Yale E; Cooperman, Barry S

    2014-10-17

    The universally conserved translation elongation factor EF-Tu delivers aminoacyl(aa)-tRNA in the form of an aa-tRNAEF-TuGTP ternary complex (TC) to the ribosome where it binds to the cognate mRNA codon within the ribosomal A-site, leading to formation of a pretranslocation (PRE) complex. Here we describe preparation of QSY9 and Cy5 derivatives of the variant E348C-EF-Tu that are functional in translation elongation. Together with fluorophore derivatives of aa-tRNA and of ribosomal protein L11, located within the GTPase associated center (GAC), these labeled EF-Tus allow development of two new FRET assays that permit the dynamics of distance changes between EF-Tu and both L11 (Tu-L11 assay) and aa-tRNA (Tu-tRNA assay) to be determined during the decoding process. We use these assays to examine: (i) the relative rates of EF-Tu movement away from the GAC and from aa-tRNA during decoding, (ii) the effects of the misreading-inducing antibiotics streptomycin and paromomycin on tRNA selection at the A-site, and (iii) how strengthening the binding of aa-tRNA to EF-Tu affects the rate of EF-Tu movement away from L11 on the ribosome. These FRET assays have the potential to be adapted for high throughput screening of ribosomal antibiotics. PMID:25126896

  5. Labeled EF-Tus for Rapid Kinetic Studies of Pretranslocation Complex Formation

    PubMed Central

    2015-01-01

    The universally conserved translation elongation factor EF-Tu delivers aminoacyl(aa)-tRNA in the form of an aa-tRNAEF-TuGTP ternary complex (TC) to the ribosome where it binds to the cognate mRNA codon within the ribosomal A-site, leading to formation of a pretranslocation (PRE) complex. Here we describe preparation of QSY9 and Cy5 derivatives of the variant E348C-EF-Tu that are functional in translation elongation. Together with fluorophore derivatives of aa-tRNA and of ribosomal protein L11, located within the GTPase associated center (GAC), these labeled EF-Tus allow development of two new FRET assays that permit the dynamics of distance changes between EF-Tu and both L11 (Tu-L11 assay) and aa-tRNA (Tu-tRNA assay) to be determined during the decoding process. We use these assays to examine: (i) the relative rates of EF-Tu movement away from the GAC and from aa-tRNA during decoding, (ii) the effects of the misreading-inducing antibiotics streptomycin and paromomycin on tRNA selection at the A-site, and (iii) how strengthening the binding of aa-tRNA to EF-Tu affects the rate of EF-Tu movement away from L11 on the ribosome. These FRET assays have the potential to be adapted for high throughput screening of ribosomal antibiotics. PMID:25126896

  6. Bacillus subtilis δ Factor Functions as a Transcriptional Regulator by Facilitating the Open Complex Formation.

    PubMed

    Prajapati, Ranjit Kumar; Sengupta, Shreya; Rudra, Paulami; Mukhopadhyay, Jayanta

    2016-01-15

    Most bacterial RNA polymerases (RNAP) contain five conserved subunits, viz. 2α, β, β', and ω. However, in many Gram-positive bacteria, especially in fermicutes, RNAP is associated with an additional factor, called δ. For over three decades since its identification, it had been thought that δ functioned as a subunit of RNAP to enhance the level of transcripts by recycling RNAP. In support of the previous observations, we also find that δ is involved in recycling of RNAP by releasing the RNA from the ternary complex. We further show that δ binds to RNA and is able to recycle RNAP when the length of the nascent RNA reaches a critical length. However, in this work we decipher a new function of δ. Performing biochemical and mutational analysis, we show that Bacillus subtilis δ binds to DNA immediately upstream of the promoter element at A-rich sequences on the abrB and rrnB1 promoters and facilitates open complex formation. As a result, δ facilitates RNAP to initiate transcription in the second scale, compared with minute scale in the absence of δ. Using transcription assay, we show that δ-mediated recycling of RNAP cannot be the sole reason for the enhancement of transcript yield. Our observation that δ does not bind to RNAP holo enzyme but is required to bind to DNA upstream of the -35 promoter element for transcription activation suggests that δ functions as a transcriptional regulator. PMID:26546673

  7. The Axin1 scaffold protein promotes formation of a degradation complex for c-Myc.

    PubMed

    Arnold, Hugh K; Zhang, Xiaoli; Daniel, Colin J; Tibbitts, Deanne; Escamilla-Powers, Julie; Farrell, Amy; Tokarz, Sara; Morgan, Charlie; Sears, Rosalie C

    2009-03-01

    Expression of the c-Myc proto-oncoprotein is tightly regulated in normal cells. Phosphorylation at two conserved residues, threonine58 (T58) and serine62 (S62), regulates c-Myc protein stability. In cancer cells, c-Myc can become aberrantly stabilized associated with altered T58 and S62 phosphorylation. A complex signalling cascade involving GSK3beta kinase, the Pin1 prolyl isomerase, and the PP2A-B56alpha phosphatase controls phosphorylation at these sites. We report here a novel role for the tumour suppressor scaffold protein Axin1 in facilitating the formation of a degradation complex for c-Myc containing GSK3beta, Pin1, and PP2A-B56alpha. Although knockdown of Axin1 decreases the association of c-Myc with these proteins, reduces T58 and enhances S62 phosphorylation, and increases c-Myc stability, acute expression of Axin1 reduces c-Myc levels and suppresses c-Myc transcriptional activity. Moreover, the regulation of c-Myc by Axin1 is impaired in several tested cancer cell lines with known stabilization of c-Myc or loss of Axin1. This study provides critical insight into the regulation of c-Myc expression, how this can be disrupted in three cancer types, and adds to our knowledge of the tumour suppressor activity of Axin1. PMID:19131971

  8. The Axin1 scaffold protein promotes formation of a degradation complex for c-Myc

    PubMed Central

    Arnold, Hugh K; Zhang, Xiaoli; Daniel, Colin J; Tibbitts, Deanne; Escamilla-Powers, Julie; Farrell, Amy; Tokarz, Sara; Morgan, Charlie; Sears, Rosalie C

    2009-01-01

    Expression of the c-Myc proto-oncoprotein is tightly regulated in normal cells. Phosphorylation at two conserved residues, threonine58 (T58) and serine62 (S62), regulates c-Myc protein stability. In cancer cells, c-Myc can become aberrantly stabilized associated with altered T58 and S62 phosphorylation. A complex signalling cascade involving GSK3? kinase, the Pin1 prolyl isomerase, and the PP2A-B56? phosphatase controls phosphorylation at these sites. We report here a novel role for the tumour suppressor scaffold protein Axin1 in facilitating the formation of a degradation complex for c-Myc containing GSK3?, Pin1, and PP2A-B56?. Although knockdown of Axin1 decreases the association of c-Myc with these proteins, reduces T58 and enhances S62 phosphorylation, and increases c-Myc stability, acute expression of Axin1 reduces c-Myc levels and suppresses c-Myc transcriptional activity. Moreover, the regulation of c-Myc by Axin1 is impaired in several tested cancer cell lines with known stabilization of c-Myc or loss of Axin1. This study provides critical insight into the regulation of c-Myc expression, how this can be disrupted in three cancer types, and adds to our knowledge of the tumour suppressor activity of Axin1. PMID:19131971

  9. Interactions between plutonism and detachments during metamorphic core complex formation, Serifos Island (Cyclades, Greece)

    NASA Astrophysics Data System (ADS)

    Rabillard, Aurélien; Arbaret, Laurent; Jolivet, Laurent; Le Breton, Nicole; Gumiaux, Charles; Augier, Romain; Grasemann, Bernhard

    2015-06-01

    In order to better understand the interactions between plutonic activity and strain localization during metamorphic core complex formation, the Miocene granodioritic pluton of Serifos (Cyclades, Greece) is studied. This pluton (11.6-9.5 Ma) intruded the Cycladic Blueschists during thinning of the Aegean domain along a system of low-angle normal faults belonging to the south dipping West Cycladic Detachment System (WCDS). Based on structural fieldwork, together with microstructural observations and anisotropy of magnetic susceptibility, we recognize a continuum of deformation from magmatic to brittle conditions within the magmatic body. This succession of deformation events is kinematically compatible with the development of the WCDS. The architecture of the pluton shows a marked asymmetry resulting from its interaction with the detachments. We propose a tectonic scenario for the emplacement of Serifos pluton and its subsequent cooling during the Aegean extension: (1) A first stage corresponds to the metamorphic core complex initiation and associated southwestward shearing along the Meghàlo Livadhi detachment. (2) In the second stage, the Serifos pluton has intruded the dome at shallow crustal level, piercing through the ductile/brittle Meghàlo Livadhi detachment. Southwest directed extensional deformation was contemporaneously transferred upward in the crust along the more localized Kàvos Kiklopas detachment. (3) The third stage was marked by synmagmatic extensional deformation and strain localization at the contact between the pluton and the host rocks resulting in nucleation of narrow shear zones, which (4) continued to develop after the pluton solidification.

  10. Preparation and evaluation of periodontal films based on polyelectrolyte complex formation.

    PubMed

    Kassem, Abeer Ahmed; Ismail, Fatma Ahmed; Naggar, Viviane Fahim; Aboulmagd, Elsayed

    2015-05-01

    Local intra-pocket drug delivery devices can provide an effective concentration of the antimicrobial agent at the site of action with avoidance of undesirable side effects. This study explored the application of chitosan-alginate and chitosan-pectin polyelectrolyte complex (PEC) films as drug release regulators for tetracycline HCl (Tc) to treat periodontal pockets. Periodontal films with 1:1 Tc:PEC ratio were prepared using 1:1 chitosan (Ch) to sodium alginate (A) or 1:3 Ch to pectin (P). The scanning electron microscope showed acceptable film appearance and differential scanning calorimetry analysis confirmed complex formation. The in vitro release studies for both films showed a burst drug release, followed by prolonged release for 70?h. A prolonged antibacterial activity of both films against Staphylococcus aureus ATCC 6538 was observed over a period of 21 days. Aging studies indicated that the five months storage period in freezer did not significantly influence the drug release profile or the antibacterial activity of both films. Clinical evaluation showed a significant reduction in pocket depth (p?

  11. Synthesis of mono(dinitrogen) complexes of molybdenum. Formation of ammonia and hydrazine

    SciTech Connect

    George, T.A.; Tisdale, R.C.

    1988-08-24

    The synthesis and reactivity of a series of mono-N/sub 2/ complexes of molybdenum are reported. Reduction of MoCl/sub 3/(triphos), where triphos = PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/, with sodium amalgam in the presence of 2L or L/sub 2/ and with a regulated amount of N/sub 2/ led to the formation of Mo(N/sub 2/)(triphos)(L/sub 2/) (1-5): 1, L = PMe/sub 2/Ph; 2, L/sub 2/ = Me/sub 2/PCH/sub 2/PMe/sub 2/, dmpm; 3, L/sub 2/ = 1,2-(Me/sub 2/As)/sub 2/C/sub 6/H/sub 4/, diars; 4, L/sub 2/ = Ph/sub 2/PCH/sub 2/PPh/sub 2/, dppm; 5, L/sub 2/ = Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/, dppe. Complexes 3 and 5 were each a mixture of two isomeric mono-N/sub 2/ complexes. Complexes 1-5 reacted with excess HX (X = Br, Cl) to afford varying yields of ammonia, hydrazine, and N/sub 2/ (and some H/sub 2/). Loss of N/sub 2/ occurred readily from 1 when it was evacuate in the solid state to give 7. Five-coordinate 7 reacted with H/sub 2/, CO, and C/sub 2/H/sub 4/ in the solid state to form MoH/sub 2/(triphos)(PMe/sub 2/Ph)/sub 2/ (8), Mo(CO)(triphos)(PMe/sub 2/Ph)/sub 2/ (9), and Mo(C/sub 2/H/sub 4/)(triphos)(PMe/sub 2/Ph)/sub 2/ (10), respectively. Reaction of solids 7, 8, and 10 with N/sub 2/ regenerated 1. Structural assignments of the new complexes are based upon /sup 31/P and /sup 1/H NMR spectral data. Triphos is shown to adopt both fac and mer configurations. 33 references, 1 table.

