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Sample records for complex formation constants

  1. 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.

  2. 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].

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

    PubMed

    Königsberger, Lan-Chi; Königsberger, 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

  5. Determination of complex formation constants by phase sensitive alternating current polarography: Cadmium-polymethacrylic acid and cadmium-polygalacturonic acid.

    PubMed

    Garrigosa, Anna Maria; Gusmão, Rui; Ariño, Cristina; Díaz-Cruz, José Manuel; Esteban, Miquel

    2007-10-15

    The use of phase sensitive alternating current polarography (ACP) for the evaluation of complex formation constants of systems where electrodic adsorption is present has been proposed. The applicability of the technique implies the previous selection of the phase angle where contribution of capacitive current is minimized. This is made using Multivariate Curve Resolution by Alternating Least Squares (MCR-ALS) in the analysis of ACP measurements at different phase angles. The method is checked by the study of the complexation of Cd by polymethacrylic (PMA) and polygalacturonic (PGA) acids, and the optimal phase angles have been ca. -10 degrees for Cd-PMA and ca. -15 degrees for Cd-PGA systems. The goodness of phase sensitive ACP has been demonstrated comparing the determined complex formation constants with those obtained by reverse pulse polarography, a technique that minimizes the electrode adsorption effects on the measured currents. PMID:19073101

  6. Stability constants for the formation of rare earth-inorganic complexes as a function of ionic strength

    NASA Astrophysics Data System (ADS)

    Millero, Frank J.

    1992-08-01

    Recent studies have been made on the distribution of the rare earths (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) in natural waters relative to their concentration in shales. These metals have also been used as models for the behavior of the trivalent actinides. The speciation of the rare earths in natural waters is modelled by using ionic interaction models which require reliable stability constants. In this paper the stability constants for the formation of lanthanide complexes ( k mx∗) with Cl -, NO 3-, SO 42-, OH -, HCO 3-, H 2PO 4-, HPO 42-, and CO 32- determined in NaClO 44 at various ionic strengths have been extrapolated to infinite dilution using the Pitzer interaction model. The activity coefficients for free ions ( γM, γx) needed for this extrapolation have been estimated from the Pitzer equations. The thermodynamic stability constants ( KMX) and activity coefficients of the various ion pairs ( γMX) were determined from In ( solK MX∗/γ Mγ x) = In K mx+ In (γ MX). The activity coefficients of the ion pairs have been used to determine Pitzer parameters ( BMX) for the rare earth complexes. The values of BMX were found to be the same for complexes of the same charge. These results make it possible to estimate the stability constants for the formation of rare earth complexes over a wide range of ionic strengths. The stability constants have been used to determine the speciation of the lanthanides in seawater and in brines. The carbonate complexes dominate for all natural waters where the carbonate alkalinity is greater than 0.001 eq/L at a pH near 8.

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

    PubMed

    Frycák, 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

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

    PubMed

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

    2016-01-01

    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 (1)H and DOSY (1)H 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

  9. 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

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

    NASA Astrophysics Data System (ADS)

    Luo, Yanxin; Millero, Frank J.

    2007-01-01

    The stability constants for the formation of lead (Pb 2+) with chloride Pb+nCl↔PbCln2-nβn(n=1,2,3) have been determined using a spectrophotometric method in NaClO 4 solutions as a function of ionic strength (0-6 m) and temperature (15-45 °C). The results have been fitted to the equations:

  11. 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−nβn(n=1,2,3) have been determined using a spectrophotometric method in NaClO4 solutions as a function of ionic strength (0–6 m) and temperature (15–45 °C). The results have been fitted to the equations: logβ1∗=logβ1+0.21I−8.61I0.5∕(1+1.2I0.5)+1927.40[I0.5∕(1+1.2I0.5)]∕Tlogβ2∗=logβ2+0.32I−4.67I0.5(1+1.2I0.5)+594.54[I0.5∕(1+1.2I0.5)]∕Tlogβ3∗=logβ3+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 β1, logβ2 and logβ3 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: logβ1=44.82+0.031T−21.21logTlogβ2=61.42+0.046T−29.51logTlogβ3=107.97+0.071T−51.46logT with standard errors of 0.05, 0.08 and 0.10, respectively. PMID:26937043

  12. 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

  13. Constant Communities in Complex Networks

    NASA Astrophysics Data System (ADS)

    Chakraborty, Tanmoy; Srinivasan, Sriram; Ganguly, Niloy; Bhowmick, Sanjukta; Mukherjee, Animesh

    2013-05-01

    Identifying community structure is a fundamental problem in network analysis. Most community detection algorithms are based on optimizing a combinatorial parameter, for example modularity. This optimization is generally NP-hard, thus merely changing the vertex order can alter their assignments to the community. However, there has been less study on how vertex ordering influences the results of the community detection algorithms. Here we identify and study the properties of invariant groups of vertices (constant communities) whose assignment to communities are, quite remarkably, not affected by vertex ordering. The percentage of constant communities can vary across different applications and based on empirical results we propose metrics to evaluate these communities. Using constant communities as a pre-processing step, one can significantly reduce the variation of the results. Finally, we present a case study on phoneme network and illustrate that constant communities, quite strikingly, form the core functional units of the larger communities.

  14. 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

  15. 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.

  16. 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

  17. 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)

  18. 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.

  19. IR spectroscopy determination of the complexation constant for a cholesterol-diisopropyl sulfoxide complex

    NASA Astrophysics Data System (ADS)

    Gabrielyan, L. S.; Melik-Ohanjanyan, L. G.; Markarian, S. A.

    2013-03-01

    We have studied the IR absorption spectra of cholesterol in the presence of diisopropyl sulfoxide in carbon tetrachloride. We show that complexation of cholesterol with diisopropyl sulfoxide occurs as a result of formation of a hydrogen bond between the hydrogen of the hydroxyl group of the cholesterol and the oxygen of the sulfoxide group of the diisopropyl sulfoxide. We have determined the complexation constant for the cholesterol—diisopropyl sulfoxide constant, K eq = 9.25 L/mol at 23°C.

  20. A 1H NMR titration study on the binding constants for D- and L-tryptophan inclusion complexes with 6-O-α-D-glucosyl-β-cyclodextrin. Formation of 1:1 and 2:1 (host:guest) complexes

    NASA Astrophysics Data System (ADS)

    Akita, Tomoki; Matsui, Yoshihisa; Yamamoto, Tatsuyuki

    2014-02-01

    A 1H NMR titration study revealed that 6-O-α-D-glucosyl-β-cyclodextrin (G1-β-CD) forms 1:1 and 2:1 (host:guest) inclusion complexes with D- and L-tryptophan in alkaline D2O solutions (pD 11.0). The binding constants (K1's) for the 1:1 complexes of D-isomer at 298 K (59 mol-1 dm3) were virtually equal to that of L-isomer (54 mol-1 dm3). On the other hand, the K2 values for 2:1 complexes of D-isomer (42 mol-1 dm3) were larger than that of L-counterpart (12 mol-1 dm3). These facts suggest that the first CD molecule includes the indole ring moiety of tryptophan, followed by inclusion with the second CD molecule in the vicinity of chiral center, α-carbon of the guest, to result in the difference in K2's for two enantiomers. Two-dimensional NMR measurement (Rotating-frame nuclear Overhauser Effect SpectroscopY, ROESY) supported this interpretation.

  1. 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.

  2. 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.

  3. 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 < 1.0 for log K1 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

  4. 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.

  5. 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.

  6. 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.

  7. Reverse hydrotropy by complex formation.

    PubMed

    Wojciechowski, Kamil; Gutberlet, Thomas; Raghuwanshi, Vikram Singh; Terry, Ann

    2015-01-14

    Self-aggregation of three di-N-alkylated diaza-18-crown-6 ethers (ACEs) was studied in non-polar solvents. The three ACEs differed by the length of the alkyl chain: n-decyl (ACE-10), n-hexadecyl (ACE-16) and n-tetracosane (ACE-24). From the previously reported interfacial tension isotherms, the formation of reverse micelles was expected above ACE concentrations of ∼10(-3) M. However, the water content analysis in conjunction with Dynamic Light Scattering (DLS), Fluorescence Correlation Spectroscopy (FCS) and (1)H NMR Diffusion Ordered Spectroscopy (DOSY) do not provide any clear proof of the existence of aggregates. Only the Small Angle Neutron Scattering (SANS) of concentrated toluene ACE solutions reveals the existence of small reverse micelles (probably ACE dimers forming small cages hosting 1-2 water molecules). On the other hand, spectrophotometric and fluorescence dye dissolution studies using eosin Y, tropaeolin OO and methyl orange suggest that ACEs can dissolve these dyes without requiring the formation of aggregates. This discrepancy was interpreted assuming the dye-ACE complexation as the driving force for dye solubilisation, providing a possible mechanism of reverse hydrotropy ("lipotropy") in non-polar solvents. This example shows that special care should be taken when dye solubilisation is used to probe self-aggregation of an amphiphile in non-polar solvents. The amphiphile-dye complex formation might be responsible for false positive results and the aggregate formation should always be confirmed with other methods. PMID:25415596

  8. 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)…

  9. 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

  10. 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.

  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

    SciTech Connect

    Giordano, T.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 (F{sub 3}CSO{sub 3}Na) was used as a supporting electrolyte. Stoichiometries and formation quotients for the complexes ZnCH{sub 3}COO{sup +}, Zn(CH{sub 3}COO){sub 2}, and Zn(CH{sub 3}COO){sub 3}{sup {minus}} were derived from the titration data by regression analysis. Stability constants at infinite dilution (K{sub n}) and other relevant thermodynamic quantities were calculated for these three complexes. 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. A new graphic method for differentiating mononuclear and polynuclear complexes and for determining their stability constants.

    PubMed

    García, D V; Ramírez, A A; Ceba, M R

    1979-03-01

    A new graphical method is proposed for differentiating mononuclear and polynuclear complexes as well as for determining the stability constant of any complex A(m)B(n). The method is based on the effect of dilution on the degree of dissociation of the complex. The resultant mathematical equation provides a simple graphical calculation which leads to the determination of the stability constant and also the molar absorptivity of the complex. PMID:18962419

  14. 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.

  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. 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.

  17. 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).

  18. Dissociation of bimolecular αIIbβ3-fibrinogen complex under a constant tensile force.

    PubMed

    Litvinov, Rustem I; Barsegov, Valeri; Schissler, Andrew J; Fisher, Andrew R; Bennett, Joel S; Weisel, John W; Shuman, Henry

    2011-01-01

    The regulated ability of integrin αIIbβ3 to bind fibrinogen plays a crucial role in platelet aggregation, adhesion, and hemostasis. Employing an optical-trap-based electronic force clamp, we studied the thermodynamics and kinetics of αIIbβ3-fibrinogen bond formation and dissociation under constant unbinding forces, mimicking the forces of physiologic blood shear on a thrombus. The distribution of bond lifetimes was bimodal, indicating that the αIIbβ3-fibrinogen complex exists in two bound states with different mechanical stability. The αIIbβ3 antagonist, abciximab, inhibited binding without affecting the unbinding kinetics, whereas Mn²(+) biased the αIIbβ3-fibrinogen complex to the strong bound state with reduced off-rate. The average bond lifetimes decreased exponentially with increasing pulling force from ∼5 pN to 50 pN, suggesting that in this force range the αIIbβ3-fibrinogen interactions are classical slip bonds. We found no evidence for catch bonds, which is consistent with the known lack of shear-enhanced platelet adhesion on fibrinogen-coated surfaces. Taken together, these data provide important quantitative and qualitative characteristics of αIIbβ3-fibrinogen binding and unbinding that underlie the dynamics of platelet adhesion and aggregation in blood flow. PMID:21190668

  19. 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.

  20. 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.

  1. 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…

  2. Determination of complex permittivity from propagation constant measurement with planar transmission lines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new two-standard calibration procedure is outlined for determining the complex permittivity of materials from the propagation constant measured with planar transmission lines. Once calibrated, a closed-form expression for the material permittivity is obtained. The effects of radiation and conducto...

  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. 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).

  5. 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.

  6. 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.

  7. 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

  8. Complex dielectric constants for selected near-millimeter-wave materials at 245 GHz

    NASA Technical Reports Server (NTRS)

    Dutta, J. M.; Jones, C. R.; Dave, H.

    1986-01-01

    A double-beam instrument developed in this laboratory has been used to measure the complex dielectric constant of selected materials at 245 GHz. It is reported here the results for crystalline quartz, fused silica (Spectrosil WF and Dynasil 4000), beryllia (iso-pressed), boron nitride (hot-pressed), and a nickel ferrite (Trans-Tech 2-111). Results are compared with the data obtained by other researchers.

  9. 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.

  10. 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

  11. 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.

  12. Cadmium(II) complex formation with glutathione.

    PubMed

    Mah, Vicky; Jalilehvand, Farideh

    2010-03-01

    Complex formation between heavy metal ions and glutathione (GSH) is considered as the initial step in many detoxification processes in living organisms. In this study the structure and coordination between the cadmium(II) ion and GSH were investigated in aqueous solutions (pH 7.5 and 11.0) and in the solid state, using a combination of spectroscopic techniques. The similarity of the Cd K-edge and L(3)-edge X-ray absorption spectra of the solid compound [Cd(GS)(GSH)]ClO(4).3H(2)O, precipitating at pH 3.0, with the previously studied cysteine compound {Cd(HCys)(2).H(2)O}(2).H(3)O(+).ClO(4) (-) corresponds to Cd(S-GS)(3)O (dominating) and Cd(S-GS)(4) four-coordination within oligomeric complexes with mean bond distances of 2.51 +/- 0.02 A for Cd-S and 2.24 +/- 0.04 A for Cd-O. For cadmium(II) solutions (C (Cd(II)) approximately 0.05 M) at pH 7.5 with moderate excess of GSH (C (GSH)/C (Cd(II)) = 3.0-5.0), a mix of Cd(S-GS)(3)O (dominating) and Cd(S-GS)(4) species is consistent with the broad (113)Cd NMR resonances in the range 632-658 ppm. In alkaline solutions (pH 11.0 and C (GSH)/C (Cd(II)) = 2.0 or 3.0), two distinct peaks at 322 and 674 ppm are obtained. The first peak indicates six-coordinated mononuclear and dinuclear complexes with CdS(2)N(2)(N/O)(2) and CdSN(3)O(2) coordination in fast exchange, whereas the second corresponds to Cd(S-GS)(4) sites. At high ligand excess the tetrathiolate complex, Cd(S-GS)(4), characterized by a sharp delta((113)Cd) NMR signal at 677 ppm, predominates. The average Cd-S distance, obtained from the X-ray absorption spectra, varied within a narrow range, 2.49-2.53 A, for all solutions (pH 7.5 and 11.0) regardless of the coordination geometry. PMID:20035360

  13. 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

  14. 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.

  15. Use of laser induced photoacoustic spectroscopy (LIPAS) to determine equilibrium constants of cation-cation complexes

    SciTech Connect

    Hannink, N.J.; Hoffman, D.C.; Silva, R.J.; Russo, R.E.

    1993-12-31

    Laser Induced PhotoAcoustic Spectroscopy (LIPAS) is a relatively new, photothermal technique to examine solutions. Studies in the past have shown it to be more sensitive than conventional absorption spectroscopy, while, yielding the same information thus allowing lower concentrations to be used. This study is using LIPAS to examine solutions to determine the equilibrium constants of cation-cation complexes. It has been found that actinyl(V) cations form cation-cation complexes with a variety of cations, including actinyl(VI) cations. The radioactive nature of the actinide elements requires special handling techniques and also require limits be placed on the amount of material that can be used. The sensitivity of some oxidation states of the actinides to oxygen also presents a problem. Preliminary results will be presented for actinyl(V)-actinyl(VI) cation-cation complexes that were studied using a remote LIPAS system incorporating fiber optics for transmission of laser signals.

  16. 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.

  17. 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 Сu(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

  18. 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

  19. 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

  20. Predicting the stability constants of metal-ion complexes from first principles.

    PubMed

    Gutten, Ondrej; Rulíšek, Lubomír

    2013-09-16

    The most important experimental quantity describing the thermodynamics of metal-ion binding with various (in)organic ligands, or biomolecules, is the stability constant of the complex (β). In principle, it can be calculated as the free-energy change associated with the metal-ion complexation, i.e., its uptake from the solution under standard conditions. Because this process is associated with the interactions of charged species, large values of interaction and solvation energies are in general involved. Using the standard thermodynamic cycle (in vacuo complexation and solvation/desolvation of the reference state and of the resulting complexes), one usually subtracts values of several hundreds of kilocalories per mole to obtain final results on the order of units or tens of kilocalories per mole. In this work, we use density functional theory and Møller-Plesset second-order perturbation theory calculations together with the conductor-like screening model for realistic solvation to calculate the stability constants of selected complexes--[M(NH3)4](2+), [M(NH3)4(H2O)2](2+), [M(Imi)(H2O)5](2+), [M(H2O)3(His)](+), [M(H2O)4(Cys)], [M(H2O)3(Cys)], [M(CH3COO)(H2O)3](+), [M(CH3COO)(H2O)5](+), [M(SCH2COO)2](2-)--with eight divalent metal ions (Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), and Hg(2+)). Using the currently available computational protocols, we show that it is possible to achieve a relative accuracy of 2-4 kcal·mol(-1) (1-3 orders of magnitude in β). However, because most of the computed values are affected by metal- and ligand-dependent systematic shifts, the accuracy of the "absolute" (uncorrected) values is generally lower. For metal-dependent systematic shifts, we propose the specific values to be used for the given metal ion and current protocol. At the same time, we argue that ligand-dependent shifts (which cannot be easily removed) do not influence the metal-ion selectivity of the particular site, and therefore it can be computed to within 2 kcal·mol(-1) average accuracy. Finally, a critical discussion is presented that aims at potential caveats that one may encounter in theoretical predictions of the stability constants and highlights the perspective that theoretical calculations may become both competitive and complementary tools to experimental measurements. PMID:24000817

  1. 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

  2. Spectroscopic study of complex formation between aliphatic amines and chromogenic calix[4]arene derivatives

    NASA Astrophysics Data System (ADS)

    Mohammed-Ziegler, I.; Kubinyi, M.; Grofcsik, A.; Grün, A.; Bitter, I.

    1999-05-01

    The complexation properties of two new calix[4]arene derivatives were studied by UV/Vis spectroscopy. They have been found to bind aliphatic amines, lithium and calcium ions in equilibrium reactions, particularly in polar solvents. The reaction is indicated through the emergence of a new band. The equilibrium constants of complex formation in the case of some ligand-substrate compositions have been determined.

  3. 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.

  4. 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.

  5. A QICAR approach for quantifying binding constants for metal-ligand complexes.

    PubMed

    Zhou, Dong-Mei; Li, Lian-Zhen; Peijnenburg, Willie J G M; Ownby, David R; Hendriks, A Jan; Wang, Peng; Li, Dan-Dan

    2011-05-01

    Relative metal-ligand complex stability is predicted by evaluating the relationships between physicochemical properties of metal ions and their experimental biotic and abiotic binding constants, K. Linear regression analysis showed that the softness index (σ(p)) and the covalent index (χ(2)(m) r) were especially useful in model construction for rainbow trout (Oncorhynchus mykiss), fathead minnows (Pimephales promelas) and crustaceansaquatic (Daphnia magna) based on RMSE and F-ratio criterion (F(observed)/F(critical) of ≥4). The absolute value of the log of the first hydrolysis constant |logK(OH)| correlated best with logK values for barley (R(2)=0.74, p=0.02) and earthworm (R(2)=0.82, p=0.01). In contrast, the ionic index Z(2)/r explained most of the variability of logK values for the two clays kaolinite and montmorillonite, while |logK(OH)| was a better predictor of the generic NICA-Donnan parameters for HA and FA (0.67

  6. Coordination of lanthanides by two polyamino polycarboxylic macrocycles: formation of highly stable lanthanide complexes

    SciTech Connect

    Loncin, M.F.; Desreux, J.F.; Merciny, E.

    1986-07-16

    The formation constants of a few lanthanide complexes with DOTA (1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid) and TETA (1,4,8,11-tetraazacyclotetradecane-N,N',N'',N'''-tetraacetic acid) have been measured by potentiometric and competition methods. The ligand DOTA forms the most stable lanthanide chelates known so far (log K/sub ML/ = 28.2-29.2) while the stability of the TETA compounds at 80 /sup 0/C (log K/sub ML/ = 14.5-16.5) is comparable to the stability of the EDTA complexes. A competition method with the oxalate anion as a probe had to be used for determining the formation constants of the DOTA lanthanide chelates because of the high stability of these compounds. The relative stability of the DOTA and TETA complexes in accounted for by steric factors with reference to known solution- and solid-state structures. 20 references, 2 tables.

  7. Complexation of Arsenite with Dissolved Organic Matter: Conditional Distribution Coefficients and Apparent Stability Constants

    PubMed Central

    Liu, Guangliang; Cai, Yong

    2010-01-01

    The complexation of arsenic (As) with dissolved organic matter (DOM), although playing an important role in regulating As mobility and transformation, is poorly characterized, as evidenced by scarce reporting of fundamental parameters of As-DOM complexes. The complexation of arsenite (AsIII) with Aldrich humic acid (HA) at different pHs was characterized using a recently developed analytical technique to measure both free and DOM-bound As. Conditional distribution coefficient (KD), describing capacity of DOM in binding AsIII from the mass perspective, and apparent stability constant (Ks), describing stability of resulting AsIII-DOM complexes, were calculated to characterize AsIII-DOM complexation. Log KD of AsIII ranged from 3.7 to 2.2 (decreasing with increase of As/DOM ratio) at pH 5.2, from 3.6 to 2.6 at pH 7, and from 4.3 to 3.2 at pH = 9.3, respectively. Two-site ligand binding models can capture the heterogeneity of binding sites and be used to calculate Ks by classifying the binding sites into strong (S1) and weak (S2) groups. Log Ks for S1 sites are 7.0, 6.5, and 5.9 for pH 5.2, 7, and 9.3, respectively, which are approximately 1–2 orders of magnitude higher than for weak S2 sites. The results suggest that AsIII complexation with DOM increases with pH, as evidenced by significant spikes in concentrations of DOM-bound AsIII and in KD values at pH 9.3. In contrary to KD, log Ks decreased with pH, in particular for S1 sites, probably due to the presence of negatively charged H2AsO3− and the involvement of metal-bridged AsIII-DOM complexation at pH 9.3. PMID:20801484

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

    SciTech Connect

    Martínez-García, Eric E.; Puerari, Ivânio 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 μm, 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 μm. 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-Hα phase shifts corroborate the CO-24 μm azimuthal offsets. Also for NGC 5194, the CO-70 μm, CO-140 μm, and CO-250 μm phase shifts indicate a corotation region.

  9. 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.

  10. Formation of complex emulsion in microfluidic channel

    NASA Astrophysics Data System (ADS)

    Choi, Chang-Hyung; Kim, Jongmin; Lee, Chang-Soo

    2012-02-01

    We first report a novel emulsification method using two binary mixtures that produces complex emulsion by phase separation, triggered by external diffusion of separation agent dissolved in continuous phase. A disperse phase consists of monomer and D-solvent (good solvent for disperse phase), while mixture of separation-triggering agent (SA) and C-solvent (good solvent for continuous phase) is used as a continuous phase. Individual droplet was formed by microfluidic system, allowing how the separation dynamically occurs as a function of time. This system consists of the three major steps involving the transformation of a single droplet into the complex emulsion. In the first, when two immiscible phases meet at cross-junction, droplets are generated and dispersed in continuous phase containing the SA. Since the SA is only selectively soluble in the monomer of disperse phase, external diffusion of SA into the droplets through the interface occurs which initiates phase separation. In transient state, the external diffusion of the SA generates both partial separated region and SA/monomer complex at the near interface of partial separated region. In the last step, where the phase separation fully occurs, single droplets transform into complex emulsion such as double emulsion or multiple emulsion with high order. In addition, we demonstrate a capability for generation of complex emulsions gives a great opportunity to fabricate functional materials using template synthesis.

  11. Studies of formation of bivalent copper complexes with native and denatured DNA.

    PubMed

    Sorokin, V A; Blagoi, Y P; Valeev, V A; Kornilova, S V; Gladchenko, G O; Reva, I D; Sokhan, V I

    1987-06-01

    The formation of Cu2+ complexes with native and denatured DNA is studied by the methods of differential UV spectroscopy, CD spectroscopy, and viscometry. On ion binding to the bases of native DNA the latter transforms into a new conformation. This transition is accompanied with a sharp increase in UV absorption and a decrease in the intrinsic viscosity though the high degree of helicity persists. Possible sites of Cu2+ ion binding on DNA of various conformations are found along with corresponding constants of complex formation. PMID:3598574

  12. Determination of stability constants of Cu(I), Cd(II) & Zn(II) complexes with thiols using fluorescent probes.

    PubMed

    Walsh, Michael J; Ahner, Beth A

    2013-11-01

    Fluorometric competing-ligand titrations were used to measure stability constants of Zn(II), Cd(II) and Cu(I) complexes of cysteine and glutathione (GSH). Cu(I)-stability constants were also determined for the dipeptides Arg-Cys and Gln-Cys which are produced by a marine alga under copper stress. The fluorescent ion indicators FluoZin-1 and BTC (Invitrogen) were used as competing ligands in titrations involving Zn(II) and Cd(II). Phen Green SK (Invitrogen) was likewise used in Cu(I) titrations. Conditional and cumulative general stability constants were determined using a least squares fit of the titration data to speciation models. The measured stability constants of Cd(II) and Zn(II) complexes were consistent with previous work, validating our method and assumptions. Our results also include the first general stability constants for Cu(I)-cysteine complexes and an alternative set for Cu(I)-GSH complexes. While these stability constants indicate that Cu(I) forms strong complexes with thiols, they are not strong enough to effectively buffer Cu(I) in seawater. PMID:23954481

  13. Tungsten speciation in sulfidic waters: Determination of thiotungstate formation constants and modeling their distribution in natural waters

    NASA Astrophysics Data System (ADS)

    Mohajerin, T. Jade; Helz, George R.; White, Christopher D.; Johannesson, Karen H.

    2014-11-01

    Using UV/VIS spectrophotometry the equilibrium constants for the formation of monothiotungstate, WO3S2- (WO42-+H2S↔WO3S2-+H2O; log K01 = 3.08 ± 0.11), dithiotungstate, WO2S22- (WO3S2-+H2S↔WO2S22-+H2O; log K12 = 3.22 ± 0.22), trithiotungstate, WOS32- (WO2S22-+H2S↔WO3S2-+H2O; log K23 = 2.76 ± 0.10), and tetrathiotungstate, WS42- (WO3S2-+H2S↔WS42-+H2O; log K34 ∼2.36) were determined. The equilibrium constants describing the formation of thiotungstates are approximately two orders of magnitude less than the equilibrium constants for the formation of the analogous thiomolybdates. These equilibrium constants for thiotungstates were used to model tungstate speciation in sulfidic waters. The model predicts that thiotungstate species are negligible in most natural waters, but are likely to be important in circum-neutral, anoxic waters with ⩾0.1 mM S(-II) concentrations. Natural waters that are conducive to thiotungstate formation include the Black Sea, Tyro and Bannock Basins, and porewaters with high rates of sulfate reduction such as those common in salt marshes. Preliminary field investigations indicate that thiotungstate formation may lead to increased W solubility.

  14. [Determination of stability constants of metal complexes by on-column derivatization reversed phase high performance liquid chromatography].

    PubMed

    Wang, X; Fu, C

    1997-03-01

    The stability constant of metal complexes is an important chemical parameter. There are many methods for its determination, but few analyst has calculated it with high performance liquid chromatography (HPLC). In the present paper a new model for determining the stability constant of metal complexes with on-column derivatization reversed phase HPLC has been proposed where complexation forming reactions are taking place in the mobile phase. Based on the retention mechanism of neutral complexes, the equation for calculation is deduced. It has been applied to some cations (Hg2+, Pb2+, Ni2+, Cu2+, Ag+, Hg+)-DDTC complexes. The results are in agreement with those given in the literature. Then, a simple, practical and rapid graphic method is studied for monovalent metal complexes. The stability constants can be obtained simply as the quotient of the line slope and the axis intercept of the linear dependence. The relations derived in this paper may be used not only for calculating the stability constants from chromatographic measurements but also for optimizing the process of separation based on the values of the stability constants available in literature. PMID:15739390

  15. Formation, structure, and reactivity of palladium superoxo complexes

    SciTech Connect

    Talsi, E.P.; Babenko, V.P.; Shubin, A.A.; Chinakov, V.D.; Nekipelov, V.M.; Zamaraev, K.I.

    1987-11-18

    The mechanism of formation of palladium superoxo complexes, their structure, and their reactivity are discussed. The formation of the palladium superoxo complexes in the reaction of palladium(II) acetate, propionate, trifluororacetate, and bis(acetylacetonate) and palladium(0) tetrakis(triphenylphosphine) with hydrogen peroxide and potassium superoxide has been detected in solution by electron proton resonance. The oxidation of olefins and carbon monoxide by these complexes is considered. Reaction mechanisms and reaction kinetics for these oxidations are reported using the palladium superoxo complexes. 44 references, 8 figures, 2 tables.

  16. Lead(II) Complex Formation with Glutathione

    PubMed Central

    Mah, Vicky

    2012-01-01

    A structural investigation of complexes formed between the Pb2+ ion and glutathione (GSH, denoted AH3 in its triprotonated form) the most abundant non2protein thiol in biological systems, was carried out for a series of aqueous solutions at pH 8.5 and CPb2+ = 10 mM, and in the solid state. The Pb LIII-edge EXAFS oscillation for a solid compound with the empirical formula [Pb(AH2)]ClO4 was modeled with one Pb-S and two short Pb-O bond distances at 2.64 ± 0.04 Å and 2.28 ± 0.04 Å, respectively. In addition Pb···Pb interactions at 4.15 ± 0.05 Å indicate dimeric species in a network where the thiolate group forms an asymmetrical bridge between two Pb2+ ions. In aqueous solution at the mole ratio GSH / Pb(II) = 2.0 (CPb2+ = 10 mM, pH 8.5), lead(II) complexes with two thiolate ligands form, characterized by a ligand-to-metal charge transfer band (LMCT) S- → Pb2+ at 317 nm in the UV-vis spectrum and mean Pb-S and Pb-(N/O) bond distances of 2.65 ± 0.04 Å and 2.51 ± 0.04 Å, respectively, from a Pb LIII-edge EXAFS spectrum. For solutions with higher mole ratios, GSH / Pb(II) ≥ 3.0, ESI-MS spectra identified a trisglutathionyl lead(II) complex, for which Pb LIII-edge EXAFS spectroscopy shows a mean Pb-S distance of 2.65 ± 0.04 Å in PbS3 coordination, 207Pb NMR spectroscopy displays a chemical shift of 2793 ppm, and in the UV-vis spectrum an S- → Pb2+ LMCT band appears at 335 nm. The complex persists at high excess of glutathione, and also at ~25 K in frozen glycerol (33%) / water glasses for GSH / Pb(II) mole ratios from 4.0 to 10 (CPb2+ = 10 mM) measured by Pb LIII-edge EXAFS spectroscopy. PMID:22594853

  17. Determination of the complexation constants of Pb(II) and Cd(II) with thymol blue using spectrophotometry, SQUAD and the HSAB principle.

    PubMed

    Balderas-Hernández, P; Rojas-Hernández, A; Galván, M; Romo, M Romero; Palomar-Pardavé, M; Ramírez-Silva, M T

    2007-01-01

    This paper presents the results concerning the determination of the formation constants of the complexes between thymol blue, TB, and the metal ions Pb(II) or Cd(II). The experimental procedure was carried out in the presence of a nitrogen atmosphere at 25 degrees C. The spectrophotometry data obtained were processed through the software SQUAD to calculate the complexation constants of the metal-indicator and to establish an adequate base of the models which considered the structure of the indicator, and the actual metal species in the aqueous solutions. For the Pb(II)-TB-H2O system the logK value calculated for the PbTB complex was 5.591+/-0.057 while for the Cd(II)-TB-H2O system, the logK value of the CdTB complex was 5.099+/-0.008. Also, supporting theoretical chemistry results on the chemical hardness of TB molecule were performed to enable establishment of a relative prediction scale of the TB complexation constants ranking in the framework of the Principle of Hard and Soft Acids and Bases or HSAB Principle. PMID:16829173

  18. 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(μ2-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

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. Simulation of Titan haze formation using a photochemical flow reactor. The optical constants of the polymer

    NASA Astrophysics Data System (ADS)

    Tran, Buu N.; Joseph, Jeffrey C.; Ferris, James P.; Persans, Peter D.; Chera, John J.

    2003-10-01

    Solar UV is the principal energy source impinging the atmosphere of Titan while the energy from the electrons in Saturn's magnetosphere is less than 0.5% of the UV light. Titan haze analogs were prepared by the photolysis of a mixture of gases that simulate the composition of its atmosphere (nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene). The real (n) and imaginary (k) parts of the complex refractive index of haze analogs formed from four different gas mixtures were calculated from the spectral properties of the solid polymer in UV-visible, near infrared and infrared wavelength spectral regions. The value of n was constant at 1.6±0.1 throughout the 0.2-2.5 μm region. The variation of k with wavelength for the values derived for Titan has a lower error than the absolute values of k so the more significant comparisons are with the slopes of the k( λ) plots in the UV-VIS region. Three of the photochemical Titan haze analogs had slopes comparable to those derived for Titan from the Voyager data (Rages and Pollack, 1980, Icarus 41, 119-130; McKay and Toon, 1992, in: Proceedings of the Symposium on Titan, in: ESA SP, Vol. 338, pp. 185-190). The slopes of the k( λ) plots for haze analogs prepared by spark discharge (Khare et al., 1984, Icarus 60, 127-137) and plasma discharge (Ramirez et al., 2002, Icarus 156, 515-529) were also comparable to Titan's. These finding show that the k( λ) plots do not differentiate between different laboratory simulations of atmospheric chemistry on Titan in the UV-VIS near IR region (0.2-2.5 microns). There is a large difference between the k( λ) in the infrared between the haze analogs prepared photochemically and analogs prepared using a plasma discharges (Khare et al., 1984, Icarus 60, 127-137; Coll et al., 1999, Planet. Space Sci. 47, 1331-1340; Khare et al., 2002, Icarus 160, 172-182). The C/N ratio in the haze analog prepared by discharges is in the 2-11 range while that of the photochemical analogs is in the 18-24 range. The use of discharges and UV light for initiating the chemistry in Titan's atmosphere is discussed.

  4. 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

  5. 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

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

    PubMed

    Pallagi, Attila; Tasi, Ágost Gyula; Peintler, Gábor; Forgo, Péter; Pálinkó, István; Sipos, Pál

    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

  7. 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 ΔJ.

    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 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. PMID:26896987

  8. 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.

  9. Rate constant for formation of chlorine nitrate by the reaction ClO + NO2 + M

    NASA Technical Reports Server (NTRS)

    Leu, M. T.; Lin, C. L.; Demore, W. B.

    1977-01-01

    The pseudo-first-order decay of ClO in a large excess of NO2 was monitored in a discharge flow/mass-spectrometer apparatus in order to measure the rate constant of the reaction ClO + NO2 + M yields ClONO2 + M for M = He, Ar, and N2 over the temperature range from 248 to 417 K. Numerical results are given for He at 248, 299, 360, and 417 K (1 to 9 torr); for Ar at 298 K (1 to 4 torr); and for N2 at 299, 360, and 417 K (1 to 6 torr). Systematic errors are estimated, and identification of the reaction product is discussed. The results obtained are shown to be in excellent agreement with other recent measurements of the same rate constant.

  10. 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

  11. 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

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

    PubMed

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

  13. Contours of constant pseudo-Brewster angle in the complex ? plane and an analytical method for the determination of optical constants.

    PubMed

    Azzam, R M; Ugbo, E E

    1989-12-15

    The locus of all points in the complex plane of the dielectric function ?[?(r) + j?(i) = |?| exp(jtheta)], that represent all possible interfaces characterized by the same pseudo-Brewster angle theta(p)B of minimum p reflectance, is derived in the polar form: |?| = l cos(zeta/3), where l = 2(tan(2)Phi(p)B)k, zeta = arccos(- costheta cos(2)Phi(p)B/k(3)), and k = (1 - 2/3 sin(2)Phi(p)B)(1/2). Families of iso-Phi(p)B contours for (I) 0 degrees 80 degrees ) is the iso-Phi(p)B contour accurately approximated as a circle. We find that |?| < 1 for Phi(p)B < 37.23 degrees , and |?| > 1 for Phi(p)B > 45 degrees . The optical constants n,k (where n + jk = ?((1/2)) is the complex refractive index) are determined from the normal incidence reflectance R(0) and Phi(p)B graphically and analytically. Nomograms that consist of iso-R(0) and iso-Phi(p)B families of contours in the nk plane are presented. Equations that permit the reader to produce his own version of the same nomogram are also given. Valid multiple solutions (n,k) for a given measurement set (R(0),phi(p)B) are possible in the domain of fractional optical constants. An analytical solution of the (R(0),Phi(p)B) ? (n,k) inversion problem is developed that involves an exact (noniterative) solution of a quartic equation in |?|. Finally, a graphic representation is developed for the determination of complex ? from two pseudo-Brewster angles measured in two different media of incidence. PMID:20556031

  14. 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.

  15. 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

  16. 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.

  17. Surface-Guided Formation of an Organocobalt Complex.

    PubMed

    Weber, Peter B; Hellwig, Raphael; Paintner, Tobias; Lattelais, Marie; Paszkiewicz, Mateusz; Casado Aguilar, Pablo; Deimel, Peter S; Guo, Yuanyuan; Zhang, Yi-Qi; Allegretti, Francesco; Papageorgiou, Anthoula C; Reichert, Joachim; Klyatskaya, Svetlana; Ruben, Mario; Barth, Johannes V; Bocquet, Marie-Laure; Klappenberger, Florian

    2016-05-01

    Organocobalt complexes represent a versatile tool in organic synthesis as they are important intermediates in Pauson-Khand, Friedel-Crafts, and Nicholas reactions. Herein, a single-molecule-level investigation addressing the formation of an organocobalt complex at a solid-vacuum interface is reported. Deposition of 4,4'-(ethyne-1,2-diyl)dibenzonitrile and Co atoms on the Ag(111) surface followed by annealing resulted in genuine complexes in which single Co atoms laterally coordinated to two carbonitrile groups undergo organometallic bonding with the internal alkyne moiety of adjacent molecules. Alternative complexation scenarios involving fragmentation of the precursor were ruled out by complementary X-ray photoelectron spectroscopy. According to density functional theory analysis, the complexation with the alkyne moiety follows the Dewar-Chatt-Duncanson model for a two-electron-donor ligand where an alkyne-to-Co donation occurs together with a strong metal-to-alkyne back-donation. PMID:27059261

  18. Formation of complex bacterial colonies via self-generated vortices

    NASA Astrophysics Data System (ADS)

    Czirók, András; Ben-Jacob, Eshel; Cohen, Inon; Vicsek, Tamás

    1996-08-01

    Depending on the environmental conditions bacterial colonies growing on agar surfaces can exhibit complex colony formation and various types of collective motion. Experimental results are presented concerning the hydrodynamics (vortices, migration of bacteria in clusters) and colony formation of a morphotype of Bacillus subtilis. Some of these features are not specific to this morphotype but also have been observed in several other bacterial strains, suggesting the presence of universal effects. A simple model of self-propelled particles is proposed, which is capable of describing the hydrodynamics on the intermediate level, including the experimentally observed rotating disks of bacteria. The colony formation is captured by a complex generic model taking into account nutrient diffusion, reproduction, and sporulation of bacteria, extracellular slime deposition, chemoregulation, and inhomogeneous population. Our model also sheds light on some possible biological benefits of this ``multicellular behavior.''

  19. 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.

  20. 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.

  1. 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.

  2. Determination of apparent association constants of steroid-cyclodextrin inclusion complexes using a modification of the Hummel-Dreyer method.

    PubMed

    Flood, K G; Reynolds, E R; Snow, N H

    2001-04-13

    A modified Hummel-Dreyer method was used to calculate the apparent association constants of steroid-cyclodextrin inclusion complexes. An external calibration technique was employed, using the y-intercept from a plot of peak area versus concentration to correct for sample solvent effects. Mobile phase temperature and sample diluent organic content were found to be critical factors affecting the accuracy and reproducibility of the results. For four of six sets of data, the modified Hummel-Dreyer method yielded statistically equivalent results to another HPLC method for determining apparent association constants. Limitations of the modified Hummel-Dreyer method are discussed. In particular, the accuracy of the method is poor when measuring small apparent association constants. PMID:11355821

  3. Electromagnetic logging apparatus with button antennas for measuring the dielectric constant of formation surrounding a borehole

    SciTech Connect

    Safinya, K.A.

    1987-03-24

    This patent describes an apparatus for investigating formations surrounding a borehole, comprising: a logging device moveable through the borehole; a member mounted on the logging device for engagement with the borehole wall; a transmitting antenna mounted in the wall-engaging face of the member; a pair of spaced receiving antennas mounted in the wall-engaging face of the member in spaced relation to the transmitting antenna; each of the antennas comprising: a conductive base having a generally cylindrical recess therein which opens toward the borehole wall, a conductive rod coaxial with the recess and extending in the recess, a conductive button within the recess, mounted at the end of the rod, a dielectric material substantially filling the remainder of the recess, and a tuning element separate from the recess, the tuning element being coupled to the rod; means for energizing the transmitting antenna to transmit electromagnetic energy into the formations by applying a signal to the tuning element with respect to the base; and means for generating an output at each of the receiving antennas representative of electromagnetic energy received from the formations by obtaining a signal across the tuning element with respect to the base.

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

    SciTech Connect

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

    2015-11-02

    High-density two-dimensional electron gas (2DEG) can be formed at complex oxide interfaces such as SrTiO{sub 3}/GdTiO{sub 3} and SrTiO{sub 3}/LaAlO{sub 3}. 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 SrTiO{sub 3} 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 Schrödinger-Poisson solver in order to study its effect on the electron distribution in a 2DEG. Using the SrTiO{sub 3}/GdTiO{sub 3} 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 SrTiO{sub 3}/LaAlO{sub 3} as well as other similar interfaces.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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.

  10. 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

  11. Rosette: Understanding Star Formation in Molecular Cloud Complexes

    NASA Astrophysics Data System (ADS)

    Wang, Junfeng

    2010-09-01

    We propose Chandra imaging of three embedded clusters in the Rosette Molecular Cloud (RMC) complex. With complementary existing Spitzer and FLAMINGOS infrared surveys, the Chandra observation is critical for us to: (1) create a complete census of the young stars in the cloud; (2) study the spatial distribution of the young stars in different evolutionary stages within the RMC and the disk frequency in the embedded clusters; (3) construct X-ray Luminosity Function (XLF) and Initial Mass Function (IMF) for the clusters to examine XLF/IMF variations; (4) elucidate star formation history in this complex.

  12. The role of plasma proteins in formation of obstructive protamine complexes

    SciTech Connect

    De Paulis, R.; Mohammad, S.F.; Chiariello, L.; Morea, M.; Olsen, D.B. )

    1991-06-01

    Formation of complexes between heparin and protamine (in saline), or heparin, plasma proteins, and protamine (in plasma) was assessed by measurements of light transmission through different test solutions. To examine the formation of these complexes, 125I-labeled protamine was used. Addition of 125I-protamine to plasma or blood resulted in the sedimentation of 125I-protamine in the form of insoluble complexes. This complex formation was not affected by the presence of heparin, suggesting that protamine-plasma protein interaction may be primarily responsible for precipitation of 125I-protamine. To assess the capability of these complexes to obstruct the pulmonary circulation, an in vitro experimental model was developed. Citrated serum, plasma, blood, or saline were allowed to flow through a glass bead column with the help of a peristaltic pump. A pressure transducer positioned before the column allowed pressure measurements at a constant flow rate during the experiment. Mixing of protamine with plasma or blood prior to their passage through the glass bead column resulted in a significant increase in pressure suggesting that the column was being clogged with insoluble complexes. The increase in pressure occurred both in the presence and absence of heparin in plasma or blood. Under identical experimental conditions, the increase in pressure was insignificant when protamine was added to saline or serum regardless of whether heparin was present or absent. This was further confirmed by the use of 125I-protamine. These observations suggest that protamine forms insoluble complexes with certain plasma proteins. Based on these observations, it is hypothesized that following intravenous administration, protamine immediately forms complexes in circulating blood.

  13. Complexes of horseradish peroxidase with formate, acetate, and carbon monoxide.

    PubMed

    Carlsson, Gunilla H; Nicholls, Peter; Svistunenko, Dimitri; Berglund, Gunnar I; Hajdu, Janos

    2005-01-18

    Carbon monoxide, formate, and acetate interact with horseradish peroxidase (HRP) by binding to subsites within the active site. These ligands also bind to catalases, but their interactions are different in the two types of enzymes. Formate (notionally the "hydrated" form of carbon monoxide) is oxidized to carbon dioxide by compound I in catalase, while no such reaction is reported to occur in HRP, and the CO complex of ferrocatalase can only be obtained indirectly. Here we describe high-resolution crystal structures for HRP in its complexes with carbon monoxide and with formate, and compare these with the previously determined HRP-acetate structure [Berglund, G. I., et al. (2002) Nature 417, 463-468]. A multicrystal X-ray data collection strategy preserved the correct oxidation state of the iron during the experiments. Absorption spectra of the crystals and electron paramagnetic resonance data for the acetate and formate complexes in solution correlate electronic states with the structural results. Formate in ferric HRP and CO in ferrous HRP bind directly to the heme iron with iron-ligand distances of 2.3 and 1.8 A, respectively. CO does not bind to the ferric iron in the crystal. Acetate bound to ferric HRP stacks parallel with the heme plane with its carboxylate group 3.6 A from the heme iron, and without an intervening solvent molecule between the iron and acetate. The positions of the oxygen atoms in the bound ligands outline a potential access route for hydrogen peroxide to the iron. We propose that interactions in this channel ensure deprotonation of the proximal oxygen before binding to the heme iron. PMID:15641789

  14. 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

  15. 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

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. Klebsiella pneumoniae nitrogenase: formation and stability of putative beryllium fluoride-ADP transition state complexes.

    PubMed

    Clarke, T A; Yousafzai, F K; Eady, R R

    1999-08-01

    Incubation of the MoFe protein (Kp1) and Fe protein (Kp2), the component proteins of Klebsiella pneumoniae nitrogenase, with BeF(3)(-) and MgADP resulted in a progressive inhibition of nitrogenase activity. We have shown that at high Kp2 to Kp1 molar ratios this inhibition is due to the formation of an inactive complex with a stoichiometry corresponding to Kp1.{Kp2.(MgADP.BeFx)2}2. At lower Kp2:Kp1 ratios, an equilibrium between this 2:1 complex, the partially active 1:1 Kp1.Kp2.(MgADP. BeFx)2 complex, and active nitrogenase components was demonstrated. The inhibition was reversible since incubation of the 1:1 complex in the absence of MgADP and beryllium resulted in complete restoration of activity over 30 h. Under pseudo-first-order conditions with regard to nitrogenase components and MgADP, the kinetics of the rate of inhibition with increasing concentrations of BeF(3)(-) showed a square dependence on [BeF(3)(-)], consistent with the binding of two Be atoms by Kp2 in the complex. Analytical fplc gel filtration profiles of Kp1.Kp2 incubation mixtures at equilibrium resolved the 2:1 complex and the 1:1 complex from free Kp1. Deconvolution of the equilibrium profiles gave concentrations of the components allowing constants for their formation of 2.1 x 10(6) and 5.6 x 10(5) M(-1) to be calculated for the 1:1 and 2:1 complexes, respectively. When the active site concentration of the different species was taken into account, values for the two constants were the same, indicating the two binding sites for Kp2 are the same for Kp1 with one or both sites unoccupied. The value for K(1) we obtain from this study is comparable with the value derived from pre-steady-state studies of nitrogenase. Analysis of the elution profile obtained on gel filtration of a 1:1 ratio incubation mixture containing 20 microM nitrogenase components showed 97% of the Kp2 present initially to be complexed. These data provide the first unequivocal demonstration that Fe protein preparations which may contain up to 50% of a species of Fe protein defective in electron transfer is nevertheless fully competent in complex formation with MoFe protein. PMID:10433697

  1. Complex formation between polyelectrolytes and oppositely charged oligoelectrolytes.

    PubMed

    Zhou, Jiajia; Barz, Matthias; Schmid, Friederike

    2016-04-28

    We study the complex formation between one long polyanion chain and many short oligocation chains by computer simulations. We employ a coarse-grained bead-spring model for the polyelectrolyte chains and model explicitly the small salt ions. We systematically vary the concentration and the length of the oligocation and examine how the oligocations affects the chain conformation, the static structure factor, the radial and axial distribution of various charged species, and the number of bound ions in the complex. At low oligocation concentration, the polyanion has an extended structure. Upon increasing the oligocation concentration, the polyanion chain collapses and forms a compact globule, but the complex still carries a net negative charge. Once the total charge of the oligocations is equal to that of the polyanion, the collapse stops and is replaced by a slow expansion. In this regime, the net charge on the complexes is positive or neutral, depending on the microion concentration in solution. The expansion can be explained by the reduction of the oligocation bridging. We find that the behavior and the structure of the complex are largely independent of the length of oligocations, and very similar to that observed when replacing the oligocations by multivalent salt cations, and conclude that the main driving force keeping the complex together is the release of monovalent counterions and coions. We speculate on the implications of this finding for the problem of controlled oligolyte release and oligolyte substitution. PMID:27131564

  2. Complex formation between polyelectrolytes and oppositely charged oligoelectrolytes

    NASA Astrophysics Data System (ADS)

    Zhou, Jiajia; Barz, Matthias; Schmid, Friederike

    2016-04-01

    We study the complex formation between one long polyanion chain and many short oligocation chains by computer simulations. We employ a coarse-grained bead-spring model for the polyelectrolyte chains and model explicitly the small salt ions. We systematically vary the concentration and the length of the oligocation and examine how the oligocations affects the chain conformation, the static structure factor, the radial and axial distribution of various charged species, and the number of bound ions in the complex. At low oligocation concentration, the polyanion has an extended structure. Upon increasing the oligocation concentration, the polyanion chain collapses and forms a compact globule, but the complex still carries a net negative charge. Once the total charge of the oligocations is equal to that of the polyanion, the collapse stops and is replaced by a slow expansion. In this regime, the net charge on the complexes is positive or neutral, depending on the microion concentration in solution. The expansion can be explained by the reduction of the oligocation bridging. We find that the behavior and the structure of the complex are largely independent of the length of oligocations, and very similar to that observed when replacing the oligocations by multivalent salt cations, and conclude that the main driving force keeping the complex together is the release of monovalent counterions and coions. We speculate on the implications of this finding for the problem of controlled oligolyte release and oligolyte substitution.

  3. DNA-histidine complex formation in isoelectric histidine buffers.

    PubMed

    Stellwagen, N C; Gelfi, C; Righetti, P G

    1999-04-01

    The free solution electrophoretic mobility of two DNA molecules of different molecular masses, 18 base pairs and 2686 base pairs, has been measured in isoelectric histidine buffers with and without added low-molecular-mass electrolytes. Extensive DNA-histidine complex formation is observed in isoelectric histidine buffer, as evidenced by distortion and splitting of the peaks in the electropherograms. Peak distortion and splitting can be decreased or eliminated by adding low-molecular-mass neutral salts to the solution, suggesting that the DNA-histidine complexes are stabilized by electrostatic interactions. The ability of various neutral salts to disrupt the DNA-histidine complexes depends on the molecular mass of the DNA and the concentration and type of added salt. PMID:10327637

  4. 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).

  5. 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.

  6. Mercury(II) Penicillamine Complex Formation in Alkaline Aqueous Solution

    SciTech Connect

    Leung, B.O.; Jalilehvand, F.; Mah, V.

    2009-06-01

    The complex formation between mercury(II) and penicillamine (H{sub 2}Pen = 3,3'-dimethyl cysteine) in alkaline aqueous solutions (pH {approx}2) has been investigated with extended X-ray absorption fine structure (EXAFS) and {sup 199}Hg NMR spectroscopy. By varying the penicillamine concentration (C{sub H{sub 2}Pen} = 0.2--1.25 M) in {approx}0.1 M Hg(II) solutions, two coexisting major species [Hg(Pen){sub 2}]{sup 2-} and [Hg(Pen){sub 3}]{sub 4-} were characterized with mean Hg-S bond distances 2.34(2) and 2.44(2) {angstrom}, respectively. The [Hg(Pen){sub 2}]{sup 2-} complex with two deprotonated penicillamine ligands forms an almost linear S-Hg-S entity with two weak chelating Hg-N interactions at the mean Hg-N distance 2.52(2) {angstrom}. The same type of coordination is also found for the corresponding [Hg(Cys){sub 2}]{sup 2-} complex in alkaline aqueous solution with the mean bond distances Hg-S 2.34(2) {angstrom} and Hg-N 2.56(2) {angstrom}. The relative amounts of the [Hg(Pen){sub 2}]{sup 2-} and [Hg(Pen){sub 3}]{sup 4-} complexes were estimated by fitting linear combinations of the EXAFS oscillations to the experimental spectra. Also their {sup 199}Hg NMR chemical shifts were used to evaluate the complex formation, showing that the [Hg(Pen){sub 3}]{sup 4-} complex dominates already at moderate excess of the free ligand ([Pen{sup 2-}] > {approx} 0.1 M).

  7. Stoichiometry and conditional stability constants of Cu(II) or Zn(II) clioquinol complexes; implications for Alzheimer's and Huntington's disease therapy.