  12. (PEO)n:Na4P2O7- a Report on Complex Formation

    NASA Astrophysics Data System (ADS)

    Bhide, Amrtha; Hariharan, K.

    2006-06-01

    A new polymer electrolyte, based on poly (ethylene oxide) complexed with Na4P2O7 is investigated. (PEO)n:Na4P2O7 polymer metal salt complexes with different n = [ethylene oxide]/ Na ratio (80,100,120,160 and 200) are prepared by solution casting method. Dissolution of the salt into the polymer host is investigated by X-ray diffraction, differential calorimetry and Scanning electron microscopy techniques. The formation of the complex has been confirmed by (i) the broadening and reduction in the intensity of the Bragg peaks (ii) the reduction in the percentage of crystallinity by DSC and (iii) the increase in the glass transition temperature of the polymer with addition of the salt. Maximum reduction in crystallinity from 76.1 % to 56.2 % is observed for (PEO)120:Na4P2O7 system. Qualitative analysis of FTIR spectra in the range 3000-500 cm-1, reveals broadening of the bands corresponding to the C-O-C symmetric stretching modes around 840 cm-1 and 1057-1160 cm-1. These conformal changes have inferred the coordination of the ether oxygen of the PEO with the metal salt ion. Compositional dependence of conductivity studies show a maximum value of 7.58 0-7 S/cm at 351 K for O:Na = 120.Conductivity of the above electrolytes proceeds via an activated conduction mechanism with two activation energies, 0.62 eV and 0.78 eV above and below the softening of the polymer. The electronic transport number measured by dc polarization technique shows that, the conducting species are ionic in nature.

  13. When constants are important

    SciTech Connect

    Beiu, V.

    1997-04-01

    In this paper the authors discuss several complexity aspects pertaining to neural networks, commonly known as the curse of dimensionality. The focus will be on: (1) size complexity and depth-size tradeoffs; (2) complexity of learning; and (3) precision and limited interconnectivity. Results have been obtained for each of these problems when dealt with separately, but few things are known as to the links among them. They start by presenting known results and try to establish connections between them. These show that they are facing very difficult problems--exponential growth in either space (i.e. precision and size) and/or time (i.e., learning and depth)--when resorting to neural networks for solving general problems. The paper will present a solution for lowering some constants, by playing on the depth-size tradeoff.

  14. The earliest phases of high-mass star formation: the NGC 6334-NGC 6357 complex

    NASA Astrophysics Data System (ADS)

    Russeil, D.; Zavagno, A.; Motte, F.; Schneider, N.; Bontemps, S.; Walsh, A. J.

    2010-06-01

    Context. Our knowledge of high-mass star formation has been mainly based on follow-up studies of bright sources found by IRAS, and has thus been incomplete for its earliest phases, which are inconspicuous at infrared wavelengths. With a new generation of powerful bolometer arrays, unbiased large-scale surveys of nearby high-mass star-forming complexes now search for the high-mass analog of low-mass cores and class 0 protostars. Aims: Following the pioneering study of Cygnus X, we investigate the star-forming region NGC 6334-NGC 6357 (~1.7 kpc). Methods: We study the complex NGC 6334-NGC 6357 in an homogeneous way following the previous work of Motte and collaborators. We used the same method to extract the densest cores which are the most likely sites for high-mass star formation. We analyzed the SIMBA/SEST 1.2 mm data presented in Munoz and coworkers, which covers all high-column density areas (A v ? 15 mag) of the NGC 6334-NGC 6357 complex and extracted dense cores following the method used for Cygnus X. We constrain the properties of the most massive dense cores (M > 100 M_?) using new molecular line observations (as SiO, N2H+,H13CO+, HCO+ (1-0) and CH3CN) with Mopra and a complete cross-correlation with infrared databases (MSX, GLIMPSE, MIPSGAL) and literature. Results: We extracted 163 massive dense cores of which 16 are more massive than 200 M_?. These high-mass dense cores have a typical FWHM size of 0.37 pc, an average mass of M ~ 600 M_?, and a volume-averaged density of ~ 1.5 105 cm-3. Among these massive dense cores, 6 are good candidates for hosting high-mass infrared-quiet protostars, 9 cores are classified as high-luminosity infrared protostars, and we find only one high-mass starless clump (~0.3 pc, ~ 4 104 cm-3) that is gravitationally bound. Conclusions: Since our sample is derived from a single molecular complex and covers every embedded phase of high-mass star formation, it provides a statistical estimate of the lifetime of massive stars. In contrast to what is found for low-mass class 0 and class I phases, the infrared-quiet protostellar phase of high-mass stars may last as long as their more well known high-luminosity infrared phase. As in Cygnus X, the statistical lifetime of high-mass protostars is shorter than found for nearby, low-mass star-forming regions which implies that high-mass pre-stellar and protostellar cores are in a dynamic state, as expected in a molecular cloud where turbulent and/or dynamical processes dominate. Based on observations made with Mopra telescope. The Mopra telescope is part of the Australia Telescope which is funded by the Commonwealth of Australia for operation as a National Facility managed by CSIRO.Table 1 and Appendix are only available in electronic form at http://www.aanda.orgProfiles as FITS files are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/515/A55

  15. Reaction time dependent formation of Pd(II) and Pt(II) complexes of bis(methyl)thiasalen podand.

    PubMed

    Dutta, Pradip Kr; Panda, Snigdha; Krishna, G Rama; Reddy, C Malla; Zade, Sanjio S

    2013-01-14

    Thiasalen podand 9 having S2N2 donor set has been synthesized by the condensation of 2-methylthiobenzaldehyde with ethylenediamine. The reaction of the thiasalen podand ligand with Pd(II) afforded two complexes depending on the reaction time. Shorter reaction time (5 min) afforded thioether complex 10; whereas with increase in reaction time (4 h) thioether-thiolate complex 11 was obtained via cleavage of one of the two S-C(Me) bonds of bis(methyl)thiasalen podand upon complexation. The reaction of 9 with Pt(II) afforded only thiolate-thioether complex 12 independent of the reaction time. The cleavage of both the S-C(Me) bonds of bis(methyl)thiasalen to afford bisthiolate complexes has never been observed. The structures of thiasalen podands and all three complexes have been determined by single crystal X-ray diffraction analysis. All three complexes possess a square planar geometry around the metal centres. Weak van der Waals interactions through C-HF interactions are present in all three complexes leading to the formation of supramolecular synthons and the supramolecular structures are stabilized by aromatic ?? interactions, which leads to the formation of 3D pseudo-double helical network packing. Under similar conditions bis(methyl)salen did not form any complexes with Pd(II) and Pt(II). PMID:23073301

  16. CONTINUOUS MULTILIGAND DISTRIBUTION MODEL USED TO PREDICT THE STABILITY CONSTANT OF CU(II) METAL COMPLEXATION WITH HUMIC MATERIAL FROM FLUORESCENCE QUENCHING DATA

    EPA Science Inventory

    We report the use of a pH-dependent continuous multiligand distribution model to determine the stability constant between Cu(II) and dissolved humic material. luorescence quenching of the humic material by Cu(II) is used to produce spectral titration curves. he values form the ti...

  17. Mercury(II) Complex Formation With Glutathione in Alkaline Aqueous Solution

    SciTech Connect

    Mah, V.; Jalilehvand, F.

    2009-05-19

    The structure and speciation of the complexes formed between mercury(II) ions and glutathione (GSH = L-glutamyl-L-cysteinyl-glycine) have been studied for a series of alkaline aqueous solutions (C{sub Hg{sup 2+}} {approx} 18 mmol dm{sup -3} and C{sub GSH} = 40-200 mmol dm{sup -3} at pH {approx} 10.5) by means of extended X-ray absorption fine structure (EXAFS) and {sup 199}Hg NMR spectroscopy at ambient temperature. The dominant complexes are [Hg(GS){sub 2}]{sup 4-} and [Hg(GS){sub 3}]{sup 7-}, with mean Hg-S bond distances of 2.32(1) and 2.42(2) {angstrom} observed in digonal and trigonal Hg-S coordination, respectively. The proportions of the Hg{sup 2+}-glutathione complexes were evaluated by fitting linear combinations of model EXAFS oscillations representing each species to the experimental EXAFS spectra. The [Hg(GS){sub 4}]{sup 10-} complex, with four sulfur atoms coordinated at a mean Hg-S bond distance of 2.52(2) {angstrom}, is present in minor amounts (<30%) in solutions containing a large excess of glutathione (C{sub GSH} {ge} 160 mmol dm{sup -3}). Comparable alkaline mercury(II) cysteine (H{sub 2}Cys) solutions were also investigated and a reduced tendency to form higher complexes was observed, because the deprotonated amino group of Cys{sup 2-} allows the stable [Hg(S,N-Cys){sub 2}]{sup 2-} chelate to form. The effect of temperature on the distribution of the Hg{sup 2+}-glutathione complexes was studied by comparing the EXAFS spectra at ambient temperature and at 25 K of a series of glycerol/water (33/67, v/v) frozen glasses with and C{sub Hg{sup 2+}} {approx} 7 mmol dm{sup -3} and C{sub GSH} = 16-81 mmol dm{sup -3}. Complexes with high Hg-S coordination numbers, [Hg(GS){sub 3}]{sup 7-} and [Hg(GS){sub 4}]{sup 10-}, became strongly favored when just a moderate excess of glutathione (C{sub GSH} {ge} 28 mmol dm{sup -3}) was used in the glassy samples, as expected for a stepwise exothermic bond formation. Addition of glycerol had no effect on the Hg(II)-glutathione speciation, as shown by the similarity of the EXAFS spectra obtained at room temperature for two parallel series of Hg(II)-glutathione solutions with C{sub Hg{sup 2+}} {approx} 7 mmol dm{sup -3}, with and without 33% glycerol. Also, the {sup 199}Hg NMR chemical shifts of a series of {approx} 18 mmol dm{sup -3} mercury(II) glutathione solutions with 33% glycerol were not significantly different from those of the corresponding series in aqueous solution.

  18. Control of cyclic photoinitiated electron transfer between cytochrome c peroxidase (W191F) and cytochrome c by formation of dynamic binary and ternary complexes.