    PubMed

    Ferrada, Evandro; Arancibia, Verónica; Loeb, Bárbara; Norambuena, Ester; Olea-Azar, Claudio; Huidobro-Toro, J Pablo

    2007-05-01

    Successful trials with 5-chloro-7-iodo-8-hydroxyquinoline (clioquinol, CQ) for Alzheimer's disease treatment prompted renewed interest in assessing whether its therapeutic action is related to the coordination of neurotoxic trace metals, such as Cu(II) and Zn(II). We now report conditional stability constants (K(C')) for CQ Cu(II) and Zn(II) complexes measured in a biological buffer containing Ca(II) and Mg(II) ions. UV-vis spectroscopy and polarography evidenced a 1:2 stoichiometry of Cu(II) and Zn(II) CQ complexes; the K(C')s calculated were: Cu(CQ)(2) 1.2x10(10), and Zn(CQ)(2) 7.0x10(8)M(-2); the CQ affinity for Cu(II) is at least an order of magnitude higher than for Zn(II). To test the possible functional relevance of the Cu(II) CQ complexes in the brain, we bioassayed free Cu(II) concentration by the metal-induced inhibition of ATP-gated currents of the P2X(4) receptor, a predominant brain P2X receptor. CQ reduced concentration-dependently the Cu(II) inhibition of the ATP-gated currents. In view that the stability constant of CQ for Zn(II) is similar to that of Abeta-amyloid for Zn(II), and the fact that CQ may form complexes with Cu(II), even in the presence of competing ions, the present results highlight that the formation of Cu(II) CQ complexes in the brain may act by diminishing free Cu(II) concentrations modifying thereby brain excitability, or favoring the degradation of beta-amyloid plaques or huntingtin, rather than through a specific effect of CQ itself. PMID:17382398

  8. Assessing the formation of weak sodium complexes with negatively charged ligands.

    PubMed

    Berto, S; Chiavazza, E; Canepa, P; Prenesti, E; Daniele, P G

    2016-05-14

    The stability of sodium complexes with poly-carboxylic and polyamino-carboxylic acids is investigated with ion-selective electrode-Na(+) potentiometry, working at strictly constant ionic strength. It is observed that the formation constants of the Na(+) complexes with monoligand stoichiometry (ML) increase with the number of charges on the ligand. For example, in poly-carboxylic acids this dependency is linear and is well captured by an experimental equation. A different behaviour is observed for the poly-amino carboxylic acids, which show higher complexation capabilities reaching a plateau of the binding energy past a specific ligand size. The experimental results are discussed qualitatively using ab initio calculations based on DFT B3LYP, and the principal electronic characteristics of the ligands under investigation are identified. As a result of the flexibility imparted by the long chains of polyamino-carboxylic ligands, both experimental and theoretical models demonstrate that nitrogen atoms in proximity of Na(+) ions can participate in the metal coordination, thus providing further stabilization for the complexes. Moreover, by increasing the ligand size the stabilization gained in terms of ΔG reached a plateau for EDTA, in agreement with experimental observations. PMID:27113137

  9. 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.

  10. Titanium complex formation of organic ligands in titania gels.

    PubMed

    Nishikiori, Hiromasa; Todoroki, Kenta; Setiawan, Rudi Agus; Teshima, Katsuya; Fujii, Tsuneo; Satozono, Hiroshi

    2015-01-27

    Thin films of organic ligand-dispersing titania gels were prepared from titanium alkoxide sols containing ligand molecules by steam treatment without heating. The formation of the ligand-titanium complex and the photoinduced electron transfer process in the systems were investigated by photoelectrochemical measurements. The complex was formed between the 8-hydroxyquinoline (HQ) and titanium species, such as the titanium ion, on the titania nanoparticle surface through the oxygen and nitrogen atoms of the quinolate. A photocurrent was observed in the electrodes containing the complex due to the electron injection from the LUMO of the complex into the titania conduction band. A bidentate ligand, 2,3-dihydroxynaphthalene (DHN), formed the complex on the titania surface through dehydration between its two hydroxyl groups of DHN and two TiOH groups of the titania. The electron injection from the HOMO of DHN to the titania conduction band was observed during light irradiation. This direct electron injection was more effective than the two-step electron injection. PMID:25535798

  11. 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

  12. Monolayer kinetic model of formation of β-cyclodextrin-β-carotene inclusion complex.

    PubMed

    Ivanova, Tz; Mircheva, K; Balashev, K; Panaiotov, I; Boury, F

    2015-11-01

    The carotenoids are sensitive molecules and their chemical integrity must be preserved from pro-oxidant elements which could affect and decrease their physiological benefits. The encapsulation based on the inclusion of the carotenoids into cage molecules is a promising approach for preserving over time of the intrinsic properties of the carotenoids. It is well known that cyclic oligosaccharide β-cyclodextrin (CD) as a cage molecule possesses strong inclusion ability to β-carotene (C) and as a result of the hydrophobic interactions forms an inclusion complex. In the present paper a monolayer kinetic model was established with the notion to extract more information about the influence of the molecular structure and organization to the interfacial interactions between the interacting species as well as about the role of the specific areas, which are often underestimated in previously studied dispersed systems. We developed the monolayer kinetic model for the formation of the inclusion CD-C complex by applying an experimental approach for following the kinetics by means of measuring the decrease of the surface area (ΔA) versus time (t) at constant surface pressure (π) and the decrease of surface pressure (π) versus time (t) at constant surface area (A). We also visualized by AFM the state of the monolayers at the initial and end points of the kinetic process. The values for the degree (d) and constant (Ka) of the association were estimated and compared with those from the studies of dispersed systems. PMID:26299748

  13. 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

  14. 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

  15. 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.

  16. Formation and Redox Interconversion of Niobium Methylidene and Methylidyne Complexes.

    PubMed

    Searles, Keith; Smith, Kyle T; Kurogi, Takashi; Chen, Chun-Hsing; Carroll, Patrick J; Mindiola, Daniel J

    2016-06-01

    The niobium methylidene [{(Ar'O)2 Nb}2 (μ2 -Cl)2 (μ2 -CH2 )] (2) can be cleanly prepared via thermolysis or photolysis of [(Ar'O)2 Nb(CH3 )2 Cl] (1) (OAr'=2,6-bis(diphenylmethyl)-4-tert-butylphenoxide). Reduction of 2 with two equivalents of KC8 results in formation of the first niobium methylidyne [K][{(Ar'O)2 Nb}2 (μ2 -CH)(μ2 -H)(μ2 -Cl)] (3) via a binuclear α-hydrogen elimination. Oxidation of 3 with two equiv of ClCPh3 reforms 2. In addition to solid state X-ray analysis, all these complexes were elucidated via multinuclear NMR experiments and isotopic labelling studies, including a crossover experiment, support the notion for a radical mechanism as well as a binuclear α-hydrogen abstraction pathway being operative in the formation of 2 from 1. PMID:27110689

  17. Theoretical calculations of stability constants and pKa values of metal complexes in solution: application to pyridoxamine-copper(II) complexes and their biological implications in AGE inhibition.

    PubMed

    Casasnovas, Rodrigo; Ortega-Castro, Joaquín; Donoso, Josefa; Frau, Juan; Muñoz, Francisco

    2013-10-14

    Accurate prediction of thermodynamic constants of chemical reactions in solution is one of the current challenges in computational chemistry. We report a scheme for predicting stability constants (log β) and pKa values of metal complexes in solution by means of calculating free energies of ligand- and proton-exchange reactions using Density Functional Theory calculations in combination with a continuum solvent model. The accuracy of the predicted log β and pKa values (mean absolute deviations of 1.4 and 0.2 units respectively) is equivalent to the experimental uncertainties. This theoretical methodology provides direct knowledge of log β and pKa values of major and minor species, so it is of potential use in combination with experimental techniques to obtain a detailed description of the microscopic equilibria. In particular, the proposed methodology is shown to be especially useful for obtaining the real acidity constants of those chelates where the metal-ligand coordination changes as a result of ligand deprotonation. The stability and acidity constants of pyridoxamine-Cu(2+) chelates calculated with the proposed methodology show that pyridoxamine is an efficient scavenging agent of Cu(2+) under physiological pH conditions. This is of special interest as Cu(2+) overload is involved in the formation of advanced glycation end-products (AGEs) and their associated degenerative medical conditions. PMID:23999915

  18. 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

  19. Electron-exciton complex formation in organic solids

    NASA Astrophysics Data System (ADS)

    Bader, G.; Caron, L.; Sanche, L.

    1981-06-01

    Sharp structure in the doubly differentiated electron transmission spectra of thin (≅ 150 Å) benzene films is shown to result from electron-exciton complex formation. The large energy shift between the electronic energy levels of the molecule and the transmission maxima is related to the electron binding energy. This is due to the polarizability difference between the Frenkel exciton and the organic molecule. From a simple Wigner-Seitz model, we show that the captured electron is localized between the exciton and the sorrounding molecules.

  20. 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.

  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. 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

  3. 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.

  4. 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.

  5. 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

  6. Interference-mediated synaptonemal complex formation with embedded crossover designation.

    PubMed

    Zhang, Liangran; Espagne, Eric; de Muyt, Arnaud; Zickler, Denise; Kleckner, Nancy E

    2014-11-25

    Biological systems exhibit complex patterns at length scales ranging from the molecular to the organismic. Along chromosomes, events often occur stochastically at different positions in different nuclei but nonetheless tend to be relatively evenly spaced. Examples include replication origin firings, formation of chromatin loops along chromosome axes and, during meiosis, localization of crossover recombination sites ("crossover interference"). We present evidence in the fungus Sordaria macrospora that crossover interference is part of a broader pattern that includes synaptonemal complex (SC) nucleation. This pattern comprises relatively evenly spaced SC nucleation sites, among which a subset are crossover sites that show a classical interference distribution. This pattern ensures that SC forms regularly along the entire length of the chromosome as required for the maintenance of homolog pairing while concomitantly having crossover interactions locally embedded within the SC structure as required for both DNA recombination and structural events of chiasma formation. This pattern can be explained by a threshold-based designation and spreading interference process. This model can be generalized to give diverse types of related and/or partially overlapping patterns, in two or more dimensions, for any type of object. PMID:25380597

  7. 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.

  8. Comprehensive Simulations of Interstellar Ice Formation and Complex Molecule Chemistry

    NASA Astrophysics Data System (ADS)

    Garrod, Robin

    Interstellar ices are present in both quiscent and star-forming regions, and contain a selection of simple organic species. These ices are widely thought to be the progenitors of the highly complex organic molecules observed in the gas phase in high-mass star- forming regions. They are also believed to be the precursors of planetary and cometary material, and may contribute important pre-biotic, and perhaps biotic, components. The formation and processing of interstellar ices is therefore of great relevance to the origins of complex biological molecules and the development of life. The upcoming James Webb Space Telescope will place an even greater focus on these topics through its unparalleled infrared spectroscopic instruments. Furthermore, the new ALMA telescope is expected in the coming years to produce discoveries of yet larger molecules, including those of biological significance, such as amino acids. However, the accurate interpretation of observational infrared ice data is severely hampered by the inadequacy of current computational models of coupled grain-surface and gas-phase chemistry. Current astrochemical models either use a simplistic treatment of ice chemistry, ignoring a number of important processes and overlooking stochastic chemical kinetic behaviour; or they remove the gas-phase chemistry entirely, modeling a simple grain chemistry network. In both cases, a uniform representative dust-grain population is assumed. Typical coupled gas-phase/grain-surface chemical models deal with surface chemistry, but do not distinguish between the surface and the bulk ices beneath, or between layers within the ices; recent experimental and theoretical studies demonstrate these structural characteristics to be highly influential. These simplifications and inaccuracies make our understanding of interstellar complex-molecule and ice formation highly approximate. Observations are thus difficult to explain, and model-based predictions are imprecise. The development of a comprehensive chemical model is proposed, for the accurate simulation of coupled gas-phase, grain-surface, and ice-mantle chemistry. Progressing from the PI's current code, the new model will explicitly treat chemistry within individual layers in the ices, and will adopt a range of dust-grain sizes, allowing observed ice compositions to be explained as an aggregate of layers and grain sizes with varying ice compositions. The model will adopt the PI's new computational method that allows fast, accurate simulation of stochastic surface processes, and will incorporate the most recent ice data from experimental/modeling studies, obtained in part by the PI. The current complex chemical network will be extended to include plausible biotic/pre-biotic molecules, including simple amino acids such as glycine. The model will be applied to a range of dynamically-evolving environments, and will trace a continuous timeline from the formation and processing of interstellar ices to the production of complex organic molecules, their evaporation, and their behavior in the gas phase. The use of a comprehensive coupled gas-phase/ice model will allow current observational results in both chemical phases (i.e. infra-red and mm/sub-mm data) to be understood in a complementary and quantitative way within individual astronomical objects. The proposed model will further our understanding of the genesis of biologically relevant organic molecules in space, and the role played in this process by granular ices, at each stage of molecular cloud evolution and star formation. A strong emphasis will be placed on making useful predictions of molecular abundances for observational astronomy with the upcoming JWST telescope, and with ALMA. The development of an accurate, and flexible, chemical model constitutes a key step in the preparation for these new telescopes, and will be crucial to fully exploit the new data that they produce.

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

    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 37°C are determined potentiometrically. The chemical equilibria in the system are simulated and the stoichiometry of formation of the complex forms is determined.

  10. Cadmium(II) Complex Formation with Cysteine and Penicillamine

    PubMed Central

    Jalilehvand, Farideh; Leung, Bonnie O.; Mah, Vicky

    2009-01-01

    The complex formation between cadmium(II) and the ligands cysteine (H2Cys) or penicillamine (H2Pen = 3, 3′-dimethylcysteine) in aqueous solutions, containing CCd(II) ∼ 0.1 mol dm-3 and CH2L = 0.2 – 2 mol dm-3, was studied at pH = 7.5 and 11.0 by means of 113Cd-NMR and Cd K- and L3-edge X-ray absorption spectroscopy. For all cadmium(II)-cysteine mole ratios the mean Cd-S and Cd-(N/O) bond distances were found in the ranges 2.52 – 2.54 Å and 2.27 – 2.35 Å, respectively. The corresponding cadmium(II)-penicillamine complexes showed slightly shorter Cd-S bonds, 2.50 – 2.53 Å, but with the Cd-(N/O) bond distances in a similar wide range, 2.28 – 2.33 Å. For the mole ratio CH2L / CCd(II) = 2, the 113Cd chemical shifts, in the range 509 – 527 ppm at both pH values, indicated complexes with distorted tetrahedral CdS2N(N/O) coordination geometry. With a large excess of cysteine (mole ratios CH2Cys / CCd(II) ≥ 10) complexes with CdS4 coordination geometry dominate, consistent with the 113Cd NMR chemical shifts, δ ∼ 680 ppm at pH 7.5 and 636 - 658 ppm at pH 11.0, and their mean Cd-S distances of 2.53 ± 0.02 Å. At pH 7.5, the complexes are almost exclusively sulfur-coordinated as [Cd(S-cysteinate)4]n-, while at higher pH the deprotonation of the amine groups promotes chelate formation, and at pH 11.0 a minor amount of the [Cd(Cys)3]4- complex with CdS3N coordination is formed. For the corresponding penicillamine solutions with mole ratios CH2Pen / CCd(II) ≥ 10, the 113Cd-NMR chemical shifts, δ ∼ 600 ppm at pH 7.5 and 578 ppm at pH 11.0, together with the average bond distances Cd-S 2.53 ± 0.02 Å and Cd-O 2.30 – 2.33 Å, indicate that [Cd(penicillaminate)3]n- complexes with chelating CdS3(N/O) coordination dominate already at pH 7.5, and become mixed with CdS2N(N/O) complexes at pH 11.0. The present study reveals differences between cysteine and penicillamine as ligands to the cadmium(II) ion that can explain why cysteine-rich metallothionines are capable of capturing cadmium(II) ions, while penicillamine, clinically useful for treating the toxic effects of mercury(II) and lead(II) exposure, is not efficient against cadmium(II) poisoning. PMID:19469490

  11. Cadmium(II) complex formation with cysteine and penicillamine.

    PubMed

    Jalilehvand, Farideh; Leung, Bonnie O; Mah, Vicky

    2009-07-01

    The complex formation between cadmium(II) and the ligands cysteine (H(2)Cys) and penicillamine (H(2)Pen = 3,3'-dimethylcysteine) in aqueous solutions, having C(Cd(II)) approximately 0.1 mol dm(-3) and C(H(2)L) = 0.2-2 mol dm(-3), was studied at pH = 7.5 and 11.0 by means of (113)Cd NMR and Cd K- and L(3)-edge X-ray absorption spectroscopy. For all cadmium(II)-cysteine molar ratios, the mean Cd-S and Cd-(N/O) bond distances were found in the ranges 2.52-2.54 and 2.27-2.35 A, respectively. The corresponding cadmium(II)-penicillamine complexes showed slightly shorter Cd-S bonds, 2.50-2.53 A, but with the Cd-(N/O) bond distances in a similar wide range, 2.28-2.33 A. For the molar ratio C(H(2)L)/C(Cd(II)) = 2, the (113)Cd chemical shifts, in the range 509-527 ppm at both pH values, indicated complexes with distorted tetrahedral CdS(2)N(N/O) coordination geometry. With a large excess of cysteine (molar ratios C(H(2)Cys)/C(Cd(II)) >or= 10), complexes with CdS(4) coordination geometry dominate, consistent with the (113)Cd NMR chemical shifts, delta approximately 680 ppm at pH 7.5 and 636-658 ppm at pH 11.0, and their mean Cd-S distances were 2.53 +/- 0.02 A. At pH 7.5, the complexes are almost exclusively sulfur-coordinated as [Cd(S-cysteinate)(4)](n-), while at higher pH, the deprotonation of the amine groups promotes chelate formation. At pH 11.0, a minor amount of the [Cd(Cys)(3)](4-) complex with CdS(3)N coordination is formed. For the corresponding penicillamine solutions with molar ratios C(H(2)Pen)/C(Cd(II)) >or= 10, the (113)Cd NMR chemical shifts, delta approximately 600 ppm at pH 7.5 and 578 ppm at pH 11.0, together with the average bond distances, Cd-S 2.53 +/- 0.02 A and Cd-(N/O) 2.30-2.33 A, indicate that [Cd(penicillaminate)(3)](n-) complexes with chelating CdS(3)(N/O) coordination dominate already at pH 7.5 and become mixed with CdS(2)N(N/O) complexes at pH 11.0. The present study reveals differences between cysteine and penicillamine as ligands to the cadmium(II) ion that can explain why cysteine-rich metallothionines are capable of capturing cadmium(II) ions, while penicillamine, clinically useful for treating the toxic effects of mercury(II) and lead(II) exposure, is not efficient against cadmium(II) poisoning. PMID:19469490

  12. 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)-κ-, κ/β-, λ-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 κ-CG and κ/β-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 κ-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

  13. 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

  14. 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

  15. 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.

  16. Formation of Cluster Complexes by Cluster-Cluster-Collisions

    NASA Astrophysics Data System (ADS)

    Ichihashi, Masahiko; Odaka, Hideho

    2015-03-01

    Multi-element clusters are interested in their chemical and physical properties, and it is expected that they are utilized as catalysts, for example. Their properties critically depend on the size, composition and atomic ordering, and it should be important to adjust the above parameters for their functionality. One of the ways to form a multi-element cluster is to employ a low-energy collision between clusters. Here, we show characteristic results obtained in the collision between a neutral Ar cluster and a size-selected Co cluster ion. Low-energy collision experiment was accomplished by using a newly developed merging-beam apparatus. Cobalt cluster ions were produced by laser ablation, and mass-selected. On the other hand, argon clusters were prepared by the supersonic expansion of Ar gas. Both cluster beams were merged together in an ion guide, and ionic cluster complexes were mass-analyzed. In the collision of Co2+ and ArN, Co2Arn+ (n = 1 - 30) were observed, and the total intensity of Co2Arn+ (n >= 1) is inversely proportional to the relative velocity between Co2+ and ArN. This suggests that the charge-induced dipole interaction between Co2+ and a neutral Ar cluster is dominant in the formation of the cluster complex, Co2+Arn.

  17. Refined theoretical study of radiative association: Cross sections and rate constants for the formation of SiN

    NASA Astrophysics Data System (ADS)

    Gustafsson, Magnus; Antipov, Sergey V.; Franz, Jan; Nyman, Gunnar

    2012-09-01

    Radiative association of silicon mononitride (SiN) in its two lowest molecular electronic states is studied through quantum and classical dynamics. Special attention is paid to the behavior of the cross section at high collision energies. A modified expression for the semiclassical cross section is presented which excludes transitions to continuum states. This gives improved agreement with quantum mechanical perturbation theory at high energies. The high energy cross section is overestimated if conventional semiclassical theory is used. The modified semiclassical theory should be valid in general for radiative association transitions from an upper to a lower electronic state. We also implement a quantum dynamical optical potential method with the same type of modification. The rate coefficient is calculated using Breit-Wigner theory and the modified semiclassical formula for the resonance and direct contributions, respectively, for temperatures from 10 K to 20 000 K. A rapid decrease in the rate constant for formation of ground state SiN is observed above 2000 K which was not seen previously.

  18. Modelling formation of complex topography by the seagrass Posidonia oceanica

    NASA Astrophysics Data System (ADS)

    Kendrick, Gary A.; Marbà, Núria; Duarte, Carlos M.

    2005-12-01

    Posidonia oceanica is a slow growing seagrass species that extends via growing rhizomes that grow only centimetres both horizontally and vertically each year. Posidonia oceanica forms topographically complex biogenic reefs of dead rhizome and sediments that are up to 4 m in height that are called "matte". This study investigates the role of slow horizontal and vertical growth of rhizomes in the formation of topographic complexity in P. oceanica matte using agent-based modelling. The simulated infilling of landscapes by P. oceanica was run over 600 iterations (years) for 10 random starts of 150 agents each. Initial infilling rates were very slow and P. oceanica had limited cover after a century of growth. Growth accelerated after 100 years but plateaued after 400 years such that after 600 years only two-thirds of the landscape was occupied by P. oceanica. The pattern of spread of agents was initially random in direction but after larger patches were formed spread was radial from these patches. The seagrass landscape was initially highly fragmented with many small separate patches made up of a few agents each, with a Landscape Division index close to 1. Between 300 and 600 years Landscape Division declined sharply to 0.42, indicating patches had coalesced into larger more continuous meadows forming a less fragmented landscape. Perimeter to area ratio of seagrass patches declined exponentially from >1 to approximately 0.2 over 600 years of simulation. The matte developed from growth of patches and its greatest height occurred in more continuously occupied cells of the grid. The topography of the reef that occupied two-thirds of the landscape after six centuries of growth could be described as a pattern of channels between reef plateaus elevated 1-2 m above channels. These results demonstrate that development in P. oceanica meadows of three-dimensional structure, in the formation of biogenic reefs, can be explained by, and is an emergent property of, slow horizontal and vertical rhizome growth rates combined with the time it takes for the accumulation of rhizomes in any region of the landscape. As such, the model provides a parsimonious explanation for the development of complex matte topography.

  19. 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

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

    PubMed Central

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

    2012-01-01

    Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO3) using a potentiometric technique. The order of –ΔG0 and –ΔH0 was found to obey Co2+ < Ni2+ < Cu2+ > Zn2+, in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K. PMID:23226992

  1. 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

  2. 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.

  3. 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

  4. Density functional theory study on aqueous aluminum-fluoride complexes: exploration of the intrinsic relationship between water-exchange rate constants and structural parameters for monomer aluminum complexes.

    PubMed

    Jin, Xiaoyan; Qian, Zhaosheng; Lu, Bangmei; Yang, Wenjing; Bi, Shuping

    2011-01-01

    Density functional theory (DFT) calculation is carried out to investigate the structures, (19)F and (27)Al NMR chemical shifts of aqueous Al-F complexes and their water-exchange reactions. The following investigations are performed in this paper: (1) the microscopic properties of typical aqueous Al-F complexes are obtained at the level of B3LYP/6-311+G**. Al-OH(2) bond lengths increase with F(-) replacing inner-sphere H(2)O progressively, indicating labilizing effect of F(-) ligand. The Al-OH(2) distance trans to fluoride is longer than other Al-OH(2) distance, accounting for trans effect of F(-) ligand. (19)F and (27)Al NMR chemical shifts are calculated using GIAO method at the HF/6-311+G** level relative to F(H(2)O)(6)(-) and Al(H(2)O)(6)(3+) references, respectively. The results are consistent with available experimental values; (2) the dissociative (D) activated mechanism is observed by modeling water-exchange reaction for [Al(H(2)O)(6-i)F(i)]((3-i)+) (i = 1-4). The activation energy barriers are found to decrease with increasing F(-) substitution, which is in line with experimental rate constants (k(ex)). The log k(ex) of AlF(3)(H(2)O)(3)(0) and AlF(4)(H(2)O)(2)(-) are predicted by three ways. The results indicate that the correlation between log k(ex) and Al-O bond length as well as the given transmission coefficient allows experimental rate constants to be predicted, whereas the correlation between log k(ex) and activation free energy is poor; (3) the environmental significance of this work is elucidated by the extension toward three fields, that is, polyaluminum system, monomer Al-organic system and other metal ions system with high charge-to-radius ratio. PMID:21133367

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. Complex formation of a calcium-dependent antibody: a thermodynamical consideration.

    PubMed

    Einhauer, Adelheid; Jungbauer, Alois

    2003-08-15

    The elution of FLAG-fusions (an octapeptide with the sequence DYKDDDDK) from immobilized anti-FLAG antibody M1 cannot be explained by a switch of the equilibrium binding constant to a lower value. To get a further insight into thermodynamics, the binding of anti-FLAG antibody M1 to the FLAG peptide was studied by real-time biosensor technology at seven different temperatures in the range from 5 to 35 degrees C. Binding studies were performed in the presence and absence of calcium. Thermodynamic parameters such as change in Gibbs free energy (deltaG), enthalpy (deltaH) and entropy (deltaS) were evaluated from the corresponding equilibrium data applying the integrated Van't Hoff equation. In contrast to similar kinetic data obtained, the contribution of deltaH and deltaS to deltaG in the presence or absence of calcium results in a different conformation of the antibody-antigen complex under binding and non-binding conditions. Therefore, complex dissociation with EDTA must be effected during a transition state of complex formation and dissociation. PMID:13677647

  12. 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)

  13. 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)

  14. Absorption spectrometric study of charge transfer complex formation between 4-acetamidophenol (paracetamol) and a series of quinones including Vitamin K 3

    NASA Astrophysics Data System (ADS)

    Saha, Avijit; Mukherjee, Asok K.

    2004-07-01

    The formation of charge transfer (CT) complexes of 4-acetamidophenol (commonly called 'paracetamol') and a series of quinones (including Vitamin K 3) has been studied spectrophotometrically in ethanol medium. The vertical ionisation potential of paracetamol and the degrees of charge transfer of the complexes in their ground state has been estimated from the trends in the charge transfer bands. The oscillator and transition dipole strengths of the complexes have been determined from the CT absorption spectra at 298 K. The complexes have been found by Job's method of continuous variation to have the uncommon 2:1 (paracetamol:quinone) stoichiometry in each case. The enthalpies and entropies of formation of the complexes have been obtained by determining their formation constants at five different temperatures.

  15. Absorption spectrometric study of charge transfer complex formation between 4-acetamidophenol (paracetamol) and a series of quinones including vitamin K3.

    PubMed

    Saha, Avijit; Mukherjee, Asok K

    2004-07-01

    The formation of charge transfer (CT) complexes of 4-acetamidophenol (commonly called 'paracetamol') and a series of quinones (including Vitamin K3) has been studied spectrophotometrically in ethanol medium. The vertical ionisation potential of paracetamol and the degrees of charge transfer of the complexes in their ground state has been estimated from the trends in the charge transfer bands. The oscillator and transition dipole strengths of the complexes have been determined from the CT absorption spectra at 298 K. The complexes have been found by Job's method of continuous variation to have the uncommon 2:1 (paracetamol:quinone) stoichiometry in each case. The enthalpies and entropies of formation of the complexes have been obtained by determining their formation constants at five different temperatures. PMID:15248945

  16. 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

  17. Infrared absorption spectroscopy of Ar- 12C 18O 2: change in the intramolecular potential upon complex formation

    NASA Astrophysics Data System (ADS)

    Ozaki, Yasushi; Horiai, Koui; Konno, Toichi; Uehara, Hiromichi

    2001-02-01

    An infrared absorption spectrum has been observed and analyzed for an Ar- 12C 18O 2 van der Waals (vdW) complex in the range of 2312-2314 cm -1. The effective structure of the complex derived from the obtained rotational constants is in essential agreement with the structure estimated from that of Ar- 12C 16O 2 based on the isotope effect on the amplitudes of vdW vibrations. The band origin for the Ar- 12C 18O 2ν4 mode shows a red shift of 0.4567 cm -1 with respect to that for 12C 18O 2ν3 mode; the change in the intramolecular potential of CO 2 upon complex formation with Ar is determined from the isotope effect on the band-origin shift.