    PubMed

    Page, Taylor R; Hoffman, Brian M

    2015-02-10

    Extensive studies of the physiological protein-protein electron-transfer (ET) complex between yeast cytochrome c peroxidase (CcP) and cytochrome c (Cc) have left unresolved questions about how formation and dissociation of binary and ternary complexes influence ET. We probe this issue through a study of the photocycle of ET between Zn-protoporphyrin IX-substituted CcP(W191F) (ZnPCcP) and Cc. Photoexcitation of ZnPCcP in complex with Fe(3+)Cc initiates the photocycle: charge-separation ET, [(3)ZnPCcP, Fe(3+)Cc] ? [ZnP(+)CcP, Fe(2+)Cc], followed by charge recombination, [ZnP(+)CcP, Fe(2+)Cc] ? [ZnPCcP, Fe(3+)Cc]. The W191F mutation eliminates fast hole hopping through W191, enhancing accumulation of the charge-separated intermediate and extending the time scale for binding and dissociation of the charge-separated complex. Both triplet quenching and the charge-separated intermediate were monitored during titrations of ZnPCcP with Fe(3+)Cc, Fe(2+)Cc, and redox-inert CuCc. The results require a photocycle that includes dissociation and/or recombination of the charge-separated binary complex and a charge-separated ternary complex, [ZnP(+)CcP, Fe(2+)Cc, Fe(3+)Cc]. The expanded kinetic scheme formalizes earlier proposals of "substrate-assisted product dissociation" within the photocycle. The measurements yield the thermodynamic affinity constants for binding the first and second Cc: KI = 10(-7) M(-1), and KII = 10(-4) M(-1). However, two-site analysis of the thermodynamics of formation of the ternary complex reveals that Cc binds at the weaker-binding site with much greater affinity than previously recognized and places upper bounds on the contributions of repulsion between the two Cc's of the ternary complex. In conjunction with recent nuclear magnetic resonance studies, the analysis further suggests a dynamic view of the ternary complex, wherein neither Cc necessarily faithfully adopts the crystal-structure configuration because of Cc-Cc repulsion. PMID:25629200

  19. Inclusion complex formation of ternary system: Fluoroscein-p-sulfonato calix[4]arene-Cu2+ by cooperative binding

    NASA Astrophysics Data System (ADS)

    Gawhale, Sharadchandra; Jadhav, Ankita; Rathod, Nilesh; Malkhede, Dipalee; Chaudhari, Gajanan

    2015-09-01

    The aqueous solution of fluorescein-para sulfonato calix[4]arene-metal ion complex has been studied based on absorption, fluorescence, 1H NMR and FTIR spectroscopic results. It was found that the fluorescence intensity quenched regularly upon addition of pSCX4 and metal ion. The quenching constants and binding constants were determined for pSCX4-FL and pSCX4-FL-Cu2+ systems. 1:1 stoichiometry is obtained for pSCX4-Cu2+ system by continuous variation method. The NMR and IR results indicates the interaction among FL, pSCX4 and Cu2+. The combined results demonstrate the cooperative binding to design the complex for ternary system. The life time for binary and ternary system has been studied.

  20. Formation of metamorphic core complex in inherited wedges: A thermomechanical modelling study

    NASA Astrophysics Data System (ADS)

    Huet, B.; Le Pourhiet, L.; Labrousse, L.; Burov, E. B.; Jolivet, L.

    2011-09-01

    Metamorphic Core Complexes (MCCs) form when a thickened domain with a low-strength lower crust is submitted to extension. These structures are characteristic of post-orogenic extension, and field observations suggest that several MCCs rework a crustal nappe-stack emplaced before extension begins. These MCCs therefore develop within heterogeneous crusts that contain pre-existing dipping heterogeneities, such as thrust faults and dipping nappes in a crustal wedge. Although very common, this first order structural inheritance has never been considered in studies modelling MCCs. Our contribution therefore investigates the effect of an inherited crustal wedge structure on the dynamics and kinematics of formation of the MCCs, using fully coupled thermomechanical modelling. The wealth of petrological, structural and time informations available in the Cycladic MCCs (Aegean domain) allows setting up more realistic initial conditions for the experiments than usual flat-lying setups. It also allows the results of the numerical computation to be directly validated with final geometries, P-T paths and exhumation rates. The experiments using dipping heterogeneities are characterised by a much more complex evolution and final structure than their flat-lying layered equivalents. Dipping heterogeneities drive lateral strength contrasts and help to re-localise the deformation on successive detachments. The dip of the inherited wedge structures imposes kinematic constraints on the flow, which provides a model that explains the regional scale asymmetry of the Cycladic MCCs. The P-T paths, the exhumation rates and the final crustal structure that come out of an initial shallow-dipping wedge model provide a much more realistic comparison with their natural counter-parts than common flat-lying models. Other parameters, like crustal-scale density inversion, thermal structure and creep law parameters are of second order when compared to the initial wedge structure. Being little dependent on these second order parameters, the proposed model for the formation of MCCs within inherited crustal wedges is likely to be applied to other areas where the MCCs formed in a nappe stack involving continental basement.

  1. Protostellar Interferometric Line Survey (PILS): Constraining the formation of complex organic molecules with ALMA

    NASA Astrophysics Data System (ADS)

    Jorgensen, Jes K.; Coutens, Audrey; Bourke, Tyler L.; Favre, Cecile; Garrod, Robin; Lykke, Julie; Mueller, Holger; Oberg, Karin I.; Schmalzl, Markus; van der Wiel, Matthijs; van Dishoeck, Ewine; Wampfler, Susanne F.

    2015-08-01

    Understanding how, when and where complex organic and potentially prebiotic molecules are formed is a fundamental goal of astrochemistry and an integral part of origins of life studies. Already now ALMA is showing its capabilities for studies of the chemistry of solar-type stars with its high sensitivity for faint lines, high spectral resolution which limits line confusion, and high angular resolution making it possible to study the structure of young protostars on solar-system scales. We here present the first results from a large unbiased survey “Protostellar Interferometric Line Survey (PILS)” targeting one of the astrochemical template sources, the low-mass protostellar binary IRAS 16293-2422. The survey is more than an order of magnitude more sensitive than previous surveys of the source and provide imaging down to 25 AU scales (radius) around each of the two components of the binary. An example of one of the early highlights from the survey is unambiguous detections of the (related) prebiotic species glycolaldehyde, ethylene glycol (two lowest energy conformers), methyl formate and acetic acid. The glycolaldehyde-ethylene glycol abundance ratio is high in comparison to comets and other protostars - but agrees with previous measurements, e.g., in the Galactic Centre clouds possibly reflecting different environments and/or evolutionary histories. Complete mapping of this and other chemical networks in comparison with detailed chemical models and laboratory experiments will reveal the origin of complex organic molecules in a young protostellar system and investigate the link between these protostellar stages and the early Solar System.

  2. Cutaneous leishmaniasis: immune complex formation and necrosis in the acute phase.

    PubMed Central

    Ridley, M. J.; Ridley, D. S.

    1984-01-01

    Twenty biopsies of lesions of cutaneous leishmaniasis were classified according to the mechanism of parasite elimination, on the basis of macrophage activation (five cases) or macrophage lysis (15 cases). The immunoperoxidase technique was used to demonstrate free Leishmania antigen, immunoglobulins, complement, lysozyme, C-reactive protein, beta-lipoprotein, alpha 1-antitrypsin, alpha 2-macroglobulin, plasminogen and factor VIII, which were quantitated and comparatively assessed. The fall in the parasite load during the course of the infection was associated with rising levels of IgG, IgM and IgE, and of the complement components of the classical pathway. Macrophage lysis supervened when there was an approximate equivalence of antigen and antibody, and was associated with the deposition of immune complex components. Lysis of the acute focal type (C response) was accompanied by a massive liberation of free Leishmania antigen, followed by a fall indicative of parasite elimination. The lysis of small numbers of macrophages scattered diffusely in the lesion, which was slow to reach completion (B response), was less effective and immunologically closer to the non-lytic (A) response. A terminal fall of the immunological factors other than the globulins, suggestive of resolution, was observed mainly in the C response. Lymphocytes may be important in macrophage activation associated with the macrophage A response and in the later stage of the B and C responses. However immunologically induced host-cell lysis is more important than macrophage activation for the elimination of Leishmania in the acute stage of most skin lesions. It is associated with, and may be caused by, the formation in situ of immune complexes of Leishmania antigen and antibody at an appropriate ratio. Images Fig. 2 Fig. 3 Fig. 4 PMID:6378241

  3. Pore-controlled formation of 0D metal complexes in anionic 3D metal-organic frameworks

    SciTech Connect

    Zhang, MW; Bosch, M; Zhou, HC

    2015-01-01

    The host-guest chemistry between a series of anionic MOFs and their trapped counterions was investigated by single crystal XRD. The PCN-514 series contains crystallographically identifiable metal complexes trapped in the pores, where their formation is controlled by the size and shape of the MOF pores. A change in the structure and pore size of PCN-518 indicates that the existence of guest molecules may reciprocally affect the formation of host MOFs.

  4. Undergraduate Analytical Chemistry Experiment: The Determination of Formation Constants for Acetate and Mono-and Dichloroacetate Salts of Primary, Secondary, and Tertiary Methyl-and Ethylamines

    ERIC Educational Resources Information Center

    D'Amelia, Ronald P.; Chiang, Stephanie; Pollut, Stephanie; Nirode, William F.

    2014-01-01

    The formation and the hydrolysis of organic salts produced by the titration of a 0.1 M solution of the following amines: methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, and triethylamine with a 0.1 M solution of acetic, chloroacetic, and dichloracetic acids are studied. The pK[subscript b] of the amine and the pH at the end point were determined

  5. Undergraduate Analytical Chemistry Experiment: The Determination of Formation Constants for Acetate and Mono-and Dichloroacetate Salts of Primary, Secondary, and Tertiary Methyl-and Ethylamines

    ERIC Educational Resources Information Center

    D'Amelia, Ronald P.; Chiang, Stephanie; Pollut, Stephanie; Nirode, William F.

    2014-01-01

    The formation and the hydrolysis of organic salts produced by the titration of a 0.1 M solution of the following amines: methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, and triethylamine with a 0.1 M solution of acetic, chloroacetic, and dichloracetic acids are studied. The pK[subscript b] of the amine and the pH at the end point were determined…

  6. Assessment of the CCSD and CCSD(T) Coupled-Cluster Methods in Calculating Heats of Formation for Zn Complexes

    PubMed Central

    Weaver, Michael N.; Yang, Yue

    2010-01-01

    Heats of formation were calculated using coupled-cluster methods for a series of zinc complexes. The calculated values were evaluated against previously conducted computational studies using density functional methods as well as experimental values. Heats of formation for nine neutral ZnXn complexes [X = -Zn, -H, -O, -F2, -S, -Cl, -Cl2, -CH3, (-CH3)2] were determined at the CCSD and CCSD(T) levels using the 631G** and TZVP basis sets, as well as the LANL2DZ-631G** (LACVP**) and LANL2DZ-TZVP hybrid basis sets. The CCSD(T)/631G** level of theory was found to predict the heat of formation for the non-alkyl Zn complexes most accurately. The alkyl Zn species were problematic in that none of the methods that were tested accurately predicted the heat of formation for these complexes. For the seven non-alkyl species, the CCSD(T)/631G** level of theory was shown to predict the most accurate heat of formation values. In instances where experimental geometric parameters were available, these were most accurately predicted by the CCSD/631G** level of theory; going to CCSD(T) did not improve agreement with the experimental values. PMID:19691272

  7. Inhibition of histidyl-tRNA-adenosine triphosphate phosphoribosyltransferase complex formation by histidine and by guanosine tetraphosphate.