  18. 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.

  19. 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

  20. 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

    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.

  1. Radiative association rate constant for the formation of CO: the importance of the first excited 1Σ+ state

    NASA Astrophysics Data System (ADS)

    Gustafsson, Magnus; Nyman, Gunnar

    2015-04-01

    The thermal rate constant for production of carbon monoxide, in its electronic ground state, through radiative association of carbon (C) and oxygen (O) atoms is computed. A combination of quantum and classical dynamics methods are employed. In particular, we investigate the importance of the mechanism where C and O approach each other on the 21Σ+ potential energy curve. Accounting for this reaction turns out to add about 75 per cent to the rate constant at 10 000 K. We expect the results to be important for studies of the chemistry in interstellar gas, particularly in metal-rich ejecta of supernovae. Since a significant isotope effect has been predicted previously both stable carbon isotopes 12C and 13C are considered in the present study.

  2. 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.

  3. The Effect of Complex Formation upon the Redox Potentials of Metallic Ions. Cyclic Voltammetry Experiments.

    ERIC Educational Resources Information Center

    Ibanez, Jorge G.; And Others

    1988-01-01

    Describes experiments in which students prepare in situ soluble complexes of metal ions with different ligands and observe and estimate the change in formal potential that the ion undergoes upon complexation. Discusses student formation and analysis of soluble complexes of two different metal ions with the same ligand. (CW)

  4. 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.

  5. 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

  6. Base flipping in open complex formation at bacterial promoters.

    PubMed

    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 RP(o)). This complex is competent to initiate RNA synthesis. Here we will review the role of σ70 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 σ70. 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 σ70. 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

  7. 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

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

    PubMed

    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

  9. Formation of a Cmcm phase in SnS at high pressure; an ab initio constant pressure study

    NASA Astrophysics Data System (ADS)

    Alptekin, Sebahaddin; Durandurdu, Murat

    2010-05-01

    The stability of SnS at high pressure is studied using a constant pressure ab initio technique. For the first time, a pressure-induced phase transformation from the Pnma structure to a Cmcm structure with the application of pressure is predicted through the simulations in this material. The Cmcm phase is still a layered structure, consisting of rocksalt-like bilayers, similar to that formed at high temperatures. The Cmcm structure is fivefold coordinated. This phase transformation gradually proceeds and is due to the significant decrease of the second neighbor distances. This phase change is also studied by total energy calculations.

  10. Hydrolysis of (CH{sub 3})Hg{sup +} in different ionic media: Salt effects and complex formation

    SciTech Connect

    Robertis, A. de; Foti, C.; Patane, G.; Sammartano, S.

    1998-11-01

    The hydrolysis of monomethylmercury(II) was studied potentiometrically, in NaNO{sub 3}, Na{sub 2}SO{sub 4}, and NaCl aqueous solution, in a wide range of ionic strengths (NaNO{sub 3}, 0 {le} I {le} 1; NaCl, 0 {le} 1 {le} 3 mol/dm{sup 3}) and at t = 25 C. For the reaction (CH{sub 3})Hg{sup +} = (CH{sub 3})Hg(OH){degree} + H{sup +}, the authors found log K{sub 1} = {minus}4.528 (I = 0 mol/dm{sup 3}). The species [(CH{sub 3})Hg]{sub 2}(OH){sup +} was also found, with log {beta}{sub 2} = {minus}2.15. Monomethylmercury(II) forms quite strong complexes with Cl{sup {minus}} (log K = 5.45, I = 0 mol/dm{sup 3}) and SO{sub 4}{sup 2{minus}} (log K = 2.64, I = 0 mol/dm{sup 3}). The dependence on ionic strength of formation constants was considered by using a Debye-Hueckel type equation. Hydrolysis and complex formation constants (at different ionic strengths) obtained were used to calculate the interaction parameters of Pitzer equations.

  11. 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

  12. 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.

  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. 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.

  15. 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.

  16. 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

  17. 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.

  18. Formation rates of complex organics in UV irradiated CH_3OH-rich ices. I. Experiments

    NASA Astrophysics Data System (ADS)

    Öberg, K. I.; Garrod, R. T.; van Dishoeck, E. F.; Linnartz, H.

    2009-09-01

    Context: Gas-phase complex organic molecules are commonly detected in the warm inner regions of protostellar envelopes, so-called hot cores. Recent models show that photochemistry in ices followed by desorption may explain the observed abundances. There is, however, a general lack of quantitative data on UV-induced complex chemistry in ices. Aims: This study aims to experimentally quantify the UV-induced production rates of complex organics in CH3OH-rich ices under a variety of astrophysically relevant conditions. Methods: The ices are irradiated with a broad-band UV hydrogen microwave-discharge lamp under ultra-high vacuum conditions, at 20-70 K, and then heated to 200 K. The reaction products are identified by reflection-absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TPD), through comparison with RAIRS and TPD curves of pure complex species, and through the observed effects of isotopic substitution and enhancement of specific functional groups, such as CH3, in the ice. Results: Complex organics are readily formed in all experiments, both during irradiation and during the slow warm-up of the ices after the UV lamp is turned off. The relative abundances of photoproducts depend on the UV fluence, the ice temperature, and whether pure CH3OH ice or CH3OH:CH4/CO ice mixtures are used. C2H6, CH3CHO, CH3CH2OH, CH3OCH3, HCOOCH3, HOCH2CHO and (CH2OH)2 are all detected in at least one experiment. Varying the ice thickness and the UV flux does not affect the chemistry. The derived product-formation yields and their dependences on different experimental parameters, such as the initial ice composition, are used to estimate the CH3OH photodissociation branching ratios in ice and the relative diffusion barriers of the formed radicals. At 20 K, the pure CH3OH photodesorption yield is 2.1(±1.0)×10-3 per incident UV photon, the photo-destruction cross section 2.6(±0.9)×10-18 cm^2. Conclusions: Photochemistry in CH3OH ices is efficient enough to explain the observed abundances of complex organics around protostars. Some complex molecules, such as CH3CH2OH and CH3OCH3, form with a constant ratio in our ices and this can can be used to test whether complex gas-phase molecules in astrophysical settings have an ice-photochemistry origin. Other molecular ratios, e.g. HCO-bearing molecules versus (CH2OH)2, depend on the initial ice composition and temperature and can thus be used to investigate when and where complex ice molecules form. Appendices are only available in electronic form at http://www.aanda.org

  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. Reactions of chloride complexes of ruthenium (IV) with formic acid and sodium formate in aqueous solutions

    SciTech Connect

    Simanova, S.A.; Krylova, G.S.; Maslov, E.I.

    1982-04-20

    Study of the reactions of (NH/sub 4/)/sub 2/RuCl/sub 6/ with formic acid and sodium formate showed that, depending on the conditions, chlorocarbonyl, chloroformatocarbonyl, or chloroformato complexes of ruthenium(III) are formed.

  1. 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.

  2. 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.

  3. 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

  4. Thermodynamic characteristics of the formation of a zinc(II) tetraphenylporphyrin complex with aromatic amines

    NASA Astrophysics Data System (ADS)

    Lebedeva, N. Sh.; Mal'kova, E. A.; Andreev, V. P.

    2015-05-01

    The processes of the formation of a molecular complex of zinc(II) tetraphenylporphyrin with amines and aniline and pyridine derivatives are studied via calorimetry and IR spectroscopy. Standard thermodynamic characteristics of the formation of zinc(II) tetraphenylporphyrin complexes with ligands are obtained, and the centers of interaction between ligands and porphyrin are determined. In the case of amino derivatives of pyridine, interaction with zinc(II) tetraphenylporphyrin proceeds on amino groups.

  5. 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.

  6. 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.

  7. 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

  8. 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

  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. 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...

  11. 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

  12. 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

    Kocyła, Anna; Pomorski, Adam; Krężel, 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 492 nm for the ZnHx(PAR)2 complex at pH7.4 in buffered water solution is 71,500 M(-1) cm(-1), and the dissociation constant of the complex in these conditions is 7.08×10(-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

  13. Substrate Binding Promotes Formation of the Skp1-Cul1-Fbxl3 (SCFFbxl3) Protein Complex*

    PubMed Central

    Yumimoto, Kanae; Muneoka, Tetsuya; Tsuboi, Tomohiro; Nakayama, Keiichi I.

    2013-01-01

    The Skp1–Cul1–F-box protein (SCF) complex is one of the most well characterized types of ubiquitin ligase (E3), with the E3 activity of the complex being regulated in part at the level of complex formation. Fbxl3 is an F-box protein that is responsible for the ubiquitylation and consequent degradation of cryptochromes (Crys) and thus regulates oscillation of the circadian clock. Here we show that formation of the SCFFbxl3 complex is regulated by substrate binding in vivo. Fbxl3 did not associate with Skp1 and Cul1 to a substantial extent in transfected mammalian cells. Unexpectedly, however, formation of the SCFFbxl3 complex was markedly promoted by forced expression of its substrate Cry1 in these cells. A mutant form of Fbxl3 that does not bind to Cry1 was unable to form an SCF complex, suggesting that interaction of Cry1 with Fbxl3 is essential for formation of SCFFbxl3. In contrast, recombinant Fbxl3 associated with recombinant Skp1 and Cul1 in vitro even in the absence of recombinant Cry1. Domain-swap analysis revealed that the COOH-terminal leucine-rich repeat domain of Fbxl3 attenuates the interaction of Skp1, suggesting that a yet unknown protein associated with the COOH-terminal domain of Fbxl3 and inhibited SCF complex formation. Our results thus provide important insight into the regulation of both SCF ubiquitin ligase activity and circadian rhythmicity. PMID:24085301

  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. An illustration of the complexity of continent formation

    NASA Technical Reports Server (NTRS)

    Burke, Kevin

    1988-01-01

    It was pointed out that a consensus may be emerging in crustal growth models, considering the clustering of most growth curves and their uncertainties. Curves most distant from this clustering represent models involving extensive recycling of continental material back into the mantle, but the author wondered if geochemical signatures for this would be recognizable considering the lack of evidence from seismic tomography for discrete mantle reservoirs, and the likelihood of core-mantle interaction based on recent high pressure experiments. Unreactivated Archean rocks represent only 2 percent of present continental area, and the author was uncomfortable about basing inferences on what the early Earth was like on such a small amount of information. He feels that the hypothesis of continental assembly that needs testing is that of banging together of island arcs, such as in Indonesia today. As an example of how complex this process can be, the author described the geology of the Caribbean arc system, which shows evidence for reversals of subduction polarity, numerous collisional events, and substantial strike-slip movements. It seemed unlikely to the author that Archean examples would have been less complicated.

  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. Modeling of the formation of complex molecules in protostellar objects

    NASA Astrophysics Data System (ADS)

    Kochina, O. V.; Wiebe, D. S.; Kalenskii, S. V.; Vasyunin, A. I.

    2013-11-01

    The results of molecular composition modeling are presented for the well studied low-mass star-forming region TMC-1 and the massive star-forming region DR21(OH), which is poorly studied from a chemical point of view. The column densities of dozens of molecules, ranging from simple diatomic to complex organic molecules, are reproduced to within an order of magnitude using a one-dimensional model for the physical and chemical structure of these regions. The chemical ages of the regions are approximately 105 years in both cases. The main desorption mechanisms that are usually included in chemical models (photodesorption, thermal desorption, and cosmic-ray-induced desorption) do not provide sufficient gasphase abundances of molecules that are synthesized in surface reactions; however, this shortcoming can be removed by introducing small amount of reactive desorption into the model. It is possible to reproduce the properties of the TMC-1 chemical composition in a standard model, without requiring additional assumptions about an anomalous C/O ratio or the recent accretion of matter enriched with atomic carbon, as has been proposed by some researchers.

  18. 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.

  19. {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.

  20. Polyphenol-Aluminum Complex Formation: Implications for Aluminum Tolerance in Plants.

    PubMed

    Zhang, Liangliang; Liu, Ruiqiang; Gung, Benjamin W; Tindall, Steven; Gonzalez, Javier M; Halvorson, Jonathan J; Hagerman, Ann E

    2016-04-20

    Natural polyphenols may play an important role in aluminum detoxification in some plants. We examined the interaction between Al(3+) and the purified high molecular weight polyphenols pentagalloyl glucose (940 Da) and oenothein B (1568 Da), and the related compound methyl gallate (184 Da) at pH 4 and 6. We used spectrophotometric titration and chemometric modeling to determine stability constants and stoichiometries for the aluminum-phenol (AlL) complexes. The structures and spectral features of aluminum-methyl gallate complexes were evaluated with quantum chemical calculations. The high molecular weight polyphenols formed Al3L2 complexes with conditional stability constants (β) ∼ 1 × 10(23) at pH 6 and AlL complexes with β ∼ 1 × 10(5) at pH 4. Methyl gallate formed AlL complexes with β = 1 × 10(6) at pH 6 but did not complex aluminum at pH 4. At intermediate metal-to-polyphenol ratios, high molecular weight polyphenols formed insoluble Al complexes but methyl gallate complexes were soluble. The high molecular weight polyphenols have high affinities and solubility features that are favorable for a role in aluminum detoxification in the environment. PMID:27022835

  1. 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...

  2. 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

  3. Henry's law constants of 2,2,2-trifluoroethyl formate, ethyl trifluoroacetate, and non-fluorinated analogous esters

    NASA Astrophysics Data System (ADS)

    Kutsuna, Shuzo; Chen, Liang; Abe, Takashi; Mizukado, Junji; Uchimaru, Tadafumi; Tokuhashi, Kazuaki; Sekiya, Akira

    Henry's law constants of two fluorinated esters [CF 3CH 2OC(O)H and C 2H 5OC(O)CF 3] and four related non-fluorinated esters [CH 3OC(O)H, C 2H 5OC(O)H, n-C 3H 7OC(O)H and C 2H 5OC(O)CH 3] were determined at 278-298 K by a column-stripping method. From the van't Hoff equation of H=Hexp[-{ΔH}/{R}({1}/{T}-{1}/{298})], the H298 (M atm -1) and Δ Hsol (kJ mol -1) values obtained were 0.55±0.04, -39±3 (CF 3CH 2OC(O)H); 0.09±0.01, -41±5 (C 2H 5OC(O)CF 3); 4.2±0.2, -33±2 (CH 3OC(O)H); 3.4±0.2, -38±2 (C 2H 5OC(O)H); 2.6±0.1, -42±1 ( n-C 3H 7OC(O)H); and 6.0±0.5, -49±3 (C 2H 5OC(O)CH 3), respectively. Errors reported are at 95% confidence levels and represent precision only. Hydrolysis was observed only for C 2H 5OC(O)CF 3. Replacement of CH 3 by CF 3 decreases H298 values by 6, 11, and 67 times, respectively, for CF 3CH 2OC(O)H, CF 3CH 2OC(O)CH 3, and C 2H 5OC(O)CF 3, while the differences in the Δ Hsol values were small with these substitutions. Sodium chloride salting-out effects are examined for all of the esters. C 2H 5OC(O)CF 3 has the largest salting coefficient (0.74). The estimated lifetime of CF 3CH 2OC(O)H suggests that dissolution into seawater serves as a tropospheric sink for this compound. On the basis of the solubility and reactivity of the esters studied herein, clouds and the ocean are discussed as possible sinks for the dissolution of tropospheric CF 3CF 2OC(O)H, which is an atmospheric oxidation product of a substitute for hydrofluorocarbons as CF 3CF 2OCH 3.

  4. Direct measurement via phage titre of the dissociation constants in solution of fusion phage-substrate complexes.

    PubMed Central

    Dyson, M R; Germaschewski, V; Murray, K

    1995-01-01

    Studies of interactions between filamentous fusion phage particles and protein or nucleic acid molecules have gained increasing importance with recent successes of screening techniques based upon random phage display libraries (biopanning). Since a number of different phage are usually obtained by biopanning, it is useful to compare quantitatively the binding affinities of individual phage for the substrate used for selection. A procedure is described for determination of relative dissociation constants (KdRel) between filamentous phage carrying peptide fusions to the coat protein gpIII and substrates in solution. This novel method is based on the measurement of phage titres. Phage selected from a random fusion phage library for binding to a monoclonal antibody or a viral structural protein exhibited KdRel values in the nanomolar and micromolar ranges for their respective substrates, thus validating the method over a wide range of binding affinities. PMID:7784206

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

    NASA Astrophysics Data System (ADS)

    Oliveira, F. C.; Denadai, A. M. L.; Fulgêncio, F. H.; Magalhães, W. F.; Alcântara, A. F. C.; Windmöller, D.; Machado, J. C.

    2012-06-01

    Positronium formation in triphenylphosphine oxide (TPPO), triphenylmethanol (TPM), and systems [TPPO(1-X)ṡTPMX] has been studied. The low probability of positronium formation in complex [TPPO0.5ṡTPM0.5] was attributed to strong hydrogen bond and sixfold phenyl embrace interactions. These strong interactions in complex reduce the possibility of the n- and π-electrons to interact with positrons on the spur and consequently, the probability of positronium formation is lower. The τ3 parameter and free volume (correlated to τ3) 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.

  6. 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

  7. Direct measurements of the total rate constant of the reaction NCN + H and implications for the product branching ratio and the enthalpy of formation of NCN.

    PubMed

    Fassheber, Nancy; Dammeier, Johannes; Friedrichs, Gernot

    2014-06-21

    The overall rate constant of the reaction (2), NCN + H, which plays a key role in prompt-NO formation in flames, has been directly measured at temperatures 962 K < T < 2425 K behind shock waves. NCN radicals and H atoms were generated by the thermal decomposition of NCN3 and C2H5I, respectively. NCN concentration-time profiles were measured by sensitive narrow-line-width laser absorption at a wavelength of λ = 329.1302 nm. The obtained rate constants are best represented by the combination of two Arrhenius expressions, k2/(cm(3) mol(-1) s(-1)) = 3.49 × 10(14) exp(-33.3 kJ mol(-1)/RT) + 1.07 × 10(13) exp(+10.0 kJ mol(-1)/RT), with a small uncertainty of ±20% at T = 1600 K and ±30% at the upper and lower experimental temperature limits.The two Arrhenius terms basically can be attributed to the contributions of reaction channel (2a) yielding CH + N2 and channel (2b) yielding HCN + N as the products. A more refined analysis taking into account experimental and theoretical literature data provided a consistent rate constant set for k2a, its reverse reaction k1a (CH + N2 → NCN + H), k2b as well as a value for the controversial enthalpy of formation of NCN, ΔfH = 450 kJ mol(-1). The analysis verifies the expected strong temperature dependence of the branching fraction ϕ = k2b/k2 with reaction channel (2b) dominating at the experimental high-temperature limit. In contrast, reaction (2a) dominates at the low-temperature limit with a possible minor contribution of the HNCN forming recombination channel (2d) at T < 1150 K. PMID:24807121

  8. Role of load in regulating eIF-4F complex formation in adult feline cardiocytes.

    PubMed

    Tuxworth, W J; Wada, H; Ishibashi, Y; McDermott, P J

    1999-10-01

    This study examined whether cardiocyte load increases eIF-4F complex formation. To increase load in vitro, adult feline cardiocytes were electrically stimulated to contract (1 Hz, 5-ms pulses). eIF-4F complex formation, measured by eIF-4G association with eIF-4E, increased 57 +/- 16% after 4 h of contraction compared with controls. eIF-4F complex formation did not increase on electrical stimulation with 2,3-butanedione monoxime (BDM), an inhibitor of active tension. Both insulin and phorbol ester increased eIF-4F complex formation, but these increases were unaffected by BDM. Insulin caused a shift of eIF-4E binding proteins (4E-BPs) into their hyperphosphorylated gamma-isoforms and dissociation of 4E-BPs from eIF-4E. Rapamycin inhibited 4E-BP phosphorylation in response to insulin but had no effect on eIF-4F complex formation. Electrically stimulated contraction caused a partial shift of 4E-BP1 and 4E-BP2 into the gamma-isoforms, but it had no effect on 4E-BP association with eIF-4E. Rapamycin blocked the increase in eIF-4F complex formation in electrically stimulated cardiocytes and depressed contractility. These data indicate that cardiocyte load causes a tension-dependent increase in eIF-4F complex formation that does not require dissociation of 4E-BPs from eIF-4E. PMID:10516161

  9. 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

  10. SEPALLATA3: the 'glue' for MADS box transcription factor complex formation

    PubMed Central

    Immink, Richard GH; Tonaco, Isabella AN; de Folter, Stefan; Shchennikova, Anna; van Dijk, Aalt DJ; Busscher-Lange, Jacqueline; Borst, Jan W; Angenent, Gerco C

    2009-01-01

    Background Plant MADS box proteins play important roles in a plethora of developmental processes. In order to regulate specific sets of target genes, MADS box proteins dimerize and are thought to assemble into multimeric complexes. In this study a large-scale yeast three-hybrid screen is utilized to provide insight into the higher-order complex formation capacity of the Arabidopsis MADS box family. SEPALLATA3 (SEP3) has been shown to mediate complex formation and, therefore, special attention is paid to this factor in this study. Results In total, 106 multimeric complexes were identified; in more than half of these at least one SEP protein was present. Besides the known complexes involved in determining floral organ identity, various complexes consisting of combinations of proteins known to play a role in floral organ identity specification, and flowering time determination were discovered. The capacity to form this latter type of complex suggests that homeotic factors play essential roles in down-regulation of the MADS box genes involved in floral timing in the flower via negative auto-regulatory loops. Furthermore, various novel complexes were identified that may be important for the direct regulation of the floral transition process. A subsequent detailed analysis of the APETALA3, PISTILLATA, and SEP3 proteins in living plant cells suggests the formation of a multimeric complex in vivo. Conclusions Overall, these results provide strong indications that higher-order complex formation is a general and essential molecular mechanism for plant MADS box protein functioning and attribute a pivotal role to the SEP3 'glue' protein in mediating multimerization. PMID:19243611

  11. 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

  12. 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

  13. 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.

  14. 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

  15. 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.

  16. From complex structures to complex processes: Percolation theory applied to the formation of a city

    NASA Astrophysics Data System (ADS)

    Bitner, Agnieszka; Hołyst, Robert; Fiałkowski, Marcin

    2009-09-01

    We investigate the morphology of the spatial pattern resulting from the division of land into the parcels that is observed in the centers of the cities, by analyzing the distribution function of the parcel areas. A simple model based on a two-dimensional bond percolation is employed to mimic the process of the formation of the city. The model reproduces the empirical distribution of the parcel areas that is found to exhibit the power law with the exponent τ=2.0 . We argue that the city emerges from a collection of separated settlements in a process that can be described as a structural phase transition.

  17. 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

  18. Generating functional analysis of complex formation and dissociation in large protein interaction networks

    NASA Astrophysics Data System (ADS)

    Coolen, A. C. C.; Rabello, S.

    2009-12-01

    We analyze large systems of interacting proteins, using techniques from the non-equilibrium statistical mechanics of disordered many-particle systems. Apart from protein production and removal, the most relevant microscopic processes in the proteome are complex formation and dissociation, and the microscopic degrees of freedom are the evolving concentrations of unbound proteins (in multiple post-translational states) and of protein complexes. Here we only include dimer-complexes, for mathematical simplicity, and we draw the network that describes which proteins are reaction partners from an ensemble of random graphs with an arbitrary degree distribution. We show how generating functional analysis methods can be used successfully to derive closed equations for dynamical order parameters, representing an exact macroscopic description of the complex formation and dissociation dynamics in the infinite system limit. We end this paper with a discussion of the possible routes towards solving the nontrivial order parameter equations, either exactly (in specific limits) or approximately.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    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.

  20. 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.

  1. 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

  2. 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

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

    PubMed

    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

  4. 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.

  5. Phosphonato complexes of platinum(II): kinetics of formation and phosphorus-31 NMR characterization studies

    SciTech Connect

    Slavin, L.L.; Bose, R.N. )

    1990-12-01

    Reactions of cis-diamminedichloroplatinum(II) with phosphonoformic acid (PFA), phosphonoacetic acid (PAA), and methylenediphosphonic acid (MDP) yield various phosphonatoplatinum(II) chelates which were characterized by phosphorus-31 NMR spectroscopy. The P-31 resonances for the chelates appear at 6-12 ppm downfield as compared to the uncomplexed ligands. All complexes exhibit monoprotic acidic behavior in the pH range 2-10. The chemical shift-pH profiles yielded acidity constants, 1.0 x 10(-4), 1.5 x 10(-4), and 1.3 x 10(-6) M-1, for the PFA, PAA, and MDP chelates. In addition to the monomeric chelate, MDP formed a bridged diplatinum(II,II) complex when it reacted with cis-Pt (NH3)2(H2O)2(2)+. The P-31 resonance for this binuclear complex appears at 22 ppm downfield from the unreacted ligand. Rate data for the complexation reactions of the phosphonate ligands with the dichloroplatinum complex are consistent with a mechanism in which a monodentate complex is formed initially through rate-limiting aquation process of the platinum complex, followed by a rapid chelation. For the PFA and PAA complexes, initial binding sites are the carboxylato oxygens. Implications of the various binding modes of the phosphonates in relationship to their antiviral activities are discussed.

  6. 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.

  7. Cation-induced formation of a macro-glucan synthase complex

    SciTech Connect

    Delmer, D.; Solomon, M.; Andrawis, A.; Amor, Y. )

    1990-05-01

    Incubation of Chaps or digitonin-solubilized membrane proteins from cotton fiber with Ca{sup 2+} in combination with Mg{sup 2+}, leads to formation of a complex which can be sedimented within 15 min at 15,000 g. The complex is enriched >10-fold in callose synthase activity and possesses a characteristic pattern of enriched polypeptides when analyzed by SDS-PAGE. Although cation dependent, formation of the complex is not dependent upon the presence of the callose synthase substrate, UDP-glc, indicating that complex formation is not due to entrapment of the enzyme by association with glucan product. The enriched polypeptides include: >200, 50, and 46 kD, all of which have been shown by direct photo-labeling to interact with {sup 92}P-UDP-glc in a Ca{sup 2+} or beta-glucoside dependent reaction are considered likely subunits of callose synthase; a 60-62 kD doublet which is recognized by our MAb 2-1 which can form an immune complex with callose synthase; 74 and 34 kD polypeptides which also interact with UDP-glc, but do not associate with callose synthase in the presence of EDTA. A similar phenomenon is also observed with solubilized membrane proteins from mung beans. Possible functions of each of the enriched polypeptides, the catalytic properties, and ultra-structure of this macro-glucan synthase complex are currently under investigation.

  8. Spectroscopic studies on the formation of molecular complexes of sulfamethoxazole with novel 2,3,5-trichloro-6-alkoxy-1,4-benzoquinones

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

    UV-Vis, 1H NMR, FT-IR, LC-MS and fluorescence spectral techniques were employed to investigate the mechanism of interaction of sulfamethoxazole with alkoxy substituted 2,3,5-trichloro-1,4-benzoquinones and to characterize the reaction products. The interactions of these quinones with sulfamethoxazole (SULF) were found to proceed through the formation of donor-acceptor complex, containing radical anion and its conversion to the product. Fluorescence quenching studies indicated that the interaction between the donor and the acceptors are spontaneous. Correlation of association constants of the CT complexes with Taft's polar and steric constants indicated that polar factor plays a significant role in governing the reactivity. The results indicated that the electronic effects of the substituents play significant role in governing the reactivity of the quinones when compared to steric factor.

  9. 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.

  10. 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...

  11. Enthalpies of complex formation of boron and aluminum bromides with organic bases of high donor power

    SciTech Connect

    Grigor-ev, A.A.; Kondrat'ev, Y.V.; Suvorov, A.V.