    PubMed Central

    Kleeman, J E; Parsons, S M

    1977-01-01

    Formation of the complex between the first enzyme of histidine biosynthesis from Salmonella typhimurium, ATP phosphoribosyltransferase [1-(5'-phosphoribosyl)-ATP: pyrophosphate phosphoribosyltransferase; EC 2.4.2.17], and histidyl-tRNA is shown to be inhibited by L-histidine and by guanosine-5'-diphosphate-3'-diphosphate in the presence of histidine. Higher histodine levels make guanosine tetraphosphate a more effective inhibitor. Relatively high concentrations of guanosine-5'-triphosphate also inhibit complex formation, but this inhibition is not enhanced by histidine. The possible implications of these observations with respect to the gene regulatory activity of this enzyme are discussed. PMID:323857

  8. Solid Eu(III) complexes studied by positron annihilation, optical and Mssbauer spectroscopies: insights on the positronium formation mechanism.

    PubMed

    Fulgncio, F; de Oliveira, F C; Ivashita, F F; Paesano, A; Windmller, D; Marques-Netto, A; Magalhes, W F; Machado, J C

    2012-06-15

    In this work, positron annihilation lifetime (PALS), Doppler broadening annihilation radiation lineshape (DBARL), Mssbauer and optical spectroscopies measurements were performed in Eu(III) dipivaloylmetanate complex, Eu(dpm)(3), at 295 and 80 K. The Eu(dpm)(3) complex is not luminescent at 298 K and does not form positronium. On the other hand, it is highly luminescent at 80K, but still does not form positronium. The absence of positronium formation at 80K cannot be explained by a ligand/metal charge transfer process. We found strong evidences that the electronic delocalization does not occur at both temperatures. Despite the Mssbauer results being inconclusive regarding the Eu(III)/Eu(II) reduction hypothesis, previous results showing positronium formation in other Eu(III) complexes suggest that this process is not occurring. Thus, more studies are needed to explain the absence of positronium in Eu(III) complexes. PMID:22466013

  9. Fault kinematics in supradetachment basin formation, Menderes core complex of western Turkey

    NASA Astrophysics Data System (ADS)

    Oner, Zeynep; Dilek, Yildirim

    2013-11-01

    The Neogene Alasehir supradetachment basin in western Turkey occurs in the footwall of the modern Alaşehir-Gediz graben and is a major component of the Aegean extensional province in Anatolia that developed during the late Cenozoic exhumation of the Menderes core complex. The size, geometry, accommodation space and internal structure-stratigraphy of this basin were strongly controlled by the kinematics and interplay of four different fault generations throughout its early Miocene-Pleistocene evolution. The ~ E - W-striking, NNE-dipping (10°-30°) Alaşehir detachment fault separates the high-grade crystalline rocks of the core complex below from the Neogene deposits of the basin in the hanging wall above. The basin-parallel, synthetic and antithetic high-angle normal faults represent a block-faulting stage of the continued horizontal extension that terminated the northerly slip along the detachment surface and produced horst-graben structures in and across the basin. These faults were also responsible for the back-tilting of the basinal strata into steeper dips and the rotation of the previously formed faults into gently dipping planes. The mutually crosscutting relationships between the intra-basinal low-angle and basement-involved high-angle and normal faults indicate their contemporaneous development and operation. The NNE-striking, basin-perpendicular oblique-slip hinge faults are reminiscent of transfer (cross) faults in both continental and oceanic extension, and divide the supradetachment basin into a series of fault blocks with their own internal structure and stratigraphy. Differential uplift and exhumation of the core complex rocks along these hinge faults and the varied displacement and slip along and across them within the basinal strata caused differential extension and block-uplift, leading to the formation of local unconformities in the supradetachment basin. Significant changes in the dip directions and strike orientations of the sedimentary beds and the observed deviations from the inferred direction of maximum extension in the adjacent fault blocks resulted from rotational deformation due to hinge faulting. Fault segmentation of the Alaşehir basin as a result of extension-parallel hinge-faulting is a characteristic feature of its supradetachment basin evolution.

  10. MIAX: a new paradigm for modeling biomacromolecular interactions and complex formation in condensed phases.

    PubMed

    Del Carpio-Muoz, Carlos Adriel; Ichiishi, Eiichiro; Yoshimori, Atsushi; Yoshikawa, Toshikazu

    2002-09-01

    A new paradigm is proposed for modeling biomacromolecular interactions and complex formation in solution (protein-protein interactions so far in this report) that constitutes the scaffold of the automatic system MIAX (acronym for Macromolecular Interaction Assessment X). It combines in a rational way a series of computational methodologies, the goal being the prediction of the most native-like protein complex that may be formed when two isolated (unbound) protein monomers interact in a liquid environment. The overall strategy consists of first inferring putative precomplex structures by identification of binding sites or epitopes on the proteins surfaces and a simultaneous rigid-body docking process using geometric instances alone. Precomplex configurations are defined here as all those decoys the interfaces of which comply substantially with the inferred binding sites and whose free energy values are lower. Retaining all those precomplex configurations with low energies leads to a reasonable number of decoys for which a flexible treatment is amenable. A novel algorithm is introduced here for automatically inferring binding sites in proteins given their 3-D structure. The procedure combines an unsupervised learning algorithm based on the self-organizing map or Kohonen network with a 2-D Fourier spectral analysis. To model interaction, the potential function proposed here plays a central role in the system and is constituted by empirical terms expressing well-characterized factors influencing biomacromolecular interaction processes, essentially electrostatic, van der Waals, and hydrophobic. Each of these procedures is validated by comparing results with observed instances. Finally, the more demanding process of flexible docking is performed in MIAX embedding the potential function in a simulated annealing optimization procedure. Whereas search of the entire configuration hyperspace is a major factor precluding hitherto systems from efficiently modeling macromolecular interaction modes and complex structures, the paradigm presented here may constitute a step forward in the field because it is shown that a rational treatment of the information available from the 3-D structure of the interacting monomers combined with conveniently selected computational techniques can assist to elude search of regions of low probability in configuration space and indeed lead to a highly efficient system oriented to solve this intriguing and fundamental biologic problem. PMID:12211037

  11. Resolving detailed molecular structures in complex organic mixtures and modeling their secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Goodman-Rendall, Kevin A. S.; Zhuang, Yang R.; Amirav, Aviv; Chan, Arthur W. H.

    2016-03-01

    Characterization of unresolved complex mixtures (UCMs) remains an ongoing challenge towards developing detailed and accurate inputs for modeling secondary organic aerosol (SOA) formation. Traditional techniques based on gas chromatography/electron impact-mass spectrometry induce excessive fragmentation, making it difficult to speciate and quantify isomers precisely. The goal of this study is to identify individual organic isomers by gas chromatography/mass spectrometry with supersonic molecular beam (SMB-GC/MS, also known as GC/MS with Cold EI) and to incorporate speciated isomers into an SOA model that accounts for the specific structures elucidated. Two samples containing atmospherically relevant UCMs are analyzed. The relative isomer distributions exhibit remarkably consistent trends across a wide range of carbon numbers. Constitutional isomers of different alkanes are speciated and individually quantified as linear, branched - for the first time by position of branching - multiply branched, or unsaturated - by degree of ring substitution and number of rings. Relative amounts of exact molecular structures are used as input parameters in an SOA box model to study the effects of molecular structures on SOA yields and volatility evolution. Highly substituted cyclic, mono-substituted cyclic, and linear species have the highest SOA yields while branched alkanes formed the least SOA. The rate of functionalization of a representative UCM is found to be in agreement with current volatility basis set (VBS) parameterizations based on detailed knowledge of composition and known oxidation mechanisms, confirming the validity of VBS parameters currently used in air quality models.

  12. Gap2 Promotes the Formation of a Stable Protein Complex Required for Mature Fap1 Biogenesis

    PubMed Central

    Echlin, Haley; Zhu, Fan; Li, Yirong; Peng, Zhixiang; Ruiz, Teresa; Bedwell, Gregory J.; Prevelige, Peter E.

    2013-01-01

    Serine-rich repeat glycoproteins (SRRPs) are important bacterial adhesins conserved in streptococci and staphylococci. Fap1, a SRRP identified in Streptococcus parasanguinis, is the major constituent of bacterial fimbriae and is required for adhesion and biofilm formation. An 11-gene cluster is required for Fap1 glycosylation and secretion; however, the exact mechanism of Fap1 biogenesis remains a mystery. Two glycosylation-associated proteins within this clusterGap1 and Gap3function together in Fap1 biogenesis. Here we report the role of the third glycosylation-associated protein, Gap2. A gap2 mutant exhibited the same phenotype as the gap1 and gap3 mutants in terms of Fap1 biogenesis, fimbrial assembly, and bacterial adhesion, suggesting that the three proteins interact. Indeed, all three proteins interacted with each other independently and together to form a stable protein complex. Mechanistically, Gap2 protected Gap3 from degradation by ClpP protease, and Gap2 required the presence of Gap1 for expression at the wild-type level. Gap2 augmented the function of Gap1 in stabilizing Gap3; this function was conserved in Gap homologs from Streptococcus agalactiae. Our studies demonstrate that the three Gap proteins work in concert in Fap1 biogenesis and reveal a new function of Gap2. This insight will help us elucidate the molecular mechanism of SRRP biogenesis in this bacterium and in pathogenic species. PMID:23475979

  13. Feedback control of prion formation and propagation by the ribosome-associated chaperone complex.

    PubMed

    Kiktev, Denis A; Melomed, Mikhail M; Lu, Caroline D; Newnam, Gary P; Chernoff, Yury O

    2015-05-01

    Cross-beta fibrous protein aggregates (amyloids and amyloid-based prions) are found in mammals (including humans) and fungi (including yeast), and are associated with both diseases and heritable traits. The Hsp104/70/40 chaperone machinery controls propagation of yeast prions. The Hsp70 chaperones Ssa and Ssb show opposite effects on [PSI(+)], a prion form of the translation termination factor Sup35 (eRF3). Ssb is bound to translating ribosomes via ribosome-associated complex (RAC), composed of Hsp40-Zuo1 and Hsp70-Ssz1. Here we demonstrate that RAC disruption increases de novo prion formation in a manner similar to Ssb depletion, but interferes with prion propagation in a manner similar to Ssb overproduction. Release of Ssb into the cytosol in RAC-deficient cells antagonizes binding of Ssa to amyloids. Thus, propagation of an amyloid formed because of lack of ribosome-associated Ssb can be counteracted by cytosolic Ssb, generating a feedback regulatory circuit. Release of Ssb from ribosomes is also observed in wild-type cells during growth in poor synthetic medium. Ssb is, in a significant part, responsible for the prion destabilization in these conditions, underlining the physiological relevance of the Ssb-based regulatory circuit. PMID:25649498

  14. Cluster formation by allelomimesis in real-world complex adaptive systems

    NASA Astrophysics Data System (ADS)

    Juanico, Dranreb Earl; Monterola, Christopher; Saloma, Caesar

    2005-04-01

    Animal and human clusters are complex adaptive systems and many organize in cluster sizes s that obey the frequency distribution D(s)∝s-τ . The exponent τ describes the relative abundance of the cluster sizes in a given system. Data analyses reveal that real-world clusters exhibit a broad spectrum of τ values, 0.7 (tuna fish schools) ⩽τ⩽4.61 (T4 bacteriophage gene family sizes). Allelomimesis is proposed as an underlying mechanism for adaptation that explains the observed broad τ spectrum. Allelomimesis is the tendency of an individual to imitate the actions of others and two cluster systems have different τ values when their component agents display unequal degrees of allelomimetic tendencies. Cluster formation by allelomimesis is shown to be of three general types: namely, blind copying, information-use copying, and noncopying. Allelomimetic adaptation also reveals that the most stable cluster size is formed by three strongly allelomimetic individuals. Our finding is consistent with available field data taken from killer whales and marmots.

  15. Floatation-spectrophotometric Determination of Thorium, Using Complex Formation with Eriochrome Cyanine R

    PubMed Central

    Shiri, Sabah; Delpisheh, Ali; Haeri, Ali; Poornajaf, Abdolhossein; Khezeli, Tahereh; Badkiu, Nadie

    2011-01-01

    A novel and sensitive floatation-spectrophotometric method is presented for determination of trace amounts of thorium in water samples. The method is based on the ion-associated formation between thorium, Eriochrome cyanine R and Brij-35 at pH = 4 media. The complex was floated in the interface of the aqueous phase and n-hexane by vigorous shaking. After removing the aqueous phase the floated particles were dissolved in methanol and the absorbance was measured at 607 nm. The influence of different important parameters such as Eriochrome cyanine R and surfactants concentration, pH, volume of n-hexane, standing time and interfering ions were evaluated. Under optimized conditions the calibration graph was linear in the range of 6–230 ng mL−1 of thorium with a correlation coefficient of 0.9985. The limit of detections (LOD), based on signal to noise ratio (S/N) of 3 was 1.7 ng mL−1. The relative standard deviations for determination of 150 and 30 ng ml−1 of thorium were 3.26 and 4.41%, respectively (n = 10). The method showed a good linearity, recoveries, as well as some advantages such as sensitivity, simplicity, affordability and a high feasibility. The method was successfully applied to determine thorium in different water and urine samples. PMID:21340019

  16. Formation and identification of unresolved complex mixtures in lacustrine biodegraded oil from Nanxiang Basin, China.

    PubMed

    Guo, Pengfei; He, Sheng; Zhu, Shukui; Chai, Derong; Yin, Shiyan; Dai, Wei; Zhang, Wanfeng

    2014-01-01

    A comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOFMS) method has been developed for the formation and identification of unresolved complex mixtures (UCMs) in lacustrine biodegraded oils that with the same source rock, similar maturity, and increasing degradation rank from Nanxiang Basin, China. Normal alkanes, light hydrocarbons, isoprenoids, steranes, and terpanes are degraded gradually from oil B330 to oil G574. The compounds in biodegraded oil (oil G574) have fewer types, the polarity difference of compounds in different types is minor, and the relative content of individual compounds is similar. All the features make the compounds in biodegraded oil coelute in GC analysis and form the raised "baseline hump" named UCMs. By injecting standard materials and analyzing mass spectrums of target compounds, it is shown that cyclic alkanes with one to five rings are the major components of UCMs. Furthermore, UCMs were divided into six classes. Classes I and II, composed of alkyl-cyclohexanes, alkyl-naphthanes, and their isomers, are originated from the enrichment of hydrocarbons resistant to degradation in normal oils. Classes III ~ VI, composed of sesquiterpenoids, tricyclic terpanes, low molecular steranes, diasteranes, norhopanes, and their isomers, are probably from some newly formed compounds during the microbial transformation of oil. PMID:25177711

  17. Decamethylytterbocene complexes of bipyridines and diazabutadines: multiconfigurational ground states and open-shell singlet formation

    SciTech Connect

    Bauer, Eric D; Booth, C H; Walter, M D; Kazhdan, D; Hu, Y - J; Lukens, Wayne; Maron, Laurent; Eisentein, Odile; Anderson, Richard

    2009-01-01

    Partial ytterbium f-orbital occupancy (i.e. intermediate valence) and open-shell singlet Draft 12/formation are established for a variety of bipyridine and diazabutadiene adducts to decamethylytterbocene, (C{sub 5}Me{sub 5}){sub 2}Yb or Cp*{sub 2}Yb. Data used to support this claim includes ytterbium valence measurements using Yb Lm-edge x-ray absorption near-edge structure (XANES) spectroscopy, magnetic susceptibility and Complete Active Space Self-Consistent Field (CASSCF) multi configurational calculations, as well as structural measurements compared to density-functional theory (DFT) calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground state wave function that has both an open-shell singlet f{sup 13} and a closed-shell singlet f{sup 14} component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the presence of intermediate valence and its lack of any significant temperature dependence. These results have implications for understanding chemical bonding not only in organolanthanide complexes, but also for organometallic chemistry in general, as well as understanding magnetic interactions in nanopartic1es and devices.

  18. A cyclo-P6 Ligand Complex for the Formation of Planar 2D Layers.

    PubMed

    Heindl, Claudia; Peresypkina, Eugenia V; Lüdeker, David; Brunklaus, Gunther; Virovets, Alexander V; Scheer, Manfred

    2016-02-01

    The all-phosphorus analogue of benzene, stabilized as middle deck in triple-decker complexes, is a promising building block for the formation of graphene-like sheet structures. The reaction of [(CpMo)2 (μ,η(6) :η(6) -P6 )] (1) with CuX (X=Br, I) leads to self-assembly into unprecedented 2D networks of [{(CpMo)2 P6 }(CuBr)4 ]n (2) and [{(CpMo)2 P6 }(CuI)2 ]n (3). X-ray structural analyses show a unique deformation of the previously planar cyclo-P6 ligand. This includes bending of one P atom in an envelope conformation as well as a bisallylic distortion. Despite this, 2 and 3 form planar layers. Both polymers were furthermore analyzed by (31) P{(1) H} magic angle spinning (MAS) NMR spectroscopy, revealing signals corresponding to six non-equivalent phosphorus sites. A peak assignment is achieved by 2D correlation spectra as well as by DFT chemical shift computations. PMID:26711699

  19. Computation of infinite dilute activity coefficients of binary liquid alloys using complex formation model

    NASA Astrophysics Data System (ADS)

    Awe, O. E.; Oshakuade, O. M.

    2016-04-01

    A new method for calculating Infinite Dilute Activity Coefficients (γ∞s) of binary liquid alloys has been developed. This method is basically computing γ∞s from experimental thermodynamic integral free energy of mixing data using Complex formation model. The new method was first used to theoretically compute the γ∞s of 10 binary alloys whose γ∞s have been determined by experiments. The significant agreement between the computed values and the available experimental values served as impetus for applying the new method to 22 selected binary liquid alloys whose γ∞s are either nonexistent or incomplete. In order to verify the reliability of the computed γ∞s of the 22 selected alloys, we recomputed the γ∞s using three other existing methods of computing or estimating γ∞s and then used the γ∞s obtained from each of the four methods (the new method inclusive) to compute thermodynamic activities of components of each of the binary systems. The computed activities were compared with available experimental activities. It is observed that the results from the method being proposed, in most of the selected alloys, showed better agreement with experimental activity data. Thus, the new method is an alternative and in certain instances, more reliable approach of computing γ∞s of binary liquid alloys.

  20. Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation

    SciTech Connect

    Booth, Corwin H.; Walter, Marc D.; Kazhdan, Daniel; Hu, Yung-Jin; Lukens, Wayne W.; Bauer, Eric D.; Maron, Laurent; Eisenstein, Odile; Andersen, Richard A.

    2009-04-22

    Partial ytterbium f-orbital occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a variety of bipyridine and diazabutadiene adducts with decamethylytterbocene, (C5Me5)2Yb, abbreviated as Cp*2Yb. Data used to support this claim include ytterbium valence measurements using Yb LIII-edge X-ray absorption near-edge structure spectroscopy, magnetic susceptibility, and complete active space self-consistent field (CASSCF) multiconfigurational calculations, as well as structural measurements compared to density functional theory calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground-state wave function that has both an open-shell singlet f13(?*)1, where pi* is the lowest unoccupied molecular orbital of the bipyridine or dpiazabutadiene ligands, and a closed-shell singlet f14 component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the lack of temperature dependence of the measured intermediate valence. These results have implications for understanding chemical bonding not only in organolanthanide complexes but also for f-element chemistry in general, as well as understanding magnetic interactions in nanoparticles and devices.

  1. Predominance of spliceosomal complex formation over polyadenylation site selection in TDP-43 autoregulation.

    PubMed

    Bembich, Sara; Herzog, Jeremias S; De Conti, Laura; Stuani, Cristiana; Avendao-Vzquez, S Erndira; Buratti, Emanuele; Baralle, Marco; Baralle, Francisco E

    2014-03-01

    TDP-43 is a nuclear protein involved in many aspects of RNA metabolism. To ensure cellular viability, its expression levels within cells must be tightly regulated. We have previously demonstrated that TDP-43 autoregulation occurs through the activation of a normally silent intron in its 3'-UTR sequence that results in the use of alternative polyadenylation sites. In this work, we analyse which is the dominant event in autoregulation: the recognition of the splice sites of 3'-UTR intron 7 or the intrinsic quality of the alternative polyadenylation sites. A panel of minigene constructs was tested for autoregulation functionality, protein production and subcellular messenger RNA localization. Our data clearly indicate that constitutive spliceosome complex formation across intron 7 does not lead to high protein production but, on the contrary, to lower TDP-43 messenger RNA and protein levels. This is due to altered nucleocytoplasmic distribution of the RNA that is mostly retained in the nucleus and degraded. This study provides a novel in-depth characterization of how RNA binding proteins can autoregulate their own levels within cells, an essential regulatory process in maintaining cellular viability. PMID:24369426

  2. Formation mechanism of a silane-PVA/PVAc complex film on a glass fiber surface.

    PubMed

    Repovsky, Daniel; Jane, Eduard; Palszegi, Tibor; Slobodnik, Marek; Velic, Dusan

    2013-10-21

    Mechanical properties of glass fiber reinforced composite materials are affected by fiber sizing. A complex film formation, based on a silane film and PVA/PVAc (polyvinyl alcohol/polyvinyl acetate) microspheres on a glass fiber surface is determined at 1) the nanoscale by using atomic force microscopy (AFM), and 2) the macroscale by using the zeta potential. Silane groups strongly bind through the Si-O-Si bond to the glass surface, which provides the attachment mechanism as a coupling agent. The silane groups form islands, a homogeneous film, as well as empty sites. The average roughness of the silanized surface is 6.5 nm, whereas it is only 0.6 nm for the non-silanized surface. The silane film vertically penetrates in a honeycomb fashion from the glass surface through the deposited PVA/PVAc microspheres to form a hexagonal close pack structure. The silane film not only penetrates, but also deforms the PVA/PVAc microspheres from the spherical shape in a dispersion to a ellipsoidal shape on the surface with average dimensions of 300/600 nm. The surface area value Sa represents an area of PVA/PVAc microspheres that are not affected by the silane penetration. The areas are found to be 0.2, 0.08, and 0.03 ?m(2) if the ellipsoid sizes are 320/570, 300/610, and 270/620 nm for silane concentrations of 0, 3.8, and 7.2 ?g mL(-1), respectively. The silane film also moves PVA/PVAc microspheres in the process of complex film formation, from the low silane concentration areas to the complex film area providing enough silane groups to stabilize the structure. The values for the residual silane honeycomb structure heights (Ha ) are 6.5, 7, and 12 nm for silane concentrations of 3.8, 7.2, and 14.3 ?g mL(-1), respectively. The pH-dependent zeta-potential results suggest a specific role of the silane groups with effects on the glass fiber surface and also on the PVA/PVAc microspheres. The non-silanized glass fiber surface and the silane film have similar zeta potentials ranging from -64 to -12 mV at pH's of 10.5 and 3, respectively. The zeta potentials for the PVA/PVAc microspheres on the glass fiber surface and within the silane film significantly decrease and range from -25 to -5 mV. The shapes of the pH-dependent zeta potentials are different in the cases of silane groups over a pH range from 7 to 4. A triple-layer model is used to fit the non-silanized glass surface and the silane film. The value of the surface-site density for ?(Xglass) and ?(Xsilane), in which X denotes the Al-O-Si group, differs by a factor of 10(-4), which suggests an effective coupling of the silane film. A soft-layer model is used to fit the silane-PVA/PVAc complex film, which is approximated as four layers. Such a simplification and compensation of the microsphere shape gives an approximation of the relevant widths of the layers as the follows: 1) the layer of the silane groups makes up 10% of the total length (27 nm), 2) the layer of the first PVA shell contributes 30% to the total length (81 nm), 3) the layer of the PVAc core contributes 30% to the total length (81 nm), and finally 4) the layer of the second PVA shell provides 30% of the total length (81 nm). The coverage simulation resulted in a value of 0.4, which corresponds with the assumption of low-order coverage, and is supported by the AFM scans. Correlating the results of the AFM scans, and the zeta potentials sheds some light on the formation mechanism of the silane-PVA/PVAc complex film. PMID:24039042