    1986-11-20

    By the calorimetric method enthalpies of complex formation were determined for boron and aluminum bromides with piperidine and hexamethylphosphoric triamide in benzene solutions and for boron bromide with pyridine in dichloroethane, and also enthalpies of solution were determined for BBr/sub 3/ and the adducts AlBr/sub 3/ x PPy and BBr/sub 2/ x Py in benzene and pyridine.

  12. Three-Coordinate Terminal Imidoiron(III) Complexes: Structure, Spectroscopy, and Mechanism of Formation

    PubMed Central

    Cowley, Ryan E.; DeYonker, Nathan J.; Eckert, Nathan A.; Cundari, Thomas R.; DeBeer, Serena; Bill, Eckhard; Ottenwaelder, Xavier; Flaschenriem, Christine; Holland, Patrick L.

    2010-01-01

    Reaction of 1-adamantyl azide with iron(I) diketiminate precursors gives metastable but isolable imidoiron(III) complexes LFe=NAd (L = bulky β-diketiminate ligand; Ad = 1-adamantyl). This paper addresses: (1) the spectroscopic and structural characterization of the Fe=N multiple bond in these interesting three-coordinate iron imido complexes, and (2) the mechanism through which the imido complexes form. The iron(III) imido complexes have been examined by 1H NMR and EPR spectroscopies and temperature-dependent magnetic susceptibility (SQUID), and structurally characterized by crystallography and/or X-ray absorption (EXAFS) measurements. These data show that the imido complexes have quartet ground states and short (1.68 ± 0.01 Å) iron-nitrogen bonds. The formation of the imido complexes proceeds through unobserved iron–RN3 intermediates, which are indicated by QM/MM computations to be best described as iron(II) with an RN3 radical anion. The radical character on the organoazide bends its NNN linkage to enable easy N2 loss and imido complex formation. The product distribution between imidoiron(III) products and hexazene-bridged diiron(II) products is solvent-dependent, and the solvent dependence can be explained by coordination of certain solvents to the iron(I) precursor prior to interaction with the organoazide. PMID:20524625

  13. 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.

  14. 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.

  15. Oligomer formation of the bacterial second messenger c-di-GMP: reaction rates and equilibrium constants indicate a monomeric state at physiological concentrations.

    PubMed

    Gentner, Martin; Allan, Martin G; Zaehringer, Franziska; Schirmer, Tilman; Grzesiek, Stephan

    2012-01-18

    Cyclic diguanosine-monophosphate (c-di-GMP) is a bacterial signaling molecule that triggers a switch from motile to sessile bacterial lifestyles. This mechanism is of considerable pharmaceutical interest, since it is related to bacterial virulence, biofilm formation, and persistence of infection. Previously, c-di-GMP has been reported to display a rich polymorphism of various oligomeric forms at millimolar concentrations, which differ in base stacking and G-quartet interactions. Here, we have analyzed the equilibrium and exchange kinetics between these various forms by NMR spectroscopy. We find that the association of the monomer into a dimeric form is in fast exchange (constant of about 1 mM. At concentrations above 100 μM, higher oligomers are formed in the presence of cations. These are presumably tetramers and octamers, with octamers dominating above about 0.5 mM. Thus, at the low micromolar concentrations of the cellular environment and in the absence of additional compounds that stabilize oligomers, c-di-GMP should be predominantly monomeric. This finding has important implications for the understanding of c-di-GMP recognition by protein receptors. In contrast to the monomer/dimer exchange, formation and dissociation of higher oligomers occurs on a time scale of several hours to days. The time course can be described quantitatively by a simple kinetic model where tetramers are intermediates of octamer formation. The extremely slow oligomer dissociation may generate severe artifacts in biological experiments when c-di-GMP is diluted from concentrated stock solution. We present a simple method to quantify c-di-GMP monomers and oligomers from UV spectra and a procedure to dissolve the unwanted oligomers by an annealing step. PMID:22142443

  16. 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.

  17. 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.

  18. 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.

  19. Anelastic (dielectric) relaxation of point defects at any concentration, with blocking effects and formation of complexes

    NASA Astrophysics Data System (ADS)

    Cordero, F.

    1993-04-01

    A derivation of the relaxation strength for anelastic and dielectric relaxation of point defects is proposed, and the calculation is extended to cases not yet treated; the formulas reported in the literature can be obtained as particular cases. The relaxation strength is expressed as the sum of the contributions of all the pairs of configurations that the defect can assume. The case of arbitrarily high concentrations with blocking, short-range interactions, and formation of defect complexes is also treated, and the formulas of the partial concentrations of the various defect configurations are provided. The proposed approach is useful if the formation of complexes and the short-range interactions occur within independent cells or subsystems into which the crystal can be divided. Two specific cases are discussed as applications: the anelastic relaxation of a four-level tunnel system and of interstitial hydrogen in the hcp rare earths with the formation of H pairs.

  20. Terabit bandwidth-adaptive transmission using low-complexity format-transparent digital signal processing.

    PubMed

    Zhuge, Qunbi; Morsy-Osman, Mohamed; Chagnon, Mathieu; Xu, Xian; Qiu, Meng; Plant, David V

    2014-02-10

    In this paper, we propose a low-complexity format-transparent digital signal processing (DSP) scheme for next generation flexible and energy-efficient transceiver. It employs QPSK symbols as the training and pilot symbols for the initialization and tracking stage of the receiver-side DSP, respectively, for various modulation formats. The performance is numerically and experimentally evaluated in a dual polarization (DP) 11 Gbaud 64QAM system. Employing the proposed DSP scheme, we conduct a system-level study of Tb/s bandwidth-adaptive superchannel transmissions with flexible modulation formats including QPSK, 8QAM and 16QAM. The spectrum bandwidth allocation is realized in the digital domain instead of turning on/off sub-channels, which improves the performance of higher order QAM. Various transmission distances ranging from 240 km to 6240 km are demonstrated with a colorless detection for hardware complexity reduction. PMID:24663520

  1. 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

  2. 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).

  3. 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

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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

  9. 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

  10. 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

  11. Effect of citrate on the local Fe coordination in ferrihydrite, arsenate binding, and ternary arsenate complex formation

    NASA Astrophysics Data System (ADS)

    Mikutta, Christian; Frommer, Jakob; Voegelin, Andreas; Kaegi, Ralf; Kretzschmar, Ruben

    2010-10-01

    In oxic environments contaminated with arsenate (As(V)), small polyhydroxycarboxylates such as citrate may impact the structure of precipitating ferrihydrite (Fh) and thus the surface speciation of As(V). In this study, '2-line' Fh was precipitated from ferric nitrate solutions that were neutralized to pH 6.5 in the presence of increasing citrate concentrations and in the absence or presence of As(V). The initial citrate/Fe and As/Fe ratios were 0-50 mol% and 5 mol%, respectively. The reaction products, enriched with up to 0.32 mol citrate per mole Fe, were characterized by X-ray diffraction, transmission electron microscopy, and Fe and As K-edge X-ray absorption spectroscopy. Citrate decreased the particle size of Fh by impairing the polymerization of Fe(O,OH) 6 octahedra via edge and corner linkages. In the presence of citrate and As(V), coordination numbers of Fe decreased by up to 28% relative to pure Fh. Citrate significantly reduced the static disorder of Fe-O bonds, implying a decreased octahedral distortion in Fh. Mean bond distances in Fh were not affected by citrate and remained constant within error at 1.98 Å for Fe-O, 3.03 Å for Fe-Fe1, and 3.45 Å for Fe-Fe2. Likewise, citrate had no effect on the As-Fe (3.31 Å) bond distance in As(V) coprecipitated with Fh. The As K-edge EXAFS data comply with the formation of (i) only monodentate binuclear ( 2C) As(V) surface complexes and (ii) combinations of 2C, monodentate mononuclear ( 1V), and outersphere As(V) surface complexes. Our results suggest that increasing citrate concentrations led to a decreasing 1V/ 2C ratio and/or that citrate increasingly impaired the formation of outersphere As(V) complexes. Moreover, citrate stabilized colloidal suspensions of Fh (pH 4.3-6.6, I ˜0.45 M) and reduced Fh formation at the expense of soluble Fe(III)-citrate complexes. At initial citrate/Fe ratios ⩾25 mol%, between 8% and 41% of total Fe was bound in Fe(III)-citrate complexes after Fh formation. Polynuclear Fe(III)-citrate species were found to bind As(V) via surface complexes indistinguishable by EXAFS from those of As(V) adsorbed to or coprecipitated with Fh. Our study implies that low molecular weight polyhydroxycarboxylates may enhance the mobility of As(V) in aqueous systems of high ionic strength (e.g., neutralizing acid mine drainage) by colloidal stabilization of suspended Fh particles and the formation of ternary As(V) complexes.

  12. 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

  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. 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

  15. 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

  16. On the Silver Effect and the Formation of Chloride-Bridged Digold Complexes

    PubMed Central

    2013-01-01

    Abstraction of chloride anion from Au(I) complexes such as JohnPhosAuCl in noncoordinating solvents with 1 equiv of a silver salt, or even larger amounts, leads to the formation of chloride-bridged dinuclear gold(I) complexes, irrespective of the counteranion, which are substantially less reactive as catalysts. This incomplete removal of chloride ligand could lead to false negative results when using the in situ generation of the gold(I) active species by silver-promoted chloride abstraction. PMID:24195441

  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. Numerical Modeling of Hydraulic Fractures Interaction in Complex Naturally Fractured Formations

    NASA Astrophysics Data System (ADS)

    Kresse, Olga; Weng, Xiaowei; Gu, Hongren; Wu, Ruiting

    2013-05-01

    A recently developed unconventional fracture model (UFM) is able to simulate complex fracture network propagation in a formation with pre-existing natural fractures. A method for computing the stress shadow from fracture branches in a complex hydraulic fracture network (HFN) based on an enhanced 2D displacement discontinuity method with correction for finite fracture height is implemented in UFM and is presented in detail including approach validation and examples. The influence of stress shadow effect from the HFN generated at previous treatment stage on the HFN propagation and shape at new stage is also discussed.

  19. Complex formation, thermal behavior and stability competition between Cu(II) ion and Cu0 nanoparticles with some new azo dyes. Antioxidant and in vitro cytotoxic activity

    NASA Astrophysics Data System (ADS)

    Gaber, M.; El-Sayed, Y. S.; El-Baradie, K. Y.; Fahmy, R. M.

    2013-04-01

    Four triazole and thiadiazole-based azo chromophores namely [(E)-4-((1H-1,2,4-triazol-3-yl)diazenyl)benzene-1,3-diol.(HL1), (E)-4-((5-(methylthio)-1H-1,2,4-triazol-3-yl)diazenyl)benzene-1,3-diol.(HL2), (E)-4-((1,3,4-thiadiazol-2-yl)diazenyl)benzene-1,3-diol.(HL3) and (E)-4-((5-mercapto-1,3,4-thiadiazol-2-yl)diazenyl)benzene-1,3-diol.(HL4)] were synthesized and characterized by elemental analyses, IR, UV-Vis as well as mass spectroscopy. Cu(II) complexes of the investigated azo dyes have been synthesized and characterized by elemental analyses, IR, electronic and ESR spectra, magnetic susceptibility and thermogravimetric analyses. 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 azodyes to copper nanoparticles was described as coordination mode of charged dye molecules on the colloidal Cu0 surface through anchoring sbnd OH- group. The apparent association constants of the colloidal copper nanoparticles azodye complexes in solution were evaluated using the spectral method and compared with the formation constant of the Cu(II) azo complexes. The antitumor and antioxidant activities of the synthesized azo dyes and their Cu(II) azo complexes have been evaluated.

  20. Almost enclosed buckyball joints: synthesis, complex formation, and computational simulations of pentypticene-extended tribenzotriquinacene.

    PubMed

    Henne, Stefan; Bredenkötter, Björn; Alaghemandi, Mohammad; Bureekaew, Sareeya; Schmid, Rochus; Volkmer, Dirk

    2014-12-01

    We report the synthesis of a tribenzotriquinacene-based (TBTQ) receptor (3) for C60 fullerene, which is extended by pentiptycene moieties to provide an almost enclosed concave ball bearing. The system serves as a model for a self-assembling molecular rotor with a flexible and adapting stator. Unexpectedly, nuclear magnetic resonance spectroscopic investigations reveal a surprisingly low complex stability constant of K1 =213±37 M(-1) for [C60 ⊂3], seemingly inconsistent with the previously reported TBTQ systems. Molecular dynamics (MD) simulations have been conducted for three different [C60 ⊂TBTQ] complexes to resolve this. Because of the dominating dispersive interactions, the binding energies increase with the contact area between guest and host, however, only for rigid host structures. By means of free-energy calculations with an explicit solvent model it can be shown that the novel flexible TBTQ receptor 3 binds weakly because of hampering entropic contributions. PMID:25234364

  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. Unique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards catalytic formation of ammonia.

    PubMed

    Tanaka, Hiromasa; Arashiba, Kazuya; Kuriyama, Shogo; Sasada, Akira; Nakajima, Kazunari; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki

    2014-01-01

    It is vital to design effective nitrogen fixation systems that operate under mild conditions, and to this end we recently reported an example of the catalytic formation of ammonia using a dinitrogen-bridged dimolybdenum complex bearing a pincer ligand, where up to twenty three equivalents of ammonia were produced based on the catalyst. Here we study the origin of the catalytic behaviour of the dinitrogen-bridged dimolybdenum complex bearing the pincer ligand with density functional theory calculations, based on stoichiometric and catalytic formation of ammonia from molecular dinitrogen under ambient conditions. Comparison of di- and mono-molybdenum systems shows that the dinitrogen-bridged dimolybdenum core structure plays a critical role in the protonation of the coordinated molecular dinitrogen in the catalytic cycle. PMID:24769530

  3. Meiotic cohesin complexes are essential for the formation of the axial element in mice

    PubMed Central

    Herrán, Yurema; García-Tuñón, Ignacio; Gutiérrez-Caballero, Cristina; de Álava, Enrique; Barbero, José Luis; Schimenti, John; de Rooij, Dirk G.; Sánchez-Martín, Manuel

    2012-01-01

    Cohesin is a conserved multisubunit protein complex that participates in chromosome segregation, DNA damage repair, chromatin regulation, and synaptonemal complex (SC) formation. Yeast, but not mice, depleted of the cohesin subunit Rec8 are defective in the formation of the axial elements (AEs) of the SC, suggesting that, in mammals, this function is not conserved. In this paper, we show that spermatocytes from mice lacking the two meiosis-specific cohesin subunits RAD21L and REC8 were unable to initiate RAD51- but not DMC1-mediated double-strand break repair, were not able to assemble their AEs, and arrested as early as the leptotene stage of prophase I, demonstrating that cohesin plays an essential role in AE assembly that is conserved from yeast to mammals. PMID:22711701

  4. Unique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards catalytic formation of ammonia

    PubMed Central

    Tanaka, Hiromasa; Arashiba, Kazuya; Kuriyama, Shogo; Sasada, Akira; Nakajima, Kazunari; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki

    2014-01-01

    It is vital to design effective nitrogen fixation systems that operate under mild conditions, and to this end we recently reported an example of the catalytic formation of ammonia using a dinitrogen-bridged dimolybdenum complex bearing a pincer ligand, where up to twenty three equivalents of ammonia were produced based on the catalyst. Here we study the origin of the catalytic behaviour of the dinitrogen-bridged dimolybdenum complex bearing the pincer ligand with density functional theory calculations, based on stoichiometric and catalytic formation of ammonia from molecular dinitrogen under ambient conditions. Comparison of di- and mono-molybdenum systems shows that the dinitrogen-bridged dimolybdenum core structure plays a critical role in the protonation of the coordinated molecular dinitrogen in the catalytic cycle. PMID:24769530

  5. HU binding to DNA: evidence for multiple complex formation and DNA bending.

    PubMed

    Wojtuszewski, K; Hawkins, M E; Cole, J L; Mukerji, I

    2001-02-27

    HU, a nonspecific histone-like DNA binding protein, participates in a number of genomic events as an accessory protein and forms multiple complexes with DNA. The HU-DNA binding interaction was characterized by fluorescence, generated with the guanosine analogue 3-methyl-8-(2-deoxy-beta-D-ribofuranosyl)isoxanthopterin (3-MI) directly incorporated into DNA duplexes. The stoichiometry and equilibrium binding constants of complexes formed between HU and 13 and 34 bp DNA duplexes were determined using fluorescence anisotropy and analytical ultracentrifugation. These measurements reveal that three HU molecules bind to the 34 bp duplexes, while two HU molecules bind to the 13 bp duplex. The data are well described by an independent binding site model, and the association constants for the first binding event for both duplexes are similar (approximately 1 x 10(6) M(-1)), indicating that HU binding affinity is independent of duplex length. Further analysis of the binding curves in terms of a nonspecific binding model is indicative that HU binding to DNA exhibits little to no cooperativity. The fluorescence intensity also increases upon HU binding, consistent with decreased base stacking and increased solvent exposure of the 3-MI fluorescence probe. These results are suggestive of a local bending or unwinding of the DNA. On the basis of these results we propose a model in which bending of DNA accompanies HU binding. Up to five complex bands are observed in gel mobility shift assays of HU binding to the 34 bp duplexes. We suggest that protein-induced bending of the DNA leads to the observation of complexes in the gel, which have the same molecular weight but different relative mobilities. PMID:11327882

  6. 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, -Δ c H o = 27334.06 ± 50.98 kJ/mol and Δf H o = 3062.90 ± 50.97 kJ/mol.

  7. Formation of complexes between PAMAM-NH2 G4 dendrimer and L-α-tryptophan and L-α-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-α-tryptophan and L-α-tyrosine in water. The number of L-α-tryptophan and L-α-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-α-tryptophan molecules with equilibrium constant K equal to 130 ± 30 and 24 ± 6 L-α-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-α-tryptophan. Our date confirmed the interactions of L-α-tryptophan and L-α-tyrosine with the dendrimer in aqueous solution and indicated a reversible character of the formed complexes.

  8. True boundary for the formation of homoleptic transition-metal hydride complexes.

    PubMed

    Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Aoki, Katsutoshi; Orimo, Shin-ichi

    2015-05-01

    Despite many exploratory studies over the past several decades, the presently known transition metals that form homoleptic transition-metal hydride complexes are limited to the Groups 7-12. Here we present evidence for the formation of Mg3 CrH8 , containing the first Group 6 hydride complex [CrH7 ](5-) . Our theoretical calculations reveal that pentagonal-bipyramidal H coordination allows the formation of σ-bonds between H and Cr. The results are strongly supported by neutron diffraction and IR spectroscopic measurements. Given that the Group 3-5 elements favor ionic/metallic bonding with H, along with the current results, the true boundary for the formation of homoleptic transition-metal hydride complexes should be between Group 5 and 6. As the H coordination number generally tends to increase with decreasing atomic number of transition metals, the revised boundary suggests high potential for further discovery of hydrogen-rich materials that are of both technological and fundamental interest. PMID:25773066

  9. Novel checkpoint response to genotoxic stress mediated by nucleolin-replication protein a complex formation.

    PubMed

    Kim, Kyung; Dimitrova, Diana D; Carta, Kristine M; Saxena, Anjana; Daras, Mariza; Borowiec, James A

    2005-03-01

    Human replication protein A (RPA), the primary single-stranded DNA-binding protein, was previously found to be inhibited after heat shock by complex formation with nucleolin. Here we show that nucleolin-RPA complex formation is stimulated after genotoxic stresses such as treatment with camptothecin or exposure to ionizing radiation. Complex formation in vitro and in vivo requires a 63-residue glycine-arginine-rich (GAR) domain located at the extreme C terminus of nucleolin, with this domain sufficient to inhibit DNA replication in vitro. Fluorescence resonance energy transfer studies demonstrate that the nucleolin-RPA interaction after stress occurs both in the nucleoplasm and in the nucleolus. Expression of the GAR domain or a nucleolin mutant (TM) with a constitutive interaction with RPA is sufficient to inhibit entry into S phase. Increasing cellular RPA levels by overexpression of the RPA2 subunit minimizes the inhibitory effects of nucleolin GAR or TM expression on chromosomal DNA replication. The arrest is independent of p53 activation by ATM or ATR and does not involve heightened expression of p21. Our data reveal a novel cellular mechanism that represses genomic replication in response to genotoxic stress by inhibition of an essential DNA replication factor. PMID:15743838

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Formation and Recondensation of Complex Organic Molecules during Protostellar Luminosity Outbursts

    NASA Astrophysics Data System (ADS)

    Taquet, Vianney; Wirström, Eva S.; Charnley, Steven B.

    2016-04-01

    During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion-molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

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

    PubMed

    Vallet, Valérie; 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

  17. 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

  18. 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

  19. Thermodynamics of formation for the 18-crown-6-triglycine molecular complex in water-dimethylsulfoxide solvents

    NASA Astrophysics Data System (ADS)

    Usacheva, T. R.; Lan, Pham Thi; Sharnin, V. A.

    2014-06-01

    The effect of a water-dimethylsulfoxide (DMSO) solvent on the formation of a molecular complex of 18-crown-6 (18C6) with triglycine (diglycylglycine, 3Gly) is studied via calorimetric titration. It is found that switching from water to an H2O-DMSO mixture with DMSO mole fraction of 0.30 is accompanied by a monotonic increase in the stability of [3Gly18C6] complex, from log K ∘ = 1.10 to log K ∘ = 2.44, and an increase in the exothermicity of the reaction of its formation, from -5.9 to -16.9 kJ/mol. It is shown that the [3Gly18C6] complex exhibits enthalpy stabilization with negative values of enthalpy and entropy over the investigated range of H2O-DMSO solvents. Analysis of the reagents' solvation characteristics reveals that the increase in the reaction's exothermicity of transfer is due to differences in the solvation of [3Gly18C6] and 18C6 with a small solvation contribution from 3Gly. It is concluded that the change in the Gibbs energy of the reaction 3Glysolv + 18C6solv ↔ [3Gly18C6]solv is due to differences in the change in the solvation state of the complex and the peptide (Δtr G ∘([3Gly18C6])-Δtr G ∘(3Gly)).

  20. 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

  1. 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

  2. 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

  3. 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.

  4. 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

  5. Germ cell differentiation and synaptonemal complex formation are disrupted in CPEB knockout mice.

    PubMed

    Tay, J; Richter, J D

    2001-08-01

    CPEB is a sequence-specific RNA binding protein that regulates translation during vertebrate oocyte maturation. Adult female CPEB knockout mice contained vestigial ovaries that were devoid of oocytes; ovaries from mid-gestation embryos contained oocytes that were arrested at the pachytene stage. Male CPEB null mice also contained germ cells arrested at pachytene. The germ cells from the knockout mice harbored fragmented chromatin, suggesting a possible defect in homologous chromosome adhesion or synapsis. Two CPE-containing synaptonemal complex protein mRNAs, which interact with CPEB in vitro and in vivo, contained shortened poly(A) tails and mostly failed to sediment with polysomes in the null mice. Synaptonemal complexes were not detected in these animals. CPEB therefore controls germ cell differentiation by regulating the formation of the synaptonemal complex. PMID:11702780

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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 1.00-7.00μgmL(-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

  11. Toward a Reduced Complexity Channel Resolving Model for Sedimentary Delta Formation

    NASA Astrophysics Data System (ADS)

    Liang, M.; Voller, V. R.; Edmonds, D. A.; Paola, C.

    2010-12-01

    Predicting styles of delta growth in restoration areas is a challenge as we try to restore impacted coastlines. Cellular and rule-based reduced complexity models offer a worthwhile means of uncovering key dynamics in delta morphodynamics without the need to fully solve the governing transport equations. In terms of modeling sedimentary delta building processes a critical ingredients is accounting for the formation and bifurcation of channels; phenomena that can be related to the formation of levees and mouth-bars. To that end, we have developed a reduced complexity model that uses a simplified shallow-water solver to study channel formation, mouth bar deposition, and delta development under different forcings. Under the assumption that the flow has a very low Froude Number (Fr2<<1), the inertia term is dropped out and only the gravitational term and friction term remain in the momentum equation. The coupled mass conservation equation becomes a non-linear diffusive equation, which is linearized by a Kirchhoff transformation. Directional diffusivity is added to this system to compensate the loss of inertia and promote spreading of the turbulent jet. We test the reduced model against flow over Gaussian-shaped bumps of various heights. Comparison of results from this model with results from a full scale commercial code (Delft3D) show a satisfactory agreement on the critical mouth bar height needed to divert flow around the bar. Based on the same diffusive equation, we develop a low-Froude water-routing method for reduced complexity morphodynamics models. The preliminary results show that the method is capable of producing reasonable channel forms and mouth bar formation, and provides a good starting point for development of a channel resolving delta building model.

  12. Tautomerization in the formation and collision-induced dissociation of alkali metal cation-cytosine complexes.

    PubMed

    Yang, Zhibo; Rodgers, M T

    2012-04-01

    Noncovalent interactions between alkali metal cations and the various low-energy tautomeric forms of cytosine are investigated both experimentally and theoretically. Threshold collision-induced dissociation (CID) of M(+)(cytosine) complexes with Xe is studied using guided ion beam tandem mass spectrometry, where M(+) = Li(+), Na(+), and K(+). In all cases, the only dissociation pathway observed corresponds to endothermic loss of the intact cytosine molecule. The cross-section thresholds are interpreted to yield 0 and 298 K bond dissociation energies (BDEs) for the M(+)(cytosine) complexes after accounting for the effects of multiple ion-neutral collisions, the kinetic and internal energy distributions of the reactants, and dissociation lifetimes. Ab initio calculations are performed at the MP2(full)/6-31G* level of theory to determine the structures of the neutral cytosine tautomers, the M(+)(cytosine) complexes, and the TSs for unimolecular tautomerization. The molecular parameters derived from these structures are employed for the calculation of the unimolecular rates for tautomerization and the thermochemical analysis of the experimental data. Theoretical BDEs of the various M(+)(cytosine) complexes and the energy barriers for the unimolecular tautomerization of these complexes are determined at MP2(full)/6-311+G(2d,2p) level of theory using the MP2(full)/6-31G* optimized geometries. In addition, BDEs for the Li(+)(cytosine) complexes are also determined at the G3 level of theory. Based upon the tautomeric mixture generated upon thermal vaporization of cytosine, calculated M(+)-cytosine BDEs and barriers to tautomerization for the low-energy tautomeric forms of M(+)(cytosine), and measured thresholds for CID of M(+)(cytosine) complexes, we conclude that tautomerization occurs during both complex formation and CID. PMID:22361913

  13. 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.

  14. A chiral ligand exchange CE essay with zinc(II)-L-valine complex for determining enzyme kinetic constant of L-amino acid oxidase.

    PubMed

    Qi, Li; Yang, Gengliang; Zhang, Haizhi; Qiao, Juan

    2010-06-15

    A new strategy for the enantioseparation of D,L-amino acids employing the principle of ligand exchange capillary electrophoresis with Zn(II)-L-valine complex as a chiral selecting system in the presence of beta-cyclodextrin has been designed. Successful enantioseparation of label free and labeled amino acids have been achieved with a buffer of 100.0mM boric acid, 5.0mM ammonium acetate, 4.0mM beta-cyclodextrin, 4.0mM ZnSO(4) and 8.0mM L-valine at pH 8.1. This new method was shown to be applicable to the quantitative analysis of label free D- and L-aromatic amino acids. Furthermore, the expanding enzymatic use of L-amino acid oxidase to incubate with different L-amino acids has allowed understanding of the substrate's specificity. An on-column incubation assay has been developed to study the L-amino acid oxidase's catalytic efficiency. It was demonstrated that the enzyme kinetic constant could be determined by using this new method. PMID:20441938

  15. In vivo dynamics of chromatin-associated complex formation in mammalian nucleotide excision repair

    PubMed Central

    Moné, 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

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. Rate of carotenoid triplet formation in solubilized light-harvesting complex II (LHCII) from spinach.