  3. Enantioseparation of mandelic acid derivatives by high performance liquid chromatography with substituted β-cyclodextrin as chiral mobile phase additive and evaluation of inclusion complex formation.

    PubMed

    Tong, Shengqiang; Zhang, Hu; Shen, Mangmang; Ito, Yoichiro; Yan, Jizhong

    2014-07-01

    The enantioseparation of ten mandelic acid derivatives was performed by reverse phase high performance liquid chromatography with hydroxypropyl-β-cyclodextrin (HP-β-CD) or sulfobutyl ether-β-cyclodextrin (SBE-β-CD) as chiral mobile phase additives, in which inclusion complex formations between cyclodextrins and enantiomers were evaluated. The effects of various factors such as the composition of mobile phase, concentration of cyclodextrins and column temperature on retention and enantioselectivity were studied. The peak resolutions and retention time of the enantiomers were strongly affected by the pH, the organic modifier and the type of β-cyclodextrin in the mobile phase, while the concentration of buffer solution and temperature had a relatively low effect on resolutions. Enantioseparations were successfully achieved on a Shimpack CLC-ODS column (150×4.6mm i.d., 5μm). The mobile phase was a mixture of acetonitrile and 0.10molL(-1) of phosphate buffer at pH 2.68 containing 20mmolL(-1) of HP-β-CD or SBE-β-CD. Semi-preparative enantioseparation of about 10mg of α-cyclohexylmandelic acid and α-cyclopentylmandelic acid were established individually. Cyclodextrin-enantiomer complex stoichiometries as well as binding constants were investigated. Results showed that stoichiometries for all the inclusion complex of cyclodextrin-enantiomers were 1:1. PMID:24893270

  4. Enantioseparation of mandelic acid derivatives by high performance liquid chromatography with substituted ?-cyclodextrin as chiral mobile phase additive and evaluation of inclusion complex formation

    PubMed Central

    Tong, Shengqiang; Zhang, Hu; Shen, Mangmang

    2014-01-01

    The enantioseparation of ten mandelic acid derivatives was performed by reverse phase high performance liquid chromatography with hydroxypropyl-?-cyclodextrin (HP-?-CD) or sulfobutyl ether-?-cyclodextrin (SBE-?-CD) as chiral mobile phase additives, in which inclusion complex formations between cyclodextrins and enantiomers were evaluated. The effects of various factors such as the composition of mobile phase, concentration of cyclodextrins and column temperature on retention and enantioselectivity were studied. The peak resolutions and retention time of the enantiomers were strongly affected by the pH, the organic modifier and the type of ?-cyclodextrin in the mobile phase, while the concentration of buffer solution and temperature had a relatively low effect on resolutions. Enantioseparations were successfully achieved on a Shimpack CLC-ODS column (1504.6 mm i.d., 5 ?m). The mobile phase was a mixture of acetonitrile and 0.10 mol L-1 of phosphate buffer at pH 2.68 containing 20 mmol L-1 of HP-?-CD or SBE-?-CD. Semi-preparative enantioseparation of about 10 mg of ?-cyclohexylmandelic acid and ?-cyclopentylmandelic acid were established individually. Cyclodextrin-enantiomer complex stoichiometries as well as binding constants were investigated. Results showed that stoichiomertries for all the inclusion complex of cyclodextrin-enantiomers were 1:1. PMID:24893270

  5. The effect of trans-resveratrol on platelet-neutrophil complex formation and neutrophil burst in hypercholesterolemic rats.

    PubMed

    Gmen, Ay?e Ye?im; Burgucu, Durmu?; Karado?an, Ihsan; Timura?ao?lu, Ay?en; Gm?l, Saadet

    2013-01-01

    Transresveratrol (t-resveratrol; 3,5,4'-trihydroxy-trans-stilbene) is a polyphenolic compound found in fresh grapes, grape juice and wine, and has been found to reduce the total cholesterol level in hypercholesterolemic rats. The objective of the present study was to assess the effects of t-resveratrol on platelet-neutrophil complex formation and neutrophil reactive oxygen species (ROS) status in control and hypercholesterolemic rats using a modified flow cytometric method. Rats (n=80) were divided into five groups (control, ethanol, resveratrol, hypercholesterolemic and resveratrol-administered hypercholesterolemic groups), comprising 16 animals per group. Serum levels of lipids and H2O2 were determined using commercially available kits, while platelet-neutrophil complex formation and neutrophil ROS status were determined using a modified flow cytometric method. Serum total cholesterol and low-density lipoprotein cholesterol levels were found to be increased and the high-density lipoprotein cholesterol level was found to be decreased in the HC group compared with the control group (P<0.001). Treatment of HC rats with t-resveratrol significantly lowered total cholesterol and low-density lipoprotein cholesterol levels (P<0.001). In the hypercholesterolemic group, levels of serum H2O2 platelet-neutrophil complex formation and neutrophil ROS status were significantly increased (P<0.001). On the other hand, in the resveratrol-administered hypercholesterolemic group, serum H2O2 levels, platelet-neutrophil complex formation and neutrophil ROS status were decreased compared with the hypercholesterolemic group (P<0.001). Serum H2O2 levels, platelet-neutrophil complex and neutrophil ROS status were positively correlated with one another. The present study is the first to demonstrate the protective effect of t-resveratrol against hypercholesterolemia-induced platelet-neutrophil complex formation and neutrophil ROS burst. Further investigations on its plausible role in antihypercholesterolemic treatment are warranted. PMID:23940447

  6. Methamphetamine-Induced Dopamine Transporter Complex Formation and Dopaminergic Deficits: The Role of D2 Receptor Activation

    PubMed Central

    Hadlock, Gregory C.; Chu, Pei-Wen; Walters, Elliot T.; Hanson, Glen R.

    2010-01-01

    Methamphetamine (METH) abuse is a serious public health issue. Of particular concern are findings that repeated high-dose administrations of METH cause persistent dopaminergic deficits in rodents, nonhuman primates, and humans. Previous studies have also revealed that METH treatment causes alterations in the dopamine transporter (DAT), including the formation of higher molecular mass DAT-associated complexes. The current study extends these findings by examining mechanisms underlying DAT complex formation. The association among DAT complex formation and other METH-induced phenomena, including alterations in vesicular monoamine transporter 2 (VMAT2) immunoreactivity, astrocytic activation [as assessed by increased glial fibrillary acidic protein (GFAP) immunoreactivity], and persistent dopaminergic deficits was also explored. Results revealed that METH-induced DAT complex formation and reductions in VMAT2 immunoreactivity precede increases in GFAP immunoreactivity. Furthermore, and as reported previously for DAT complexes, pretreatment with the D2 receptor antagonist eticlopride [S-(?)-3-chloro-5-ethyl-N-[(1-ethyl-2-pyrrolidinyl)methyl]-6-hydroxy-2-methoxybenzamide hydrochloride] attenuated the decrease in VMAT2 immunoreactivity as assessed 24 h after METH treatment. DAT complexes distinct from those present 24 h after METH treatment, decreases in VMAT2 immunoreactivity, and increased GFAP immunoreactivity were present 48 to 72 h after METH treatment. Pretreatment with eticlopride attenuated each of these phenomena. Finally, DAT complexes were present 7 days after METH treatment, a time point at which VMAT2 and DAT monomer immunoreactivity were also reduced. Eticlopride pretreatment attenuated each of these phenomena. These findings provide novel insight into not only receptor-mediated mechanisms underlying the effects of METH but also the interaction among factors that probably are associated with the persistent dopaminergic deficits caused by the stimulant. PMID:20622144

  7. Influence of the lipid environment on valinomycin structure and cation complex formation

    NASA Astrophysics Data System (ADS)

    Halsey, Christopher M.; Benham, Derek A.; JiJi, Renee D.; Cooley, Jason W.

    2012-10-01

    Carrier-type molecular ionophores, such as the cyclic dodecadepsipeptide valinomycin, often must undergo structural changes during the binding and transport of a cation across the lipid membrane. Observing the structural fluctuations that occur during this process experimentally has proven extremely difficult due to the complexities of spectroscopic analysis of protein structure/dynamics in native lipid bilayer environments. Currently, our understanding of how valinomycin selectively transports ions across membranes is derived from atomic structures solved of the cyclic macromolecule solvated in various organic solvents and complimentary in silico dynamics experiments. We have shown recently that deep-UV excited resonance Raman spectroscopy (DUVRR) has a unique ability to characterize secondary structure content and simultaneously provide information about the relative solvation of the probed peptide backbone C.M. Halsey, J. Xiong, O. Oshokoya, J.A. Johnson, S. Shinde, J.T. Beatty, G. Ghirlanda, R.D. JiJi, J.W. Cooley, Simultaneous observation of peptide backbone lipid solvation and a-helical structure by deep-UV resonance Raman spectroscopy, ChemBioChem 12 (2011) 2125-2128, [16]. Interpretation of DUVRR spectra of valinomycin in swelled lipid and unilamellar lipid bilayer environments indicate that the uncomplexed valinomycin molecule dynamically samples both the open and closed conformations as described for the structures derived from polar and non-polar organic solvents, respectively. Upon introduction of potassium, the structure of valinomycin in swelled lipid environments resembles more closely that of the open conformation. The shift in structure upon complexation is accompanied by a significant decrease in the valinomycin DUVRR spectral amide I intensity, indicating that the open conformation is more water solubilized and is seemingly "trapped" or predominantly located close to the lipid-water interface. The trapping of the valinomycin in the act of complex of potassium at the bilayer-solvent interface and its analysis by DUVRR represents the first spectroscopic description of this state. Conversely, an opposite trend is observed in the amide I intensity upon potassium complexation in unilamellar (or extruded) vesicles, implying the predominant conformation upon potassium binding in native bilayers is one where the peptide backbone of valinomycin is desolvated as would be expected if the molecule were more readily able to traverse a bilayer interior. Interpretation of the DUVRR spectral features is also consistent with the loss or formation of hydrogen bonds observed in the open and closed structures, respectively. Valinomycin must then sample several conformations in the absence of appropriate ions depending upon its locale in the lipid bilayer until potassium causes a greater degree of closure of the open conformer and an increased residency within the more non-polar interior. The potassium induced decreased solubility enables diffusion across the membrane where potassium release can occur by equilibration at the opposite lipid water interface.