    PubMed Central

    Schödel, R; Irrgang, K D; Voigt, J; Renger, G

    1998-01-01

    In the present study the rate of triplet transfer from chlorophyll to carotenoids in solubilized LHCII was investigated by flash spectroscopy using laser pulses of approximately 2 ns for both pump and probe. Special attention has been paid to calibration of the experimental setup and to avoid saturation effects. Carotenoid triplets were identified by the pronounced positive peak at approximately 507 nm in the triplet-singlet difference spectra. DeltaOD (507 nm) exhibits a monoexponential relaxation kinetics with characteristic lifetimes of 2-9 micros (depending on the oxygen content) that was found to be independent of the pump pulse intensity. The rise of DeltaOD (507 nm) was resolved via a pump probe technique where an optical delay of up to 20 ns was used. A thorough analysis of these experimental data leads to the conclusion that the kinetics of carotenoid triplet formation in solubilized LHCII is almost entirely limited by the lifetime of the excited singlet state of chlorophyll but neither by the pulse width nor by the rate constant of triplet-triplet transfer. Within the experimental error the rate constant of triplet-triplet transfer from chlorophyll to carotenoids was estimated to be kTT > (0.5 ns)-1. This value exceeds all data reported so far by at least one order of magnitude. The implications of this finding are briefly discussed. PMID:9826635

  1. Complex Formation and Interactions between Transcription Factors Essential for Human Prolactin Receptor Gene Transcription ▿

    PubMed Central

    Kang, Jung-Hoon; Tsai-Morris, Chon-Hwa; Dufau, Maria L.

    2011-01-01

    The protein association of estrogen receptor α ERα with DNA-bound SP1 and C/EBPβ is essential for the 17β-estradiol (E2)-induced activation of human prolactin receptor (hPRLR) gene transcription. Protein-protein interaction and complex formation at the hPIII promoter of hPRLR was investigated. The basic region and leucine zipper (bZIP) of C/EBPβ, zinc finger (ZF) motifs of SP1, and the DNA binding domain of ERα were identified as regions responsible for the interactions between transfactors. The E2-induced interaction was confirmed by bioluminescence resonance energy transfer (BRET) assays of live cells. The combination of BRET/bimolecular luminescence complementation assay revealed that ERα exists as a constitutive homodimer, and E2 induced a change(s) in ERα homodimer conformation favorable for its association with C/EBPβ and SP1. Chromatin immunoprecipitation and small interfering RNA knockdown of members of the complex in breast cancer cells demonstrated the endogenous recruitment of components of the complex onto the hPIII promoter of the hPRLR gene. SP1 is the preferred transfactor for the recruitment of ERα to the complex that facilitates the C/EBPβ association. The E2/ERα-induced hPRLR transcription was demonstrated in ERα-negative breast cancer cells. This study indicates that the enhanced complex formation of ERα dimer with SP1 and C/EBPβ by E2 has an essential role in the transcriptional activation of the hPRLR gene. PMID:21670145

  2. Formation of host-guest complexes of β-cyclodextrin and perfluorooctanoic acid.

    PubMed

    Karoyo, Abdalla H; Borisov, Alex S; Wilson, Lee D; Hazendonk, Paul

    2011-08-11

    Structural characterization and dynamic properties of solid-state inclusion complexes of β-cyclodextrin (β-CD) with perfluorooctanoic acid (PFOA) were investigated by (19)F/(13)C solid-state and (19)F/(1)H solution NMR spectroscopy. The complexes in the solid state were prepared using dissolution and slow cool methods, where thermal analyses (DSC and TGA), PXRD, and FT-IR results provided complementary support that inclusion complexes were formed between β-CD and PFOA with variable stoichiometry and inclusion geometry. (19)F DP (direct polarization) and (13)C CP (cross-polarization) with magic-angle spinning (MAS) solids NMR, along with (19)F/(1)H solution NMR were used to characterize the complexes in the solid and solution phases, respectively. The dynamics of the guest molecules in the inclusion complexes (ICs) were studied using variable temperature (VT) (19)F DP/MAS NMR experiments in the solid state. The guest molecules were observed to be in several different molecular environments, providing strong evidence of variable host-guest stoichiometry and inclusion geometry, in accordance with the preparation method of the complex and the conformational preference of PFOA. It was concluded from PXRD that β-CD and PFOA form inclusion complexes with "channel-type" structures. Variable spin rate (VSR) (19)F DP/MAS NMR was used to assess the phase purity of the complexes, and it was revealed that slow cooling resulted in relatively pure phases. In the solution state, (1)H and (19)F NMR complexation-induced chemical shifts (CISs) of β-CD and PFOA, respectively, provided strong support for the formation of 1:1 and 2:1 β-CD/PFOA inclusion complexes. The dynamics of the guest molecule in the β-CD/PFOA complexes in D(2)O solutions were probed using VT (19)F NMR and revealed some guest conformational and exchange dynamics as a function of temperature and the relative concentrations of the host and guest. PMID:21688796

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. Drop formation, pinch-off dynamics and liquid transfer of simple and complex fluids

    NASA Astrophysics Data System (ADS)

    Dinic, Jelena; Sharma, Vivek

    Liquid transfer and drop formation processes underlying jetting, spraying, coating, and printing - inkjet, screen, roller-coating, gravure, nanoimprint hot embossing, 3D - often involve formation of unstable columnar necks. Capillary-driven thinning of such necks and their pinchoff dynamics are determined by a complex interplay of inertial, viscous and capillary stresses for simple, Newtonian fluids. Micro-structural changes in response to extensional flow field that arises within the thinning neck give rise to additional viscoelastic stresses in complex, non- Newtonian fluids. Using FLOW-3D, we simulate flows realized in prototypical geometries (dripping and liquid bridge stretched between two parallel plates) used for studying pinch-off dynamics and influence of microstructure and viscoelasticity. In contrast with often-used 1D or 2D models, FLOW-3D allows a robust evaluation of the magnitude of the underlying stresses and extensional flow field (both uniformity and magnitude). We find that the simulated radius evolution profiles match the pinch-off dynamics that are experimentally-observed and theoretically-predicted for model Newtonian fluids and complex fluids.

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

    PubMed

    Pallagi, Attila; Bajnóczi, Éva G; Canton, Sophie E; Bolin, Trudy; Peintler, Gábor; Kutus, Bence; Kele, Zoltán; Pálinkó, István; Sipos, Pál

    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 β213 = 8.03) and [Ca3Gluc2(OH)4](0) (log β324 = 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

  9. Inhibition of a Golgi Complex Lysophospholipid Acyltransferase Induces Membrane Tubule Formation and Retrograde Trafficking

    PubMed Central

    Drecktrah, Daniel; Chambers, Kimberly; Racoosin, Esther L.; Cluett, Edward B.; Gucwa, Amy; Jackson, Brian; Brown, William J.

    2003-01-01

    Recent studies have suggested that formation of Golgi membrane tubules involves the generation of membrane-associated lysophospholipids by a cytoplasmic Ca2+-independent phospholipase A2 (PLA2). Herein, we provide additional support for this idea by showing that inhibition of lysophospholipid reacylation by a novel Golgi-associated lysophosphatidylcholine acyltransferase (LPAT) induces the rapid tubulation of Golgi membranes, leading in their retrograde movement to the endoplasmic reticulum. Inhibition of the Golgi LPAT was achieved by 2,2-dimethyl-N-(2,4,6-trimethoxyphenyl)dodecanamide (CI-976), a previously characterized antagonist of acyl-CoA cholesterol acyltransferase. The effect of CI-976 was similar to that of brefeldin A, except that the coatomer subunit β-COP remained on Golgi-derived membrane tubules. CI-976 also enhanced the cytosol-dependent formation of tubules from Golgi complexes in vitro and increased the levels of lysophosphatidylcholine in Golgi membranes. Moreover, preincubation of cells with PLA2 antagonists inhibited the ability of CI-976 to induce tubules. These results suggest that Golgi membrane tubule formation can result from increasing the content of lysophospholipids in membranes, either by stimulation of a PLA2 or by inhibition of an LPAT. These two opposing enzyme activities may help to coordinately regulate Golgi membrane shape and tubule formation. PMID:12925777

  10. Cloud fluid compression and softening in spiral arms and the formation of giant molecular cloud complexes

    NASA Technical Reports Server (NTRS)

    Cowie, L. L.

    1981-01-01

    With regard to the galactodynamics of the cloudy interstellar medium, the paper considers the response of such a gas to a forcing potential in the tight-winding density wave theory. The cloud fluid is treated in the hydrodynamic limit with an equation of state which softens at high densities. It is shown that in the inner regions of the galaxy, cooling of the cloud fluid in the arms can result in gravitational instability and the formation of large bound complexes of clouds which are identified with the giant molecular clouds (GMCs). Masses, dimensions, distributions, and scale heights of the GMCs are predicted by the theory. It is suggested that the interstellar gas density in the disk is regulated by the gravitational instability mechanism in the arms which siphons material into star formation. Implications for the evolution of individual GMCs and for galactic morphology are discussed.

  11. 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.

  12. 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

  13. 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

  14. 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.

  15. Mechanism of water splitting and oxygen-oxygen bond formation by a mononuclear ruthenium complex.

    PubMed

    Yang, Xinzheng; Hall, Michael B

    2010-01-13

    Density functional theory (DFT) predicts a detailed mechanism for the reported potential photocatalytic system for solar hydrogen production from water, (P-da-PNN)RuH(CO) (1, P-da = dearomatized at the phosphorus side arm, PNN = (2-(di-tert-butylphosphinomethyl)-6-diethylaminomethyl)pyridine) (Science 2009, 324, 74). In the initial thermal reaction, the coordination of a water molecule is followed by cleavage of an O-H bond and aromatization of the PNN ligand to form (PNN)RuH(CO)(OH) (3'), the most stable complex in the reaction. This low-barrier step is followed by the rate-determining dearomatization and formation of H(2). Next, a second water molecule is activated, resulting in the formation of the cis-dihydroxo complex (PNN)Ru(CO)(OH)(2) (7), which photolytically eliminates H(2)O(2). Time-dependent DFT calculations predict that the breaking of the two strong Ru-O bonds and the formation of the O-O bond in this photolytic reaction involve low-energy triplet states and singlet-triplet crossings. Rather than regeneration of initial complex 1 after the light-induced H(2)O(2) evolution in the catalytic cycle, the DFT calculations predict a new route with a lower energy barrier via the regeneration of 1', an isomer of 1 with the unsaturated carbon at the nitrogen side arm of the PNN ligand. This new route involves hydride transfer from the methylene group at the nitrogen side, rather than the previously proposed regeneration of 1 through hydride transfer from the phosphorus side arm of the PNN ligand. PMID:19957936

  16. Effect of fat type in baked bread on amylose-lipid complex formation and glycaemic response.

    PubMed

    Lau, Evelyn; Zhou, Weibiao; Henry, Christiani Jeyakumar

    2016-06-01

    The formation of amylose-lipid complexes (ALC) had been associated with reduced starch digestibility. A few studies have directly characterised the extent of ALC formation with glycaemic response. The objectives of this study were to investigate the effect of using fats with varying degree of saturation and chain length on ALC formation as well as glycaemic and insulinaemic responses after consumption of bread. Healthy men consumed five test breads in a random order: control bread without any added fats (CTR) and breads baked with butter (BTR), coconut oil (COC), grapeseed oil (GRP) or olive oil (OLV). There was a significant difference in glycaemic response between the different test breads (P=0·002), primarily due to COC having a lower response than CTR (P=0·016), but no significant differences between fat types were observed. Insulinaemic response was not altered by the addition of fats/oils. Although BTR was more insulinotropic than GRP (P<0·05), postprandial β-cell function did not differ significantly. The complexing index (CI), a measure of ALC formation, was significantly higher for COC and OLV compared with BTR and GRP (P<0·05). CI was significantly negatively correlated with incremental AUC (IAUC) of change in blood glucose concentrations over time (IAUCglucose) (r -0·365, P=0·001). Linear regression analysis showed that CI explained 13·3 % of the variance and was a significant predictor of IAUCglucose (β=-1·265, P=0·001), but IAUCinsulin did not predict IAUCglucose. Our study indicated that a simple way to modulate glycaemic response in bread could lie in the choice of fats/oils, with coconut oil showing the greatest attenuation of glycaemic response. PMID:27102847

  17. 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.

  18. Doping and impurity-vacancy complex formation during vapour-phase epitaxy of gallium arsenide

    NASA Astrophysics Data System (ADS)

    Bobrovnikova, I. A.; Lavrent'eva, L. G.; Rusaikin, M. P.; Vilisova, M. D.

    1992-10-01

    The kinetics of the incorporation of impurities in the form of donors, acceptors and impurity-vacancy complexes (IVC) was studied experimentally for VPE GaAs doped with group IV and group VI impurities (Ge, Sn, S, Te). It was found that the concentration of donors increases linearly, whereas the IVC concentration appears to increase quadrically with the impurity pressure. A model of impurity incorporation is discussed, according to which the simple substitution occurs due to the capture of absorbed atoms, and the IVC formation is caused by the capture of adsorbed diatomic impurity molecules with their subsequent dissociation.

  19. 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

  20. Arachidonic acid stimulates formation of a novel complex containing nucleolin and RhoA.

    PubMed

    Garcia, Melissa C; Williams, Jason; Johnson, Katina; Olden, Kenneth; Roberts, John D

    2011-02-18

    Arachidonic acid (AA) stimulates cell adhesion through a p38 mitogen activated protein kinase-mediated RhoA signaling pathway. Here we report that a proteomic screen following AA-treatment identified nucleolin, a multifunctional nucleolar protein, in a complex with the GTPase, RhoA, that also included the Rho kinase, ROCK. AA-stimulated cell adhesion was inhibited by expression of nucleolin-targeted shRNA and formation of the multiprotein complex was blocked by expression of dominant-negative RhoA. AA-treatment also induced ROCK-dependent serine phosphorylation of nucleolin and translocation of nucleolin from the nucleus to the cytoplasm, where it appeared to co-localize with RhoA. These data suggest the existence of a new signaling pathway through which the location and post-translational state of nucleolin are modulated. PMID:21281639

  1. 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

  2. Cadmium(II) N-acetylcysteine complex formation in aqueous solution.

    PubMed

    Jalilehvand, Farideh; Amini, Zahra; Parmar, Karnjit; Kang, Eun Young

    2011-12-21

    The complex formation between Cd(II) ions and N-acetylcysteine (H(2)NAC) in aqueous solution was investigated using Cd K- and L(3)-edge X-ray absorption and (113)Cd NMR spectroscopic techniques. Two series of 0.1 M Cd(II) solutions with the total N-acetylcysteine concentration c(H2NAC) varied between 0.2-2 M were studied at pH 7.5 and 11.0, respectively. At pH = 11 a novel mononuclear [Cd(NAC)(4)](6-) complex with the average Cd-S distance 2.53(2) Å and the chemical shift δ((113)Cd) = 677 ppm was found to dominate at a concentration of the free deprotonated ligand [NAC(2-)] > 0.1 M, consistent with our previous reports on cadmium tetrathiolate complex formation with cysteine and glutathione. At pH 7.5 much higher ligand excess ([HNAC(-)] > 0.6 M) is required to make this tetrathiolate complex the major species. The (113)Cd NMR spectrum of a solution containing c(Cd(II)) = 0.5 M and c(H2NAC) = 1.0 M measured at 288 K showed three broad signals at 421, 583 and 642 ppm, which can be attributed to CdS(3)O(3), CdS(3)O and CdS(4) coordination sites, respectively, in oligomeric Cd(II)-NAC species with single thiolate bridges between the cadmium ions. PMID:22012146

  3. 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.

  4. Structure of Soybean Serine Acetyltransferase and Formation of the Cysteine Regulatory Complex as a Molecular Chaperone*

    PubMed Central

    Yi, Hankuil; Dey, Sanghamitra; Kumaran, Sangaralingam; Lee, Soon Goo; Krishnan, Hari B.; Jez, Joseph M.

    2013-01-01

    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. Formation of the cysteine regulatory complex (CRC) is a critical biochemical control feature in plant sulfur metabolism. Here we present the 1.75–3.0 Å resolution x-ray crystal structures of soybean (Glycine max) SAT (GmSAT) in apoenzyme, serine-bound, and CoA-bound forms. The GmSAT-serine and GmSAT-CoA structures provide new details on substrate interactions in the active site. The crystal structures and analysis of site-directed mutants suggest that His169 and Asp154 form a catalytic dyad for general base catalysis and that His189 may stabilize the oxyanion reaction intermediate. Glu177 helps to position Arg203 and His204 and the β1c-β2c loop for serine binding. A similar role for ionic interactions formed by Lys230 is required for CoA binding. The GmSAT structures also identify Arg253 as important for the enhanced catalytic efficiency of SAT in the CRC and suggest that movement of the residue may stabilize CoA binding in the macromolecular complex. Differences in the effect of cold on GmSAT activity in the isolated enzyme versus the enzyme in the CRC were also observed. A role for CRC formation as a molecular chaperone to maintain SAT activity in response to an environmental stress is proposed for this multienzyme complex in plants. PMID:24225955

  5. 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 60-100°C/km to 35-60°C/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.

  6. Asymmetrical macromolecular complex formation of lysophosphatidic acid receptor 2 (LPA2) mediates gradient sensing in fibroblasts.

    PubMed

    Ren, Aixia; Moon, Changsuk; Zhang, Weiqiang; Sinha, Chandrima; Yarlagadda, Sunitha; Arora, Kavisha; Wang, Xusheng; Yue, Junming; Parthasarathi, Kaushik; Heil-Chapdelaine, Rick; Tigyi, Gabor; Naren, Anjaparavanda P

    2014-12-26

    Chemotactic migration of fibroblasts toward growth factors relies on their capacity to sense minute extracellular gradients and respond to spatially confined receptor-mediated signals. Currently, mechanisms underlying the gradient sensing of fibroblasts remain poorly understood. Using single-particle tracking methodology, we determined that a lysophosphatidic acid (LPA) gradient induces a spatiotemporally restricted decrease in the mobility of LPA receptor 2 (LPA2) on chemotactic fibroblasts. The onset of decreased LPA2 mobility correlates to the spatial recruitment and coupling to LPA2-interacting proteins that anchor the complex to the cytoskeleton. These localized PDZ motif-mediated macromolecular complexes of LPA2 trigger a Ca(2+) puff gradient that governs gradient sensing and directional migration in response to LPA. Disruption of the PDZ motif-mediated assembly of the macromolecular complex of LPA2 disorganizes the gradient of Ca(2+) puffs, disrupts gradient sensing, and reduces the directional migration of fibroblasts toward LPA. Our findings illustrate that the asymmetric macromolecular complex formation of chemoattractant receptors mediates gradient sensing and provides a new mechanistic basis for models to describe gradient sensing of fibroblasts. PMID:25542932

  7. 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

  8. Multinuclear NMR studies of the formation of platinum(II)-adenine nucleotide complexes

    SciTech Connect

    Viola, R.E.; Bose, R.N.; Cornelius, R.D.

    1986-05-01

    There has been considerable interest in the mode of interaction of the simple antitumor agent cis-platin (cis-dichlorodiammineplatinum(II)) with nucleic acids. The authors have recently shown that Pt(II) has a high affinity for inorganic phosphate and polyphosphate ligands, and forms a variety of species that have been characterized. Phosphorus-31, carbon-13, and proton NMR studies of the adenine nucleotide complexes of Pt(II) have shown that the phosphate groups of these ligands do play a role in metal ion binding, in contrast to previous work that had indicated no interaction of the phosphate oxygens with PT(II). Kinetic studies have indicated that Pt(II) binding is a two-step process in which the initial complex that is formed is slowly converted to the final products. NMR studies have suggested that a phosphate-bound intermediate is formed initially, since coordination shifts due to complex formation are observed in the /sup 31/P spectra at an early stage in the reaction time course, while shifts are observed considerably later in the proton spectra. At least two final products are observed in the binding of Pt(II) to either AMP, ADP, or ATP. All of the final Pt(II) nucleotide complexes appear to involve interactions with the phosphate groups.

  9. Hedgehog induces formation of PKA-Smoothened complexes to promote Smoothened phosphorylation and pathway activation

    PubMed Central

    Li, Shuang; Ma, Guoqiang; Wang, Bing; Jiang, Jin

    2015-01-01

    Hedgehog (Hh) is a secreted glycoprotein that binds its receptor Patched to activate the G protein-coupled receptor-like protein Smoothened (Smo). In Drosophila, protein kinase A (PKA) phosphorylates and activates Smo in cells stimulated with Hh. In unstimulated cells, PKA phosphorylates and inhibits the transcription factor Cubitus interruptus (Ci). Here, we found that in cells exposed to Hh, the catalytic subunit of PKA (PKAc) bound to the juxtamembrane region of the C terminus of Smo. PKA-mediated phosphorylation of Smo further enhanced its association with PKAc to form stable kinase-substrate complexes that promoted the PKA-mediated trans-phosphorylation of Smo dimers. We identified multiple basic residues in the C-terminus of Smo that were required for interaction with PKAc, Smo phosphorylation, and Hh pathway activation. Hh induced a switch from the association of PKAc with a cytosolic complex of Ci and the kinesin-like protein Costal2 (Cos2) to a membrane-bound Smo-Cos2 complex. Thus, our study uncovers a previously uncharacterized mechanism for regulation of PKA activity and demonstrates that the signal-regulated formation of kinase-substrate complexes plays a central role in Hh signal transduction. PMID:24985345

  10. Asymmetrical Macromolecular Complex Formation of Lysophosphatidic Acid Receptor 2 (LPA2) Mediates Gradient Sensing in Fibroblasts*

    PubMed Central

    Ren, Aixia; Moon, Changsuk; Zhang, Weiqiang; Sinha, Chandrima; Yarlagadda, Sunitha; Arora, Kavisha; Wang, Xusheng; Yue, Junming; Parthasarathi, Kaushik; Heil-Chapdelaine, Rick; Tigyi, Gabor; Naren, Anjaparavanda P.

    2014-01-01

    Chemotactic migration of fibroblasts toward growth factors relies on their capacity to sense minute extracellular gradients and respond to spatially confined receptor-mediated signals. Currently, mechanisms underlying the gradient sensing of fibroblasts remain poorly understood. Using single-particle tracking methodology, we determined that a lysophosphatidic acid (LPA) gradient induces a spatiotemporally restricted decrease in the mobility of LPA receptor 2 (LPA2) on chemotactic fibroblasts. The onset of decreased LPA2 mobility correlates to the spatial recruitment and coupling to LPA2-interacting proteins that anchor the complex to the cytoskeleton. These localized PDZ motif-mediated macromolecular complexes of LPA2 trigger a Ca2+ puff gradient that governs gradient sensing and directional migration in response to LPA. Disruption of the PDZ motif-mediated assembly of the macromolecular complex of LPA2 disorganizes the gradient of Ca2+ puffs, disrupts gradient sensing, and reduces the directional migration of fibroblasts toward LPA. Our findings illustrate that the asymmetric macromolecular complex formation of chemoattractant receptors mediates gradient sensing and provides a new mechanistic basis for models to describe gradient sensing of fibroblasts. PMID:25542932

  11. 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.

  12. Arp2/3 Complex Is Important for Filopodia Formation, Growth Cone Motility, and Neuritogenesis in Neuronal Cells

    PubMed Central

    Korobova, Farida

    2008-01-01

    A role of Arp2/3 complex in lamellipodia is well established, whereas its roles in filopodia formation remain obscure. We addressed this question in neuronal cells, in which motility is heavily based on filopodia, and we found that Arp2/3 complex is involved in generation of both lamellipodia and filopodia in growth cones, and in neuritogenesis, the processes thought to occur largely in Arp2/3 complex-independent manner. Depletion of Arp2/3 complex in primary neurons and neuroblastoma cells by small interfering RNA significantly decreased the F-actin contents and inhibited lamellipodial protrusion and retrograde flow in growth cones, but also initiation and dynamics of filopodia. Using electron microscopy, immunochemistry, and gene expression, we demonstrated the presence of the Arp2/3 complex-dependent dendritic network of actin filaments in growth cones, and we showed that individual actin filaments in filopodia originated at Arp2/3 complex-dependent branch points in lamellipodia, thus providing a mechanistic explanation of Arp2/3 complex functions during filopodia formation. Additionally, Arp2/3 complex depletion led to formation of multiple neurites, erratic pattern of neurite extension, and excessive formation of stress fibers and focal adhesions. Consistent with this phenotype, RhoA activity was increased in Arp2/3 complex-depleted cells, indicating that besides nucleating actin filaments, Arp2/3 complex may influence cell motility by altering Rho GTPase signaling. PMID:18256280

  13. 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

  14. 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

  15. 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…

  16. 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

  17. PROSTAGLANDIN E2 MODIFIES SMAD2 AND PROMOTES SMAD2-SMAD4 COMPLEX FORMATION

    PubMed Central

    Yang, Chen; Chen, Chen; Sorokin, Andrey

    2014-01-01

    We report that PGE2 promotes Smad2-Smad4 complex formation and this phenomenon could be blocked by DIDS, an anion transporter inhibitor. Our data suggest that PGE2 had no effects on Smad2 phosphorylation, suggesting that PGE2-mediated Smad2-Smad4 complex formation is independent of TGF-β signaling and that PGE2 induced Smad2 modification which is different from TGF-β-mediated phosphorylation. We demonstrate that in primary human glomerular mesangial cells PGE2 caused modification of Smad2 as detected by Smad2N antibody, raised against a peptide near the N-terminus of Smad2. We hypothesize that Smad2 protein is post-translationaly modified by PGE2. Direct evidence of Smad2 modification by PGE2 was achieved by avidin pulldown assay which showed that endogenous Smad2 and recombinant Smad2 protein were attached by biotin-labeled PGE2. Taken together, our results provided evidence that post-translational modification of Smad2 could be a mechanism for the action of PGE2 in the pathogenesis of human pathologies. PMID:24613014

  18. Rayleigh-Benard Natural Convection Heat Transfer: Pattern Formation, Complexity and Predictability

    SciTech Connect

    Dinh, T.N.; Yang, Y.Z.; Tu, J.P.; Nourgaliev, R.R.; Theofanous, T.G.

    2004-07-01

    This paper is concerned with fundamental issues in predicting the onset and pattern formation in Rayleigh-Benard thermal convection in a fluid layer heated from below. Theoretically, thermal convection has long been a challenging subject in physics because of the complexity embedded in such unstably stratified flows. Practically, Rayleigh-Benard convection is central to many technologies and situations. In particular, core melt progression in a hypothetical severe accident in a nuclear reactor is governed by heat transfer (and therefore energy splitting) in molten metal/oxide layers. In previous studies, we conducted large-scale experiments and numerical simulations to quantify melt pool heat transfer models. In the present study, we developed a novel experimental approach and used an advanced diagnostic method to obtain first-of-a-kind thermometry data on transient natural convection heat transfer. The data are used to assess whether and to what extent Navier-Stokes and energy equations and their numerical methods are capable of preserving and correctly predicting complexity in thermal convection, i.e. onset and pattern formation. Uncertainty of physical measurements and numerical solutions are discussed. (authors)

  19. 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.

  20. 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

  1. The thermodynamic parameters of complex formation between the copper(II) Ion and β-alanine in aqueous solution

    NASA Astrophysics Data System (ADS)

    Kochergina, L. A.; Drobilova, O. M.

    2008-09-01

    The heats of formation of β-alanine complexes with the doubly charged copper(II) ion were determined calorimetrically. The heat effects of interaction of a solution of the amino acid with a solution of copper(II) were measured at 288.15, 298.15, and 308.15 K and ionic strengths of 0.50, 0.75, and 1.00 against the background of KNO3. The heats of dilution of a solution of copper nitrate with solutions of the background electrolyte were also determined for the introduction of the corresponding corrections. The standard thermodynamic characteristics of complex formation were calculated. The influence of temperature on the thermal effects of complex formation in the β-alanine-copper(II) ions system were considered. The standard enthalpies of formation of CuAla+ and CuAla2 complex particles in aqueous solution were calculated.

  2. 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

  3. Frataxin Accelerates [2Fe-2S] Cluster Formation on the Human Fe-S Assembly Complex.

    PubMed

    Fox, Nicholas G; Das, Deepika; Chakrabarti, Mrinmoy; Lindahl, Paul A; Barondeau, David P

    2015-06-30

    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

  4. 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.

  5. PRELP Protein Inhibits the Formation of the Complement Membrane Attack Complex*

    PubMed Central

    Happonen, Kaisa E.; Fürst, Camilla Melin; Saxne, Tore; Heinegård, Dick; Blom, Anna M.

    2012-01-01

    PRELP is a 58-kDa proteoglycan found in a variety of extracellular matrices, including cartilage and at several basement membranes. In rheumatoid arthritis (RA), the cartilage tissue is destroyed and fragmented molecules, including PRELP, are released into the synovial fluid where they may interact with components of the complement system. In a previous study, PRELP was found to interact with the complement inhibitor C4b-binding protein, which was suggested to locally down-regulate complement activation in joints during RA. Here we show that PRELP directly inhibits all pathways of complement by binding C9 and thereby prevents the formation of the membrane attack complex (MAC). PRELP does not interfere with the interaction between C9 and already formed C5b-8, but inhibits C9 polymerization thereby preventing formation of the lytic pore. The alternative pathway is moreover inhibited already at the level of C3-convertase formation due to an interaction between PRELP and C3. This suggests that PRELP may down-regulate complement attack at basement membranes and on damaged cartilage and therefore limit pathological complement activation in inflammatory disease such as RA. The net outcome of PRELP-mediated complement inhibition will highly depend on the local concentration of other complement modulating molecules as well as on the local concentration of available complement proteins. PMID:22267731

  6. 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.

  7. Effects of the Preparation Method on the Formation of True Nimodipine SBE-β-CD/HP-β-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-β-CD) and 2-hydroxypropyl-b-cyclodextrin (HP-β-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-β-CD and ND/HP-β-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-β-CD and ND/HP-β-CD, respectively. The water-solubility of ND was significantly increased in an average of 22- and 8-fold for SBE-β-CD and HP-β-CD, respectively. DSC results showed the formation of true inclusion complexes between the drug and both SBE-β-CD and HP-β-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

  8. 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

  9. 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.

  10. 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

  11. BAG3 regulates formation of the SNARE complex and insulin secretion.

    PubMed

    Iorio, V; Festa, M; Rosati, A; Hahne, M; Tiberti, C; Capunzo, M; De Laurenzi, V; Turco, M C

    2015-01-01

    Insulin release in response to glucose stimulation requires exocytosis of insulin-containing granules. Glucose stimulation of beta cells leads to focal adhesion kinase (FAK) phosphorylation, which acts on the Rho family proteins (Rho, Rac and Cdc42) that direct F-actin remodeling. This process requires docking and fusion of secretory vesicles to the release sites at the plasma membrane and is a complex mechanism that is mediated by SNAREs. This transiently disrupts the F-actin barrier and allows the redistribution of the insulin-containing granules to more peripheral regions of the β cell, hence facilitating insulin secretion. In this manuscript, we show for the first time that BAG3 plays an important role in this process. We show that BAG3 downregulation results in increased insulin secretion in response to glucose stimulation and in disruption of the F-actin network. Moreover, we show that BAG3 binds to SNAP-25 and syntaxin-1, two components of the t-SNARE complex preventing the interaction between SNAP-25 and syntaxin-1. Upon glucose stimulation BAG3 is phosphorylated by FAK and dissociates from SNAP-25 allowing the formation of the SNARE complex, destabilization of the F-actin network and insulin release. PMID:25766323

  12. BAG3 regulates formation of the SNARE complex and insulin secretion

    PubMed Central

    Iorio, V; Festa, M; Rosati, A; Hahne, M; Tiberti, C; Capunzo, M; De Laurenzi, V; Turco, M C

    2015-01-01

    Insulin release in response to glucose stimulation requires exocytosis of insulin-containing granules. Glucose stimulation of beta cells leads to focal adhesion kinase (FAK) phosphorylation, which acts on the Rho family proteins (Rho, Rac and Cdc42) that direct F-actin remodeling. This process requires docking and fusion of secretory vesicles to the release sites at the plasma membrane and is a complex mechanism that is mediated by SNAREs. This transiently disrupts the F-actin barrier and allows the redistribution of the insulin-containing granules to more peripheral regions of the β cell, hence facilitating insulin secretion. In this manuscript, we show for the first time that BAG3 plays an important role in this process. We show that BAG3 downregulation results in increased insulin secretion in response to glucose stimulation and in disruption of the F-actin network. Moreover, we show that BAG3 binds to SNAP-25 and syntaxin-1, two components of the t-SNARE complex preventing the interaction between SNAP-25 and syntaxin-1. Upon glucose stimulation BAG3 is phosphorylated by FAK and dissociates from SNAP-25 allowing the formation of the SNARE complex, destabilization of the F-actin network and insulin release. PMID:25766323

  13. Ternary complex formation by vaccinia virus RNA polymerase at an early viral promoter: analysis by native gel electrophoresis.

    PubMed Central

    Hagler, J; Shuman, S

    1992-01-01

    We have resolved, by native gel electrophoresis, two intermediates in the transcription of a vaccinia virus early gene by the virus-encoded RNA polymerase. Polymerase holoenzyme containing the vaccinia virus early transcription factor (VETF) forms a complex of VETF bound to the promoter as the first step in a pathway leading to establishment of a committed ternary elongation complex. Formation of the VETF-DNA complex is stimulated by magnesium but is uninfluenced by nucleoside triphosphates. A stable binary complex of RNA polymerase bound to DNA is not detected. Assembly of a gel-stable polymerase-DNA complex depends on conditions permissive for RNA synthesis. Nucleotide omission experiments suggest that at least a tetrameric RNA must be made before a ternary complex is stabilized. RNA analysis indicates that complexes containing nascent transcripts 20 nucleotides long are stable and active. Ternary complex formation requires hydrolyzable ATP. This is consistent with an essential role for the ATPase activity of VETF at a step subsequent to DNA binding, as proposed by Broyles (S. S. Broyles, J. Biol. Chem. 266:15545-15548, 1991). The ternary complex, once formed, is resistant to dissociation by competitor DNA, as well as by salt, Sarkosyl, and heparin. The effects of these inhibitory agents on transcription complex formation suggest that they target different steps in the assembly pathway. Images PMID:1373199

  14. 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.

  15. 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

  16. Erythromycin, roxithromycin, and clarithromycin: use of slow-binding kinetics to compare their in vitro interaction with a bacterial ribosomal complex active in peptide bond formation.

    PubMed

    Dinos, George P; Connell, Sean R; Nierhaus, Knud H; Kalpaxis, Dimitrios L

    2003-03-01

    In a cell-free system derived from Escherichia coli, it is shown that clarithromycin and roxithromycin, like their parent compound erythromycin, do not inhibit the puromycin reaction (i.e., the peptide bond formation between puromycin and AcPhe-tRNA bound at the P-site of 70S ribosomes programmed with heteropolymeric mRNA). Nevertheless, all three antibiotics compete for binding on the ribosome with tylosin, a 16-membered ring macrolide that behaves as a slow-binding, slowly reversible inhibitor of peptidyltransferase. The mutually exclusive binding of these macrolides to ribosomes is also corroborated by the fact that they protect overlapping sites in domain V of 23S rRNA from chemical modification by dimethyl sulfate. From this competition effect, detailed kinetic analysis revealed that roxithromycin or clarithromycin (A), like erythromycin, reacts rapidly with AcPhe-tRNA.MF-mRNA x 70S ribosomal complex (C) to form the encounter complex CA which is then slowly isomerized to a more tight complex, termed C*A. The value of the overall dissociation constant, K, encompassing both steps of macrolide interaction with complex C, is 36 nM for erythromycin, 20 nM for roxithromycin, and 8 nM for clarithromycin. Because the off-rate constant of C*A complex does not significantly differ among the three macrolides, the superiority of clarithromycin as an inhibitor of translation in E. coli cells and many Gram-positive bacteria may be correlated with its greater rate of association with ribosomes. PMID:12606769

  17. 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

  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. Al-O complex formation in ion implanted Czochralski and floating-zone Si substrates

    NASA Astrophysics Data System (ADS)

    La Ferla, A.; Torrisi, L.; Galvagno, G.; Rimini, E.; Ciavola, G.; Carnera, A.; Gasparotto, A.

    1993-01-01

    Aluminum ions at 100 MeV were implanted into floating-zone (FZ) and Czochralski (CZ) grown Si substrates. At this energy the influence of the surface on the subsequent thermal treatment is negligible. In FZ samples the electrical active dose, as measured by spreading resistance profilometry, is independent of the annealing time at 1200 °C. In the CZ samples instead it considerably decreases with time. Secondary ion mass spectrometry analysis in CZ samples have revealed the presence of a multipeak structure around the projected range region for both Al and O signals. In FZ the structure is just detectable. The results imply that the Al-O complex formation is enhanced by the presence of oxygen but that it is catalyzed by the damage created during the implant. The carrier profiles coincide in both CZ and FZ diffused substrates by predeposition of Al from a solid source, i.e., in damage-free samples.

  20. Thermodynamics of Complex Sulfide Inclusion Formation in Ca-Treated Al-Killed Structural Steel

    NASA Astrophysics Data System (ADS)

    Guo, Yin-tao; He, Sheng-ping; Chen, Gu-jun; Wang, Qian

    2016-05-01

    Controlling the morphology of the sulfide inclusion is of vital importance in enhancing the properties of structural steel. Long strip-shaped sulfides in hot-rolled steel can spherize when, instead of the inclusion of pure single-phase MnS, the guest is a complex sulfide, such as an oxide-sulfide duplex and a solid-solution sulfide particle. In this study, the inclusions in a commercial rolled structural steel were investigated. Spherical and elongated oxide-sulfide duplex as well as single-phase (Mn,Ca)S solid solution inclusions were observed in the steel. A thermodynamic equilibrium between the oxide and sulfide inclusions was proposed to understand the oxide-sulfide duplex inclusion formation. Based on the equilibrium solidification principle, thermodynamic discussions on inclusion precipitation during the solidification process were performed for both general and resulfurized structural steel. The predicted results of the present study agreed well with the experimental ones.

  1. Spontaneous formation of complex structures made from elastic membranes in an aluminum-hydroxide-carbonate system.

    PubMed

    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. PMID:26117121

  2. 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.

  3. 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.

  4. 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 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

  5. Complexity in the Smallest Galaxies: Star Formation History of the Sculptor Dwarf Spheroidal

    NASA Astrophysics Data System (ADS)

    Cole, Andrew

    2006-07-01

    The Sculptor dwarf spheroidal galaxy {Scl dSph} is one of the most luminous of the Milky Way dSph satellites, suffers virtually no foreground confusion or reddening because of its high galactic latitude, and is nearby at 80 kpc from the Sun. It is of great interest to astronomy to understand the detailed histories of dSph galaxies because they may be survivors of the hierarchical merging process that created giant galaxies like our own. Despite this, the age distribution of stars in Scl dSph remains remarkably poorly constrained because of a dearth of high-quality color-magnitude diagrams {CMDs} of its central regions. Scl dSph is known to be complex on the basis of shallower photometry, radial velocity studies, and investigations of the metallicity; however, the age range of significant star-formation and the proportion of stars older and younger than 10 Gyr is still completely unknown. The age of the centrally concentrated, metal-rich population has never been measured. We propose to obtain deep optical images of the core of Scl dSph with WFPC2 in order to measure the temporal evolution of its star-formation rate over its entire lifetime. The ONLY way to reliably measure the variation in star-formation rate on Gyr timescales at ages of 10-13 Gyr is with photometry of a large number of stars at and below the oldest main-sequence turnoffs to magnitudes of {B,I} = {25.1, 24.5}. Because of the high stellar density and resulting image crowding, it is impossible to achieve the required level of photometric precision except with diffraction-limited imaging. These data will permit the first reliable measurement of the star-formation history of the main body of Scl dSph; limited inferences from WFPC2 data in an outer field have been made, but they were hindered not only by small number statistics but by the subsequent revelation of extremely strong population gradients in Scl dSph, such that the stars in the existing WFPC2 field are not representative of the galaxy as a whole. Our proposed program will shed strong new light on the formation processes of the smallest galaxies. Only by measuring the detailed early histories of galaxies like Scl dSph can we evaluate the impact of outside influences like ram-pressure stripping, tidal stirring, and photoionization feedback on the evolution of small galaxies.

  6. 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.

  7. 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

  8. When Does E = Mc2? Conditions Under Which Extension Leads To Metamorphic Core Complex Formation

    NASA Astrophysics Data System (ADS)

    Wijns, C.; Gessner, K.; Weinberg, R.; Moresi, L.

    Metamorphic core complexes (MC2) form during continental extension when stretch- ing is strongly localised onto relatively few normal fault systems, each accomodating large displacements, and resulting in exhumation of the lower crust. Extending litho- sphere is assumed to be mechanically stratified with a "weak" ductile lower crust overlain by a "strong" brittle upper crust. Our work shows that the formation of an MC2 may be a direct consequence of the localising nature of the rheological layering, rather than depending upon lateral rheological contrasts. In the absence of lateral het- erogeneities, the ratio of upper to lower crustal strength determines whether the upper crust is completely dissected (MC2 mode), or whether densely spaced faults occur, with limited slip on each fault, and no exposure of lower crustal rocks. We use a two-dimensional Lagrangian Integration Point finite element code to explore the different behaviours of the crust during extension. This particle-in-cell approach allows simulations to develop very large strains comparable to those found in analogue models, while still tracking strain history accurately for the constitutive laws. We con- sider viscoplastic materials with strain and/or strain-rate weakening behaviour, which gives rise to the localisation of deformation and necking of layers. Lateral hetero- geneities in intrinsic rock strength or in heat flow may be included, acting as nuclei for the formation of large-scale detachment faults. The Central Menderes metamorphic core complex in Turkey is the field example against which we match results of our simulations. We compare temperature-time paths and pressure-temperature paths with field data from apatite fission-track ther- mochronology in order to assess the numerical models.

  9. Solventless Formation of G-Quartet Complexes Based on Alkali and Alkaline Earth Salts on Au(111).

    PubMed

    Zhang, Chi; Wang, Likun; Xie, Lei; Kong, Huihui; Tan, Qinggang; Cai, Liangliang; Sun, Qiang; Xu, Wei

    2015-07-20

    Template cations have been extensively employed in the formation, stabilization and regulation of structural polymorphism of G-quadruplex structures in vitro. However, the direct addition of salts onto solid surfaces, especially under ultra-high-vacuum (UHV) conditions, to explore the feasibility and universality of the formation of G-quartet complexes in a solventless environment has not been reported. By combining UHV-STM imaging and DFT calculations, we have shown that three different G-quartet-M (M: Na/K/Ca) complexes can be obtained on Au(111) using alkali and alkaline earth salts as reactants. We have also identified the driving forces (intra-quartet hydrogen bonding and electrostatic ionic bonding) for the formation of these complexes and quantified the interactions involved. Our results demonstrate a novel route to fabricate G-quartet-related complexes on solid surfaces, providing an alternative feasible way to bring metal elements to surfaces for constructing metal-organic systems. PMID:25917128

  10. 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.

  11. Generalized additive models reveal the intrinsic complexity of wood formation dynamics.

    PubMed

    Cuny, Henri E; Rathgeber, Cyrille B K; Kiessé, Tristan Senga; Hartmann, Felix P; Barbeito, Ignacio; Fournier, Meriem

    2013-04-01

    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

  12. 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.

  13. 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

  14. 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.

  15. 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

  16. 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

  17. 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

  18. 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.

  19. Localization and dynamics of amylose-lipophilic molecules inclusion complex formation in starch granules.

    PubMed

    Manca, Marianna; Woortman, Albert J J; Mura, Andrea; Loos, Katja; Loi, Maria Antonietta

    2015-03-28

    Inclusion complex formation between lipophilic dye molecules and amylose polymers in starch granules is investigated using laser spectroscopy and microscopy. By combining confocal laser scanning microscopy (CLSM) with spatial resolved photoluminescence (PL) spectroscopy, we are able to discriminate the presence of amylose in the peripheral region of regular and waxy granules from potato and corn starch, associating a clear optical fingerprint with the interaction between starch granules and lipophilic dye molecules. We show in particular that in the case of regular starch the polar head of the lipophilic dye molecules remains outside the amylose helix experiencing a water-based environment. The measurements performed on samples that have been extensively washed provide a strong proof of the specific interaction between lipid dye molecules and amylose chains in regular starch. These measurements also confirm the tendency of longer amylopectin chains, located in the hilum of waxy starch granules, to form inclusion complexes with ligands. Through real-time recording of CLSM micrographs, within a time frame of tens of seconds, we measured the dynamics of occurrence of the inclusion process between lipids and amylose located at the periphery of starch granules. PMID:25715960

  20. 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.

    2013-09-03

    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.

  1. Affinity capillary electrophoresis to evaluate the complex formation between poliovirus and nanobodies.

    PubMed

    Halewyck, Hadewych; Schotte, Lise; Oita, Iuliana; Thys, Bert; Van Eeckhaut, Ann; Vander Heyden, Yvan; Rombaut, Bart

    2014-12-01

    It was demonstrated that nanobodies with an in vitro neutralizing activity against poliovirus type 1 interact with native virions. Here, the use of capillary electrophoresis was investigated as an alternative technique for the evaluation of the formation of nanobody-poliovirus complexes, and therefore predicting the in vitro neutralizing activity of the nanobodies. The macromolecules are preincubated offline in a specific nanobody-to-virus ratio and analyzed by capillary electrophoresis with UV detection. At low nanobody-to-virus ratios, a clear shift in migration time of the viral peak was observed. A broad peak was obtained, indicating the presence of a heterogeneous population of nanobody-virion complexes, caused by the binding of different numbers of nanobodies to the virus particle. At elevated nanobody-to-virus ratios, a cluster of peaks appeared, showing an additional increase in migration times. It was shown that, at these high molar excesses, aggregates were formed. The developed capillary electrophoresis method can be used as a rapid, qualitative screening for the affinity between poliovirus and nanobodies, based on a clearly visible and measurable shift in migration time. The advantages of this technique include that there is no need for antigen immobilization as in enzyme-linked immunosorbent assays or surface plasmon resonance for the use of radiolabeled virus or for the performance of labor- and time-intensive plaque-forming neutralization assays. PMID:25298084

  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. Formation of a ternary complex between chitosan and ion pairs of strontium carbonate.

    PubMed

    Piron, E; Domard, A

    1998-08-01

    This work deals essentially with the study of the interactions between chitosan and an alkaline-earth metal: 85Sr. We showed that addition of carbonate ions is necessary to observe this interaction, but only for pH values over 11. The use of an appropriate calculation software allowed us to determine the nature of the strontium ionic species present in solution. In order to understand the mechanism of interaction, the influence of various parameters on the complexation was studied. Thus, the interaction was maximum for a CO3(2-) concentration close to 10(-2) mol/l, the lowest ionic strength, the most expanded physical form (lyophilisate) and the lowest degree of acetylation of the polymer. We conclude to the formation of a ternary complex between the ion pair Sr2+ CO3(2-) and the amino groups of chitosan. We also showed the presence of interactions between chitosan and carbonate ions which hinder further interactions with strontium ions. PMID:9730164

  4. 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

  5. MOZ increases p53 acetylation and premature senescence through its complex formation with PML

    PubMed Central

    Rokudai, Susumu; Laptenko, Oleg; Arnal, Suzzette M.; Taya, Yoichi; Kitabayashi, Issay; Prives, Carol

    2013-01-01

    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

  6. 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-tRNA·EF-Tu·GTP 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

  7. Influence of RNA Strand Rigidity on Polyion Complex Formation with Block Catiomers.

    PubMed

    Hayashi, Kotaro; Chaya, Hiroyuki; Fukushima, Shigeto; Watanabe, Sumiyo; Takemoto, Hiroyasu; Osada, Kensuke; Nishiyama, Nobuhiro; Miyata, Kanjiro; Kataoka, Kazunori

    2016-03-01

    Polyion complexes (b-PICs) are prepared by mixing single- or double-stranded oligo RNA (aniomer) with poly(ethylene glycol)-b-poly(l-lysine) (PEG-PLL) (block catiomer) to clarify the effect of aniomer chain rigidity on association behaviors at varying concentrations. Here, a 21-mer single-stranded RNA (ssRNA) (persistence length: 1.0 nm) and a 21-mer double-stranded RNA (small interfering RNA, siRNA) (persistence length: 62 nm) are compared. Both oligo RNAs form a minimal charge-neutralized ionomer pair with a single PEG-PLL chain, termed unit b-PIC (uPIC), at low concentrations (<≈0.01 mg mL(-1) ). Above the critical association concentration (≈0.01 mg mL(-1) ), ssRNA b-PICs form secondary associates, PIC micelles, with sizes up to 30-70 nm, while no such multimolecular assembly is observed for siRNA b-PICs. The entropy gain associated with the formation of a segregated PIC phase in the multimolecular PIC micelles may not be large enough for rigid siRNA strands to compensate with appreciably high steric repulsion derived from PEG chains. Chain rigidity appears to be a critical parameter in polyion complex association. PMID:26765970

  8. The development of folds and cleavages in slate belts by underplating in accretionary complexes: A comparison of the Kodiak Formation, Alaska and the Calaveras Complex, California

    NASA Astrophysics Data System (ADS)

    Paterson, Scott R.; Sample, James C.

    1988-08-01

    The development of folds and cleavages in slate and graywacke belts is commonly attributed to arc-continent or continent-continent collisions. However, the Kodiak Formation of southern Alaska and the Calaveras Complex of the western Sierra Nevada, California, are two slate and graywacke belts in which folds and slaty cleavages developed during simple underthrusting and underplating within accretionary wedges. The Maastrichtian Kodiak Formation is composed dominantly of coherent turbidites but includes lesser pebbly mudstone, minor conglomerate, and rare chert. The Kodiak Formation is part of a large accretionary complex that youngs in age seaward, but bedding tops generally show landward younging. A progression of structures has been determined by crosscutting relationships and includes (1) syndeformational depositional features; (2) broken formation; (3) slaty cleavage, folds, and thrust faults; (4) crenulations and crenulation cleavage; (5) late brittle thrust faults; and (6) right-lateral strike-slip faults. Broken formation, slaty cleavage, thrust faults, and folds developed during underthrusting and underplating within an accretionary wedge. Crenulations and brittle thrust faults are related to subsequent intrawedge shortening. Based on peak metamorphism in the uppermost zeolite to prehnite-pumpellyite facies, underplating occurred at a minimum depth of 10 km. The Calaveras Complex is composed of argillite, chert, graywacke, pebbly mudstone, limestone, and volcanic rocks. Its age of deposition has a maximum range from Permian to Early Jurassic. Overall, the unit appears to young westward, but local facing indicators show eastward younging of individual blocks. The sequence of structures developed in the Calaveras Complex is (1) syn-depositional olistostromes; (2) broken formation; (3) slaty cleavage, folds, and thrust faults; and (4) younger Jura-Triassic folds and crenulation cleavages. Broken formation and slaty cleavage developed during underthrusting and underplating in an accretionary wedge, in an analogous fashion to the Kodiak Formation. Greenschist facies metemorphism during underplating suggests that the Calaveras Complex was accreted at deeper levels, or in a wedge with a higher geothermal gradient, than the Kodiak Formation. Some other probable examples of slate/graywacke belts that became folded and well-foliated during underplating include part of the Dunnage Zone (Newfoundland), the Southern Uplands complex (Scotland), the Torlesse terrane (New Zealand), part of the Hamburg klippe (Pennsylvania), and the Taconic allochthons (New York). Peak metamorphism in these belts indicates that they were accreted in accretionary wedges with geothermal gradients higher than usually assumed for such tectonic settings; such wedges may have been fairly common features at convergent margins.

  9. Complement C1q formation of immune complexes with milk caseins and wheat glutens in schizophrenia

    PubMed Central

    Severance, Emily G.; Gressitt, Kristin; Halling, Meredith; Stallings, Cassie R.; Origoni, Andrea E.; Vaughan, Crystal; Khushalani, Sunil; Alaedini, Armin; Dupont, Didier; Dickerson, Faith B.; Yolken, Robert H.

    2012-01-01

    Immune system factors including complement pathway activation are increasingly linked to the etiology and pathophysiology of schizophrenia. Complement protein, C1q, binds to and helps to clear immune complexes composed of immunoglobulins coupled to antigens. The antigenic stimuli for C1q activation in schizophrenia are not known. Food sensitivities characterized by elevated IgG antibodies to bovine milk caseins and wheat glutens have been reported in individuals with schizophrenia. Here, we examined the extent to which these food products might comprise the antigen component of complement C1q immune complexes in individuals with recent onset schizophrenia (n=38), non-recent onset schizophrenia (n=61) and non-psychiatric controls (n=63). C1q seropositivity was significantly associated with both schizophrenia groups (recent onset, odds ratio (OR)=8.02, p≤0.008; non-recent onset, OR=3.15, p≤0.03) compared to controls (logistic regression models corrected for age, sex, race and smoking status). Casein- and/or gluten-IgG binding to C1q was significantly elevated in the non-recent onset group compared to controls (OR=4.36, p≤0.01). Significant amounts of C1q-casein/gluten-related immune complexes and C1q correlations with a marker for gastrointestinal inflammation in non-recent onset schizophrenia suggests a heightened rate of food antigens in the systemic circulation, perhaps via a disease-associated altered intestinal permeability. In individuals who are in the early stages of disease onset, C1q activation may reflect the formation of immune complexes with non-casein- or non-gluten-related antigens, the presence of C1q autoantibodies, and/or a dissociated state of immune complex components. In conclusion, complement activation may be a useful biomarker to diagnose schizophrenia early during the course of the disease. Future prospective studies should evaluate the impacts of casein- and gluten-free diets on C1q activation in schizophrenia. PMID:22801085

  10. 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.

  11. (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.

  12. Sequential insertion of CO into rhodium-nitrogen. mu. -imido/amido bonds: Formation of isocyanate and dimetallocycloimide complexes

    SciTech Connect

    Ge, Y.W.; Sharp, P.R.

    1988-01-01

    Catalytic carbonylations of organoazides and nitroaryls are frequently postulated to proceed via metal imido intermediates. In support of this proposal imido complexes have been isolated from reactions of metal complexes with organoazides, nitroaryls, and nitrosoaryls. In the catalytic processes the formation of nitrogen-carbon bonds is a key step. In most cases, isocyanate (formed by coupling of the imido ligand and CO) is the final product or is a probable precursor to the final product. However, until recently the isolated imido complexes have given little, if any, isocyanates or products derived from isocyanates when treated with CO under mild conditions. This communication reports the facile formation of isocyanate and dimetallocycloimide complexes and free isocyanates and ureas by the formal single and double insertion of CO into the metal-nitrogen bonds of rhodium {mu}-imido/amido A-frame complexes.