  8. Influence of the lipid environment on valinomycin structure and cation complex formation.

    PubMed

    Halsey, Christopher M; Benham, Derek A; JiJi, Renee D; Cooley, Jason W

    2012-10-01

    Carrier-type molecular ionophores, such as the cyclic dodecadepsipeptide valinomycin, often must undergo structural changes during the binding and transport of a cation across the lipid membrane. Observing the structural fluctuations that occur during this process experimentally has proven extremely difficult due to the complexities of spectroscopic analysis of protein structure/dynamics in native lipid bilayer environments. Currently, our understanding of how valinomycin selectively transports ions across membranes is derived from atomic structures solved of the cyclic macromolecule solvated in various organic solvents and complimentary in silico dynamics experiments. We have shown recently that deep-UV excited resonance Raman spectroscopy (DUVRR) has a unique ability to characterize secondary structure content and simultaneously provide information about the relative solvation of the probed peptide backbone C.M. Halsey, J. Xiong, O. Oshokoya, J.A. Johnson, S. Shinde, J.T. Beatty, G. Ghirlanda, R.D. JiJi, J.W. Cooley, Simultaneous observation of peptide backbone lipid solvation and a-helical structure by deep-UV resonance Raman spectroscopy, ChemBioChem 12 (2011) 2125-2128, [16]. Interpretation of DUVRR spectra of valinomycin in swelled lipid and unilamellar lipid bilayer environments indicate that the uncomplexed valinomycin molecule dynamically samples both the open and closed conformations as described for the structures derived from polar and non-polar organic solvents, respectively. Upon introduction of potassium, the structure of valinomycin in swelled lipid environments resembles more closely that of the open conformation. The shift in structure upon complexation is accompanied by a significant decrease in the valinomycin DUVRR spectral amide I intensity, indicating that the open conformation is more water solubilized and is seemingly "trapped" or predominantly located close to the lipid-water interface. The trapping of the valinomycin in the act of complex of potassium at the bilayer-solvent interface and its analysis by DUVRR represents the first spectroscopic description of this state. Conversely, an opposite trend is observed in the amide I intensity upon potassium complexation in unilamellar (or extruded) vesicles, implying the predominant conformation upon potassium binding in native bilayers is one where the peptide backbone of valinomycin is desolvated as would be expected if the molecule were more readily able to traverse a bilayer interior. Interpretation of the DUVRR spectral features is also consistent with the loss or formation of hydrogen bonds observed in the open and closed structures, respectively. Valinomycin must then sample several conformations in the absence of appropriate ions depending upon its locale in the lipid bilayer until potassium causes a greater degree of closure of the open conformer and an increased residency within the more non-polar interior. The potassium induced decreased solubility enables diffusion across the membrane where potassium release can occur by equilibration at the opposite lipid water interface. PMID:22683555

  9. Formative Assessment in an Online Learning Environment to Support Flexible On-the-Job Learning in Complex Professional Domains

    ERIC Educational Resources Information Center

    van Gog, Tamara; Sluijsmans, Dominique M. A.; Joosten-ten Brinke, Desiree; Prins, Frans J.

    2010-01-01

    This article describes a blueprint for an online learning environment that is based on prominent instructional design and assessment theories for supporting learning in complex domains. The core of this environment consists of formative assessment tasks (i.e., assessment "for" learning) that center on professional situations. For each professional

  10. Monitoring the formation of carbide crystal phases during the thermal decomposition of 3d transition metal dicarboxylate complexes

    SciTech Connect

    Huba, ZJ; Carpenter, EE

    2014-06-06

    Single molecule precursors can help to simplify the synthesis of complex alloys by minimizing the amount of necessary starting reagents. However, single molecule precursors are time consuming to prepare with very few being commercially available. In this study, a simple precipitation method is used to prepare Fe, Co, and Ni fumarate and succinate complexes. These complexes were then thermally decomposed in an inert atmosphere to test their efficiency as single molecule precursors for the formation of metal carbide phases. Elevated temperature X-ray diffraction was used to identify the crystal phases produced upon decomposition of the metal dicarboxylate complexes. Thermogravimetric analysis coupled with an infrared detector was used to identify the developed gaseous decomposition products. All complexes tested showed a reduction from the starting M2+ oxidation state to the M oxidation state, upon decomposition. Also, each complex tested showed CO2 and H2O as gaseous decomposition products. Nickel succinate, iron succinate, and iron fumarate complexes were found to form carbide phases upon decomposition. This proves that transition metal dicarboxylate salts can be employed as efficient single molecule precursors for the formation of metal carbide crystal phases.

  11. The proliferative and antiapoptotic effects of substance P are facilitated by formation of a ?-arrestin-dependent scaffolding complex

    PubMed Central

    DeFea, K. A.; Vaughn, Z. D.; O'Bryan, E. M.; Nishijima, D.; Dry, O.; Bunnett, N. W.

    2000-01-01

    A requirement for scaffolding complexes containing internalized G protein-coupled receptors and ?-arrestins in the activation and subcellular localization of extracellular signal-regulated kinases 1 and 2 (ERK1/2) has recently been proposed. However, the composition of these complexes and the importance of this requirement for function of ERK1/2 appear to differ between receptors. Here we report that substance P (SP) activation of neurokinin-1 receptor (NK1R) stimulates the formation of a scaffolding complex comprising internalized receptor, ?-arrestin, src, and ERK1/2 (detected by gel filtration, immunoprecipitation, and immunofluorescence). Inhibition of complex formation, by expression of dominant-negative ?-arrestin or a truncated NK1R that fails to interact with ?-arrestin, inhibits both SP-stimulated endocytosis of the NK1R and activation of ERK1/2, which is required for the proliferative and antiapoptotic effects of SP. Thus, formation of a ?-arrestin-containing complex facilitates the proliferative and antiapoptotic effects of SP, and these effects of SP could be diminished in cells expressing truncated NK1R corresponding to a naturally occurring variant. PMID:10995467

  12. Nudel is crucial for the WAVE complex assembly in vivo by selectively promoting subcomplex stability and formation through direct interactions

    PubMed Central

    Wu, Shuang; Ma, Li; Wu, Yibo; Zeng, Rong; Zhu, Xueliang

    2012-01-01

    The WAVE regulatory complex (WRC), consisting of WAVE, Sra, Nap, Abi, and HSPC300, activates the Arp2/3 complex to control branched actin polymerization in response to Rac activation. How the WRC is assembled in vivo is not clear. Here we show that Nudel, a protein critical for lamellipodia formation, dramatically stabilized the Sra1-Nap1-Abi1 complex against degradation in cells through a dynamic binding to Sra1, whereas its physical interaction with HSPC300 protected free HSPC300 from the proteasome-mediated degradation and stimulated the HSPC300-WAVE2 complex formation. By contrast, Nudel showed little or no interactions with the Sra1-Nap1-Abi1-WAVE2 and the Sra1-Nap1-Abi1-HSPC300 complexes as well as the mature WRC. Depletion of Nudel by RNAi led to general subunit degradation and markedly attenuated the levels of mature WRC. It also abolished the WRC-dependent actin polymerization in vitro and the Rac1-induced lamellipodial actin network formation during cell spreading. Therefore, Nudel is important for the early steps of the WRC assembly in vivo by antagonizing the instability of certain WRC subunits and subcomplexes. PMID:22453242

  13. Linking megathrust earthquakes to faulting and mineral vein formation in a fossil accretionary complex

    NASA Astrophysics Data System (ADS)

    Dielforder, Armin; Herwegh, Marco; Berger, Alfons

    2015-04-01

    Geodetic and seismological data recorded at active subduction zones suggest that megathrust earthquakes induce transient stress changes in the upper plate, which shift the wedge into an unstable state and trigger >Mw 6 aftershocks. These stress changes have, however, never been linked to geological structures that are preserved within fossil accretionary wedges, although plate interface of palaeo-subduction zones has been studied. The conditions under which accretionary wedges fail have therefore remained controversial. Here we show that faulting and associated vein formation in the palaeo-accretionary complex of the European Alps record stress changes generated by the subduction earthquake cycle. Our data integrate wedge deformation over millions of years but still demonstrate the dominance of specific fracture modes at different depths within the wedge. We trace the subduction of sediments by means of the 87Sr/86Sr isotope-systematics of mineral veins, which became more radiogenic at deeper levels. By combining our field observations and geochemical data with a dynamic Mohr-Coulomb wedge analysis, we show that early veins were formed in shallow levels by bedding-parallel shear during coseismic compression of the outer wedge. In contrast, later veins originated at deeper levels during normal faulting and extensional fracturing recording coseismic extension of the inner wedge. Our study shows how mineral veins can be used to reveal the dynamics of outer and inner wedges, which response in opposite ways to megathrust earthquakes by compressional and extensional faulting, respectively. We emphasise, that coseismic fracturing implicates an increase in permeability within the hanging wall of megathrusts. Understanding how fractures are generated throughout the subduction earthquake cycle is therefore essential to better contstrain the nature of postseismic fluid flow and to assess the seismic hazard of hydraulically driven aftershocks.

  14. Petrological and geochemical constraints on granitoid formation: The Waldoboro Pluton Complex, Maine

    SciTech Connect

    Barton, M. . Dept. of Geological Science); Sidle, W.S. )

    1992-01-01

    The Waldoboro Pluton Complex (WPC) comprises seven units ranging from qtz-diorite to aplite. The country rocks are biotite-rich metagraywackes with minor shales mostly belonging to the Proterozoic Z-Ordovician Bucksport Formation. Field evidence strongly suggests that the WPC formed in-situ: contacts with the country rock are cryptic, transitional and concordant; restitic minerals in the granitoids are identical to those in the country rocks; prolific metasedimentary enclaves in the WPC are locally derived. Major and trace element data for country rock and the most voluminous units of the WPC define consistent linear trends suggesting limited melt segregation and retention of a high proportion of restite. Mixing models and partial melting models require 54--76% melting for generation of the gneissic granites and two-mica granites. Garnet-biotite geothermometry and garnet-Al[sub 2]SiO[sub 5]-SiO[sub 2]-plagioclase geobarometry indicate that the WPC formed at T = 740--780 C and P = 0.4--0.7 GPa. Published experimental data show that < 50% melting is likely under these conditions if melting is controlled by dehydration reactions. Bucksport lithologies contain < 20% biotite, suggesting that the maximum amount of melt that could have formed by dehydration melting is < 20%, even if all biotite was consumed during melting. It seems probable that a free fluid phase was required to generate the WPC. Migmatization is apparent in all lithologies (including amphibolites) in the vicinity of the WPC, consistent with fluid-present melting. Fluid may have ingressed along the St. George thrust, but the source of the fluid is unknown.

  15. Electrocatalytic Oxidation of Formate by [Ni(PR2NR`2)2(CH3CN)]2+ Complexes

    SciTech Connect

    Galan, Brandon R.; Schoffel, Julia; Linehan, John C.; Seu, Candace; Appel, Aaron M.; Roberts, John A.; Helm, Monte L.; Kilgore, Uriah J.; Yang, Jenny Y.; DuBois, Daniel L.; Kubiak, Cliff

    2011-09-07

    New [Ni(PR2NR`2)2(CH3CN)]2+ complexes with R = Ph, R` = 4-MeOPh; R = Cy, R` = Ph and a mixed ligand [Ni(PR2NR`2)(PR``2NR`2)]2+ with R = Cy, R` = Ph, R`` = Ph have been synthesized and characterized by single crystal X-ray crystallography. These complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO2, protons, and electrons with rates which are first order in catalyst and in formate at formate concentrations below approximately 0.05 M. For the catalysts studied, maximum observed turnover frequencies vary from <1.1 s-1 to 12.5 s-1 at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. A mechanistic scheme is proposed which involves an initial nickel complex bound ?1-OC(O)H followed by a rate limiting hydride transfer step. An acetate complex demonstrating the ?1-OC(O)CH3 binding mode to nickel has also been synthesized and characterized by single crystal X-ray crystallography. The pendant amines have been demonstrated to be essential for this electrocatalytic activity as no activity toward formate was found for the similar [Ni(depe)2][BF4]2 (depe = diethylphosphinoethane) complex. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  16. He-ThO(1?+) interactions at low temperatures: Elastic and inelastic collisions, transport properties, and complex formation in cold 4He gas

    NASA Astrophysics Data System (ADS)

    Tscherbul, T. V.; Sayfutyarova, E. R.; Buchachenko, A. A.; Dalgarno, A.

    2011-04-01

    We present an ab initio study of cold 4He + ThO(1?+) collisions based on an accurate potential energy surface (PES) evaluated by the coupled cluster method with single, double, and noniterative triple excitations using an extended basis set augmented by bond functions. Variational calculations of rovibrational energy levels show that the 4He-ThO van der Waals complex has a binding energy of 10.9 cm-1 in its ground J = 0 rotational state. The calculated energy levels are used to obtain the temperature dependence of the chemical equilibrium constant for the formation of the He-ThO complex. We find that complex formation is thermodynamically favored at temperatures below 1 K and predict the maximum abundance of free ground-state ThO(v = 0, j = 0) molecules between 2 and 3 K. The calculated cross sections for momentum transfer in elastic He + ThO collisions display a rich resonance structure below 5 cm-1 and decline monotonically above this collision energy. The cross sections for rotational relaxation accompanied by momentum transfer decline abruptly to zero at low collision energies (<0.1 cm-1). We find that Stark relaxation in He + ThO collisions can be enhanced by applying an external dc electric field of less than 100 kV/cm. Finally, we present calculations of thermally averaged diffusion cross sections for ThO in He gas, and find these to be insensitive to small variations of the PES at temperatures above 1 K.

  17. Formation of mono(dithiolene)-thiocarboxamido complexes in reactions of thio(dithiocarbamato)-Mo/W complexes and dimethyl acetylenedicarboxylate.

    PubMed

    Lim, Patrick J; Slizys, Damian A; Tiekink, Edward R T; Young, Charles G

    2005-01-10

    Reactions of TpMS(S(2)CNEt(2)) with dimethyl acetylenedicarboxylate in dichloromethane produce olive green/black TpM{S(2)C(2)(CO(2)Me)(2)}(SCNEt(2)-kappa(2)S,C) (M = Mo (1), W (2); Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate). The seven-coordinate complexes exhibit pseudo-octahedral (1) and distorted pentagonal bipyramidal (2) coordination spheres comprised of tridentate fac-Tp, bidentate dithiolene, and thiocarboxamido-kappa(2)S,C ligands. In the solid state, molecules of 1 exhibit pseudo-C(s)() symmetry, with the thiocarboxamide NEt(2) group in a cleft in the Tp ligand. Molecules of 2 have C(1) symmetry in the solid state; here, the thiocarboxamide unit is orientated along one of the W-S(dithiolene) bonds with its NEt(2) group projecting away from the Tp ligand. Both complexes possess effective C(s)() symmetry in solution. Reaction of TpMoI(CO)(3) with AgS(2)CNEt(2) affords olive green TpMo(S(2)CNEt(2))(CO)(2) (3), which reacts with propylene sulfide in a new synthesis for TpMoS(S(2)CNEt(2)), the starting material for 1. Complex 3 exhibits a distorted pentagonal bipyramidal structure, the axial sites being defined by a Tp nitrogen atom and a carbonyl ligand, the pentagonal plane by the remaining nitrogen and carbonyl donors and the two sulfur atoms of the bidentate dithiocarbamate ligand. PMID:15627367

  18. P62 Regulates resveratrol-mediated Fas/Cav-1 complex formation and transition from autophagy to apoptosis

    PubMed Central

    Zhang, Jun; Ma, Ke; Qi, Tingting; Wei, Xiaoning; Zhang, Qing; Li, Guanwu; Chiu, Jen-Fu

    2015-01-01

    Resveratrol is a potential polyphenol drug used in cancer treatment. We examined the relationship between autophagy and apoptosis in RSV-treated non-small lung adenocarcinoma A549 cells. Resveratrol treatment increased autophagy and autophagy-mediated degradation of P62. Immunocytochemistry revealed P62 co-localized with Fas/Cav-1 complexes, known to induce apoptosis. However, siRNA-mediated P62 downregulation enhanced formation of Fas/Cav-1 complexes, suggesting that P62 inhibited Fas/Cav-1 complex formation. Fas/Cav-1 complexes triggered caspase-8 activation and cleavage of Beclin-1, releasing a C-terminal Beclin-1 peptide that translocated to the mitochondria and initiate apoptosis. Inhibition of autophagy by siRNA-mediated repression of Beclin-1 also blocked RSV-induced apoptosis, showing a dependence of apoptosis on autophagy. P62 knockdown by siRNA accelerated the activation of caspase-8 and initiate apoptosis, while Cav-1 knockdown inhibited apoptosis, but increased autophagy. Inhibition of autophagy by 3-MA prevented both P62 degradation and induction of apoptosis, whereas inhibition of apoptosis by z-IETD-FMK or z-DEVD-FMK enhanced both P62 induction and autophagic cell death. In conclusion, P62 links resveratrol-induced autophagy to apoptosis. P62 blocks apoptosis by inhibiting Fas/Cav-1 complex formation, but RSV-induced autophagic degradation of P62 enables formation of Fas/Cav-1 complexes which then activate caspase-8-mediated Beclin-1 cleavage, resulting in translocation of the Beclin-1 C-terminal fragment to the mitochondria to initiate apoptosis. PMID:25596736

  19. Effects of chemical and enzymatic modifications on starch-stearic acid complex formation.

    PubMed

    Arijaje, Emily Oluwaseun; Wang, Ya-Jane; Shinn, Sara; Shah, Utkarsh; Proctor, Andrew

    2014-04-01

    Debranched unacetylated and acetylated potato starches with two degrees of substitution, 0.041 (low) and 0.078 (high), combined with or without ?-amylase hydrolysis were prepared to form soluble and insoluble complexes with stearic acid. The effects of modifications on the complexation, thermal properties, and X-ray patterns of soluble and insoluble complexes were investigated. Acetylation decreased the recovery of insoluble complexes but increased that of soluble complexes. Low acetylated, ?-amylase-treated starch had a significantly increased amount of complexed stearic acid (123.1 mg/g) for insoluble complexes; high acetylated, ?-amylase-treated starch had the highest complexed stearic acid (61.2 mg/g) for the soluble complexes. The melting temperature of the complexes decreased with acetylation. All ?-amylase-treated acetylated complexes displayed the V-type diffraction pattern with peaks at 2? = 7.4, 12.9, and 20. These results suggest that starch can be modified by acetylation, debranching, and/or ?-amylase to produce significant quantities of soluble starch-stearic acid complexes. PMID:24641427

  20. Formation of an iron phosphine-borane complex by formal insertion of BH₃ into the Fe-P bond.

    PubMed

    Frank, Nicolas; Hanau, Katharina; Flosdorf, Kimon; Langer, Robert

    2013-08-21

    A unique hydrido phosphine-borane iron(II) complex [(dppa)(Ph₂P-N-P(BH₃)Ph₂)Fe(H)] (1) was obtained by the reaction of iron(II) chloride and two equivalents of bis(diphenylphosphino)amine (dppa) with an excess of sodium borohydride in acetonitrile-ethanol mixtures. Detailed investigations of the reaction revealed that a mixture of cis- and trans-[(dppa)₂Fe(NCMe)₂]²⁺ is formed prior to the reduction by sodium borohydride. Depending on the solvent, different products were obtained by the reduction: in acetonitrile-ethanol mixtures the hydrido phosphine-borane complex 1 is formed by formal insertion of BH₃, while the reduction in pure acetonitrile results in the formation of the cationic complex trans-[(dppa)₂Fe(H)(NCMe)](BH₄) (4). Complex 4 is remarkably stable in ethanol and does not undergo phosphine-borane formation, even in the presence of excess sodium borohydride. This observation suggests that the phosphine-borane complex is generated by the reaction with the first equivalent of sodium borohydride with the participation of ethanol, followed by deprotonation or dihydrogen elimination. Experiments with similar diphosphine ligands, such as bis(diphenylphosphino)methane, did not yield a phosphine-borane complex, indicating the crucial role of the amine group in the observed reactivity. PMID:23811820

  1. Formation, Detection and the Distribution of Complex Organic Molecules with the Atacama Large Millimeter/submillimeter Array (ALMA)

    NASA Astrophysics Data System (ADS)

    Remijan, Anthony John

    2015-08-01

    The formation and distribution of complex organic material in astronomical environments continues to be a focused research area in astrochemistry. For several decades now, emphasis has been placed on the millimeter/submillimeter regime of the radio spectrum for trying to detect new molecular species and to constrain the chemical formation route of complex molecules by comparing and contrasting their relative distributions towards varying astronomical environments. This effort has been extremely laborious as millimeter/submillimeter facilities have been only able to detect and map the distribution of the strongest transition(s) of the simplest organic molecules. Even then, these single transition "chemical maps" have been very low spatial resolution because early millimeter/submillimeter facilities did not have access to broadband spectral coverage or the imaging capabilities to truly ascertain the morphology of the molecular emission. In the era of ALMA, these limitations have been greatly lifted. Broadband spectral line surveys now hold the key to uncovering the full molecular complexity in astronomical environments. In addition, searches for complex organic material is no longer limited to investigating the strongest lines of the simplest molecules toward the strongest sources of emission in the Galaxy. ALMA is issuing a new era of exploration as the search for complex molecules will now be available to an increased suite of sources in the Galaxy and our understanding of the formation of this complex material will be greatly increased as a result. This presentation will highlight the current and future ALMA capabilities in the search for complex molecules towards astronomical environments, highlight the recent searches that ALMA scientists have conducted from the start of ALMA Early Science and provide the motivation for the next suite of astronomical searches to investigate our pre-biotic origins in the universe.

  2. Experimental determination of the solubility constant for magnesium chloride hydroxide hydrate (Mg 3Cl(OH) 54H 2O, phase 5) at room temperature, and its importance to nuclear waste isolation in geological repositories in salt formations<