  13. 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

  14. 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

  15. Double-decker phthalocyanine complex: Scanning tunneling microscopy study of film formation and spin properties

    NASA Astrophysics Data System (ADS)

    Komeda, Tadahiro; Katoh, Keiichi; Yamashita, Masahiro

    2014-05-01

    We review recent studies of double-decker and triple-decker phthalocyanine (Pc) molecules adsorbed on surfaces in terms of the bonding configuration, electronic structure and spin state. The Pc molecule has been studied extensively in surface science. A Pc molecule can contain various metal atoms at the center, and the class of the molecule is called as metal phthalocyanine (MPc). If the center metal has a large radius, like as lanthanoid metals, it becomes difficult to incorporate the metal atom inside of the Pc ring. Pc ligands are placed so as to sandwich the metal atom, where the metal atom is placed out of the Pc plane. The molecule in this configuration is called as a multilayer-decker Pc molecule. After the finding that the double-decker Pc lanthanoid complex shows single-molecule magnet (SMM) behavior, it has attracted a large attention. This is partly due to a rising interest for the ‘molecular spintronics’, in which the freedoms of spin and charge of an electron are applied to the quantum process of information. SMMs represent a class of compounds in which a single molecule behaves as a magnet. The reported blocking temperature, below which a single SMM molecule works as an quantum magnet, has been increasing with the development in the molecular design and synthesis techniques of multiple-decker Pc complex. However, even the bulk properties of these molecules are promising for the use of electronic materials, the films of multi-decker Pc molecules is less studied than those for the MPc molecules. An intriguing structural property is expected for the multi-decker Pc molecules since the Pc planes are linked by metal atoms. This gives an additional degree of freedom to the rotational angle between the two Pc ligands, and they can make a wheel-like symmetric rotation. Due to a simple and well-defined structure of a multi-decker Pc complex, the molecule can be a model molecule for molecular machine studies. The multi-decker Pc molecules can provide interesting spin configuration. The center metal atom, including a lanthanoid metal of Tb, tends to be 3+ cation, while the Pc ligand to be 2- anion. This realizes two-spin system, in which spins from 4f electrons and π radical coexist. Though the spins of 4f orbitals of those molecules have been studied, the importance of the π radicals has been highlighted recently from the measurement of electronic conductance properties of these molecules. In this article, recent researches on multi-decker Pc molecules are reviewed. The manuscript is organized with groups of chapters as follows: (1) Film formation, (2) Spin of TbPc2 film and Kondo resonance observation, (3) Rotation of double-decker Pc complex and chemical modification for spin control, (4) Device formation using double-decker Pc complex.

  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. Stability constant estimator user`s guide

    SciTech Connect

    Hay, B.P.; Castleton, K.J.; Rustad, J.R.

    1996-12-01

    The purpose of the Stability Constant Estimator (SCE) program is to estimate aqueous stability constants for 1:1 complexes of metal ions with ligands by using trends in existing stability constant data. Such estimates are useful to fill gaps in existing thermodynamic databases and to corroborate the accuracy of reported stability constant values.

  18. 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.

  19. 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.

  20. The formation of host-guest complexes between surfactants and cyclodextrins.

    PubMed

    Valente, Artur J M; Söderman, Olle

    2014-03-01

    Cyclodextrins are able to act as host molecules in supramolecular chemistry with applications ranging from pharmaceutics to detergency. Among guest molecules surfactants play an important role with both fundamental and practical applications. The formation of cyclodextrin/surfactant host-guest compounds leads to an increase in the critical micelle concentration and in the solubility of surfactants. The possibility of changing the balance between several intermolecular forces, and thus allowing the study of, e.g., dehydration and steric hindrance effects upon association, makes surfactants ideal guest molecules for fundamental studies. Therefore, these systems allow for obtaining a deep insight into the host-guest association mechanism. In this paper, we review the influence on the thermodynamic properties of CD-surfactant association by highlighting the effect of different surfactant architectures (single tail, double-tailed, gemini and bolaform), with special emphasis on cationic surfactants. This is complemented with an assessment of the most common analytical techniques used to follow the association process. The applied methods for computation of the association stoichiometry and stability constants are also reviewed and discussed; this is an important point since there are significant discrepancies and scattered data for similar systems in the literature. In general, the surfactant-cyclodextrin association is treated without reference to the kinetics of the process. However, there are several examples where the kinetics of the process can be investigated, in particular those where volumes of the CD cavity and surfactant (either the tail or in special cases the head group) are similar in magnitude. This will also be critically reviewed. PMID:24011696

  1. Complex formation of cadmium with sugar residues, nucleobases, phosphates, nucleotides, and nucleic acids.

    PubMed

    Sigel, Roland K O; Skilandat, Miriam; Sigel, Astrid; Operschall, Bert P; Sigel, Helmut

    2013-01-01

    Cadmium(II), commonly classified as a relatively soft metal ion, prefers indeed aromatic-nitrogen sites (e.g., N7 of purines) over oxygen sites (like sugar-hydroxyl groups). However, matters are not that simple, though it is true that the affinity of Cd(2+) towards ribose-hydroxyl groups is very small; yet, a correct orientation brought about by a suitable primary binding site and a reduced solvent polarity, as it is expected to occur in a folded nucleic acid, may facilitate metal ion-hydroxyl group binding very effectively. Cd(2+) prefers the guanine(N7) over the adenine(N7), mainly because of the steric hindrance of the (C6)NH(2) group in the adenine residue. This Cd(2+)-(N7) interaction in a guanine moiety leads to a significant acidification of the (N1)H meaning that the deprotonation reaction occurs now in the physiological pH range. N3 of the cytosine residue, together with the neighboring (C2)O, is also a remarkable Cd(2+) binding site, though replacement of (C2)O by (C2)S enhances the affinity towards Cd(2+) dramatically, giving in addition rise to the deprotonation of the (C4)NH(2) group. The phosphodiester bridge is only a weak binding site but the affinity increases further from the mono- to the di- and the triphosphate. The same also holds for the corresponding nucleotides. Complex stability of the pyrimidine-nucleotides is solely determined by the coordination tendency of the phosphate group(s), whereas in the case of purine-nucleotides macrochelate formation takes place by the interaction of the phosphate-coordinated Cd(2+) with N7. The extents of the formation degrees of these chelates are summarized and the effect of a non-bridging sulfur atom in a thiophosphate group (versus a normal phosphate group) is considered. Mixed ligand complexes containing a nucleotide and a further mono- or bidentate ligand are covered and it is concluded that in these species N7 is released from the coordination sphere of Cd(2+). In the case that the other ligand contains an aromatic residue (e.g., 2,2'-bipyridine or the indole ring of tryptophanate) intramolecular stack formation takes place. With buffers like Tris or Bistris mixed ligand complexes are formed. Cd(2+) coordination to dinucleotides and to dinucleoside monophosphates provides some insights regarding the interaction between Cd(2+) and nucleic acids. Cd(2+) binding to oligonucleotides follows the principles of coordination to its units. The available crystal studies reveal that N7 of purines is the prominent binding site followed by phosphate oxygens and other heteroatoms in nucleic acids. Due to its high thiophilicity, Cd(2+) is regularly used in so-called thiorescue experiments, which lead to the identification of a direct involvement of divalent metal ions in ribozyme catalysis. PMID:23430775

  2. Thermochemical study of processes of complex formation of Cu2+ ions with L-glutamine in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Gorboletova, G. G.; Gridchin, S. N.; Lutsenko, A. A.

    2010-11-01

    Heats of the interaction of Cu(NO3)2 solutions with L-glutamine solutions were measured directly by calorimetry at a temperature of 298.15 K and ionic strength values of 0.5, 1.0, and 1.5 (KNO3). Using RRSU universal software, the experimental data were subjected to rigorous mathematical treatment with allowances made for several concurrent processes in the system. The heats of formation of the CuL+ and CuL2 complexes were calculated from the calorimetric measurements. The standard heats of the complex formation of Cu2+ with L-glutamine were obtained by extrapolation to zero ionic strength. The complete thermodynamic characteristic (Δr H o, Δr G o, Δr S o) of the complex formation processes in a Cu2+—L-glutamine system was obtained.

  3. 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.

  4. Polyprotein-Driven Formation of Two Interdependent Sets of Complexes Supporting Hepatitis C Virus Genome Replication

    PubMed Central

    Gomes, Rafael G. B.; Isken, Olaf; Tautz, Norbert; McLauchlan, John

    2015-01-01

    ABSTRACT Hepatitis C virus (HCV) requires proteins from the NS3-NS5B polyprotein to create a replicase unit for replication of its genome. The replicase proteins form membranous compartments in cells to facilitate replication, but little is known about their functional organization within these structures. We recently reported on intragenomic replicons, bicistronic viral transcripts expressing an authentic replicase from open reading frame 2 (ORF2) and a second duplicate nonstructural (NS) polyprotein from ORF1. Using these constructs and other methods, we have assessed the polyprotein requirements for rescue of different lethal point mutations across NS3-5B. Mutations readily tractable to rescue broadly fell into two groupings: those requiring expression of a minimum NS3-5A and those requiring expression of a minimum NS3-5B polyprotein. A cis-acting mutation that blocked NS3 helicase activity, T1299A, was tolerated when introduced into either ORF within the intragenomic replicon, but unlike many other mutations required the other ORF to express a functional NS3-5B. Three mutations were identified as more refractile to rescue: one that blocked cleavage of the NS4B5A boundary (S1977P), another in the NS3 helicase (K1240N), and a third in NS4A (V1665G). Introduced into ORF1, these exhibited a dominant negative phenotype, but with K1240N inhibiting replication as a minimum NS3-5A polyprotein whereas V1665G and S1977P only impaired replication as a NS3-5B polyprotein. Furthermore, an S1977P-mutated NS3-5A polyprotein complemented other defects shown to be dependent on NS3-5A for rescue. Overall, our findings suggest the existence of two interdependent sets of protein complexes supporting RNA replication, distinguishable by the minimum polyprotein requirement needed for their formation. IMPORTANCE Positive-strand RNA viruses reshape the intracellular membranes of cells to form a compartment within which to replicate their genome, but little is known about the functional organization of viral proteins within this structure. We have complemented protein-encoded defects in HCV by constructing subgenomic HCV transcripts capable of simultaneously expressing both a mutated and functional polyprotein precursor needed for RNA genome replication (intragenomic replicons). Our results reveal that HCV relies on two interdependent sets of protein complexes to support viral replication. They also show that the intragenomic replicon offers a unique way to study replication complex assembly, as it enables improved composite polyprotein complex formation compared to traditional trans-complementation systems. Finally, the differential behavior of distinct NS3 helicase knockout mutations hints that certain conformations of this enzyme might be particularly deleterious for replication. PMID:26719260

  5. 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.

  6. 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.

  7. Formation of Complex Organic molecules from Formaldehyde Chemistry in Cometary Ice Analogues

    NASA Astrophysics Data System (ADS)

    Duvernay, fabrice; Vinogradoff, Vassilissa; Danger, Grégoire; Theulé, Patrice; Chiavassa, Thierry

    2015-04-01

    There is convincing evidence that the formation of complex organic molecules occurred in a variety of astrophysical environments. Among them, precursors of biomolecules are of particular significance due to their exobiological implications. Hexamethylenetetramine (HMT, C6H12N4) and the polyoxymethylene (POM, -(CH2-O)n-) are of prime interest since they are supposed to be present in cometary environments. They are also ones of the main components of the organic residue formed from the warming of photolysed interstellar/cometary ice analogs. In this work, we study the warming of water-dominated cometary ice analogs containing formaldehyde (H2CO). Based on infrared and mass spectrometry measurements, and complemented by quantum chemical calculations, we report that NH2CH2OH, HOCH2OH, and POM are the only reaction products when the ice also contains NH3. The branching ratio between the three products strongly depends on the initial H2CO/NH3 concentration ratio. Moreover, the influence of the initial ice composition on the formation of POM oligomers (HO-(CH2O)n-H, n<5) as well as their thermal instability between 200 and 320 K are investigated. Finally, the implications of these results with respect to cometary nucleus chemistry and their impact on POM detection by the Rosetta mission are discussed. In addition, the mechanism for HMT formation in interstellar or cometary ice analogs containing H2CO, NH3, and HCOOH has been determined by combining laboratory experiments and DFT calculations. We show that HMT is thermally formed from H2CO and NH3 activated by HCOOH. Two intermediates has been unambiguously detected: NH2CH2OH and the trimer of CH2NH (1,3,5-triazinane, TMT). Unlike to what it was previously thought, HMT is not an indicator of ice photochemistry, but an indicator of thermal processing of ice. These results strengthen the hypothesis that HMT and its intermediates should be present in comets, where they may be detected with the COSAC or COSIMA instrument of the Rosetta mission.

  8. 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

  9. Immune reactions in polysaccharide media. Investigation on complex-formation between some polysaccharides, albumin and immunoglobulin G

    PubMed Central

    Hellsing, Krister

    1969-01-01

    Serum albumin and immunoglobulin G were chromatographed on columns of dextran, hyaluronate and chondroitin 4-sulphate. The partition of the two proteins between hyaluronate and buffer was also measured by equilibrium dialysis. The results accord with the view that there is no complex-formation between the polysaccharides and the proteins in 0·05m-phosphate buffer, pH7·4, containing sodium chloride (0·1m). The observations support the hypothesis that the previously described polysaccharide enhancement of the precipitin reaction is due to exclusion and not to non-specific complex-formation. PMID:5817720

  10. 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

  11. Methodological approach to the study of the formation and physicochemical properties of phosphate-metal-humic complexes in solution.

    PubMed

    Guardado, Iñaki; Urrutia, Oscar; Garcia-Mina, Jose M

    2005-11-01

    The aim of this work is to study the suitability of the complementary use of ultrafiltration (UF) and the interaction with an anion-exchange resin (AR) to characterize of phosphate-metal-humic complexes in solution. The results indicate that a methodological approach consisting of the validation and calibration of the AR method by the UF method and the further use of the AR method is suitable for characterizing phosphate-metal complexes. Such an approach has proven to be useful for calculating the phosphate maximum binding capacity of iron-humic complexes and stability constants. It might also be used to obtain valuable purified phosphate-metal-humic complexes for further structural characterization. PMID:16248570

  12. Influence of substituent position and cavity size of the regioisomers of monocarboxymethyl-α-, β-, and γ-cyclodextrins on the apparent stability constants of their complexes with both enantiomers of Tröger's base.

    PubMed

    Řezanka, Pavel; Řezanková, Klára; Sedláčková, Helena; Mašek, Jindřich; Rokosová, Lenka; Bláhová, Markéta; Řezanka, Michal; Jindřich, Jindřich; Sýkora, David; Král, Vladimír

    2016-03-01

    Enantiomers of Tröger's base were separated by capillary electrophoresis using 2(I) -O-, 3(I) -O-, and 6(I) -O-carboxymethyl-α-, β-, and γ-cyclodextrin and native α-, β-, and γ-cyclodextrin as chiral additives at 0-12 mmol/L for β-cyclodextrin and its derivatives and 0-50 mmol/L for α- and γ-cyclodextrins and their derivatives in a background electrolyte composed of sodium phosphate buffer at 20 mmol/L concentration and pH 2.5. Apparent stability constants of all cyclodextrin-Tröger's base complexes were calculated based on capillary electrophoresis data. The obtained results showed that the position of the carboxymethyl group as well as the cavity size of the individual cyclodextrin significantly influences the apparent stability constants of cyclodextrin-Tröger's base complexes. PMID:26695522

  13. 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.

  14. 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

  15. 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…

  16. 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

  17. 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.

  18. SEPT12-Microtubule Complexes Are Required for Sperm Head and Tail Formation

    PubMed Central

    Kuo, Pao-Lin; Chiang, Han-Sun; Wang, Ya-Yun; Kuo, Yung-Che; Chen, Mei-Feng; Yu, I-Shing; Teng, Yen-Ni; Lin, Shu-Wha; Lin, Ying-Hung

    2013-01-01

    The septin gene belongs to a highly conserved family of polymerizing GTP-binding cytoskeletal proteins. SEPTs perform cytoskeletal remodeling, cell polarity, mitosis, and vesicle trafficking by interacting with various cytoskeletons. Our previous studies have indicated that SEPTIN12+/+/+/− chimeras with a SEPTIN12 mutant allele were infertile. Spermatozoa from the vas deferens of chimeric mice indicated an abnormal sperm morphology, decreased sperm count, and immotile sperm. Mutations and genetic variants of SEPTIN12 in infertility cases also caused oligozoospermia and teratozoospermia. We suggest that a loss of SEPT12 affects the biological function of microtublin functions and causes spermiogenesis defects. In the cell model, SEPT12 interacts with α- and β-tubulins by co-immunoprecipitation (co-IP). To determine the precise localization and interactions between SEPT12 and α- and β-tubulins in vivo, we created SEPTIN12-transgene mice. We demonstrate how SEPT12 interacts and co-localizes with α- and β-tubulins during spermiogenesis in these mice. By using shRNA, the loss of SEPT12 transcripts disrupts α- and β-tubulin organization. In addition, losing or decreasing SEPT12 disturbs the morphogenesis of sperm heads and the elongation of sperm tails, the steps of which are coordinated and constructed by α- and β-tubulins, in SEPTIN12+/+/+/− chimeras. In this study, we discovered that the SEPTIN12-microtubule complexes are critical for sperm formation during spermiogenesis. PMID:24213608

  19. Formation and Identification of Unresolved Complex Mixtures in Lacustrine Biodegraded Oil from Nanxiang Basin, China

    PubMed Central

    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

  20. Feedback control of prion formation and propagation by the ribosome-associated chaperone complex

    PubMed Central

    Kiktev, Denis A.; Melomed, Mikhail M.; Lu, Caroline D.; Newnam, Gary P.; Chernoff, Yury O.

    2015-01-01

    Summary 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 due to 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

  1. Plasmodium falciparum origin recognition complex subunit 5: functional characterization and role in DNA replication foci formation

    PubMed Central

    Gupta, Ashish; Mehra, Parul; Dhar, Suman Kumar

    2008-01-01

    The mechanism of DNA replication initiation and progression is poorly understood in the parasites, including human malaria parasite Plasmodium falciparum. Using bioinformatics tools and yeast complementation assay, we identified a putative homologue of Saccharomyces cerevisiae origin recognition complex subunit 5 in P. falciparum (PfORC5). PfORC5 forms distinct nuclear foci colocalized with the replication foci marker proliferating cell nuclear antigen (PfPCNA) and co-immunoprecipitates with PCNA during early-to-mid trophozoite stage replicating parasites. Interestingly, these proteins separate from each other at the non-replicating late schizont stage, citing the evidence of the presence of both PCNA and ORC components in replication foci during eukaryotic DNA replication. PfORC1, another ORC subunit, colocalizes with PfPCNA and PfORC5 at the beginning of DNA replication, but gets degraded at the late schizont stage, ensuring the regulation of DNA replication in the parasites. Further, we have identified putative PCNA-interacting protein box in PfORC1 that may explain in part the colocalization of PfORC and PfPCNA. Additionally, use of specific DNA replication inhibitor hydroxyurea affects ORC5/PCNA foci formation and parasitic growth. These results strongly favour replication factory model in the parasites and confer great potential to understand the co-ordination between ORC and PCNA during eukaryotic DNA replication in general. PMID:18554328

  2. SipB-SipC complex is essential for translocon formation.

    PubMed

    Myeni, Sebenzile K; Wang, Lu; Zhou, Daoguo

    2013-01-01

    The delivery of effector proteins by Salmonella across the host cell membrane requires a subset of effectors secreted by the type III secretion system (TTSS) known as translocators. SipC and SipB are translocator proteins that are inserted into host membranes and presumably form a channel that translocates type III effectors into the host cell. The molecular events of how these translocators insert into the host cell membrane remain unknown. We have previously shown that the SipC C-terminal amino acid region (321-409) is required for the translocation of effectors into host cells. In this study, we demonstrate that the ability to form SipC-SipB complex is essential for their insertion into the host membrane. The SipB-interacting domain of SipC is near its C-terminal amino acid region (340-409). In the absence of SipB, SipC was not detected in the membrane fraction. Furthermore, SipC mutants that no longer interact with SipB are defective in inserting into the host cell membrane. We propose a mechanism whereby SipC binds SipB through its C-terminal region to facilitate membrane-insertion and subsequent translocon formation in the host cell membrane. PMID:23544147

  3. 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.

  4. A novel complex of membrane proteins required for formation of a spherical nucleus.

    PubMed

    Siniossoglou, S; Santos-Rosa, H; Rappsilber, J; Mann, M; Hurt, E

    1998-11-16

    Two membrane proteins were identified through their genetic interaction with the nucleoporin Nup84p and shown to participate in nuclear envelope morphogenesis in yeast. One component is a known sporulation factor Spo7p, and the other, Nem1p, a novel protein whose C-terminal domain is conserved during eukaryotic evolution. Spo7p and Nem1p localize to the nuclear/ER membrane and behave biochemically as integral membrane proteins. Nem1p binds to Spo7p via its conserved C-terminal domain. Although cells without Spo7p or Nem1p are viable, they exhibit a drastically altered nuclear morphology with long, pore-containing double nuclear membrane extensions. These protrusions emanate from a core nucleus which contains the DNA, and penetrate deeply into the cytoplasm. Interestingly, not only Spo7(-) and Nem1(-), but also several nucleoporin mutants are defective in sporulation. Thus, Spo7p and Nem1p, which exhibit a strong genetic link to nucleoporins of the Nup84p complex, fulfil an essential role in formation of a spherical nucleus and meiotic division. PMID:9822591

  5. 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.

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. A cyclo‐P6 Ligand Complex for the Formation of Planar 2D Layers

    PubMed Central

    Heindl, Claudia; Peresypkina, Eugenia V.; Lüdeker, David; Brunklaus, Gunther; Virovets, Alexander V.

    2016-01-01

    Abstract 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,η6:η6‐P6)] (1) with CuX (X=Br, I) leads to self‐assembly into unprecedented 2D networks of [{(CpMo)2P6}(CuBr)4]n (2) and [{(CpMo)2P6}(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 31P{1H} 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

  11. Structure Formation of Ultrathin PEO Films at Solid Interfaces—Complex Pattern Formation by Dewetting and Crystallization

    PubMed Central

    Braun, Hans-Georg; Meyer, Evelyn

    2013-01-01

    The direct contact of ultrathin polymer films with a solid substrate may result in thin film rupture caused by dewetting. With crystallisable polymers such as polyethyleneoxide (PEO), molecular self-assembly into partial ordered lamella structures is studied as an additional source of pattern formation. Morphological features in ultrathin PEO films (thickness < 10 nm) result from an interplay between dewetting patterns and diffusion limited growth pattern of ordered lamella growing within the dewetting areas. Besides structure formation of hydrophilic PEO molecules, n-alkylterminated (hydrophobic) PEO oligomers are investigated with respect to self-organization in ultrathin films. Morphological features characteristic for pure PEO are not changed by the presence of the n-alkylgroups. PMID:23385233

  12. Spectrofluorimetric Determination of Famotidine in Pharmaceutical Preparations and Biological Fluids through Ternary Complex Formation with Some Lanthanide Ions: Application to Stability Studies

    PubMed Central

    Walash, M. I.; El-Brashy, A.; El-Enany, N.; Wahba, M. E. K.

    2009-01-01

    A simple, sensitive and specific method was developed for the determination of famotidine (FMT) in pharmaceutical preparations and biological fluids. The proposed method is based on ternary complex formation of famotidine (FMT) with EDTA and terbium chloride TbCl3 in acetate buffer of pH 4. Alternatively, the complex is formed via the reaction with hexamine and either lanthanum chloride LaCl3, or cerous chloride CeCl3 in borate buffer of pH6.2 and 7.2 respectively. In all cases, the relative fluorescence intensity of the formed complexes was measured at 580 nm after excitation at 290 nm. The fluorescence intensity - concentration plots were rectilinear over the concentration range of 10-100, 5-70, and 5-60 ng/ml, with minimum quantification limits (LOQ) of 2.4, 2.2, and 5.2 ng/ml, and minimum limits of detection (LOD) of 0.79, 0.74, and 1.7 ng/ml upon using TbCl3, LaCl3, and CeCl3 respectively. The proposed method was applied successfully for the analysis of famotidine in dosage forms and in human plasma. The kinetics of both alkaline and oxidative induced degradation of the drug was studied using the proposed method. The apparent first order rate constant and half life time were calculated. A proposal of the reaction pathways is presented. PMID:23675130

  13. 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

  14. 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 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-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 (150×4.6 mm i.d., 5 μm). 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-β-CD or SBE-β-CD. Semi-preparative enantioseparation of about 10 mg 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 stoichiomertries for all the inclusion complex of cyclodextrin-enantiomers were 1:1. PMID:24893270

  15. 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

  16. The effect of trans-resveratrol on platelet-neutrophil complex formation and neutrophil burst in hypercholesterolemic rats

    PubMed Central

    Göçmen, Ayşe Yeşim; Burgucu, Durmuş; Karadoğan, İhsan; Timurağaoğlu, Ayşen; Gümüşlü, 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

  17. Metal complexes of cyclen and cyclam derivatives useful for medical applications: a discussion based on thermodynamic stability constants and structural data.

    PubMed

    Delgado, Rita; Félix, Vítor; Lima, Luís M P; Price, David W

    2007-07-14

    A series of the most common chelators used in magnetic resonance imaging (MRI) and in radiopharmaceuticals for medical diagnosis and tumour therapy, H(4)dota, H(4)teta, H(8)dotp and H(8)tetp, is examined from a chemical point of view. Differences between 12- and 14-membered tetraazamacrocyclic derivatives with methylcarboxylate and methylphosphonate pendant arms and their chelates with divalent first-series transition metal and trivalent lanthanide ions are discussed on the basis of their thermodynamic stability constants, X-ray structures and theoretical studies. PMID:17592589

  18. 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

  19. Titanium oxide complexes with dinitrogen. Formation and characterization of the side-on and end-on bonded titanium oxide-dinitrogen complexes in solid neon.

    PubMed

    Zhou, Mingfei; Zhuang, Jia; Zhou, Zijian; Li, Zhen Hua; Zhao, Yanying; Zheng, Xuming; Fan, Kangnian

    2011-06-23

    The reactions of titanium oxide molecules with dinitrogen have been studied by matrix isolation infrared spectroscopy. The titanium monoxide molecule reacts with dinitrogen to form the TiO(N(2))(x) (x = 1-4) complexes spontaneously on annealing in solid neon. The TiO(η(1)-NN) complex is end-on bonded and was predicted to have a (3)A'' ground state arising from the (3)Δ ground state of TiO. Argon doping experiments indicate that TiO(η(1)-NN) is able to form complexes with one or more argon atoms. Argon atom coordination induces a large red-shift of the N-N stretching frequency. The TiO(η(2)-N(2))(2) complex was characterized to have C(2v) symmetry, in which both the N(2) ligands are side-on bonded to the titanium metal center. The tridinitrogen complex TiO(η(1)-NN)(3) most likely has C(3v) symmetry with three end-on bonded N(2) ligands. The TiO(η(1)-NN)(4) complex was determined to have a C(4v) structure with four equivalent end-on bonded N(2) ligands. In addition, evidence is also presented for the formation of the TiO(2)(η(1)-NN)(x) (x = 1-4) complexes, which were predicted to be end-on bonded. PMID:21604730

  20. 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

  1. 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.

  2. Hemolymph Melanization in the Silkmoth Bombyx mori Involves Formation of a High Molecular Mass Complex That Metabolizes Tyrosine*

    PubMed Central

    Clark, Kevin D.; Strand, Michael R.

    2013-01-01

    The phenoloxidase (PO) cascade regulates the melanization of blood (hemolymph) in insects and other arthropods. Most studies indicate that microbial elicitors activate the PO cascade, which results in processing of the zymogen PPO to PO. PO is then thought to oxidize tyrosine and o-diphenols to quinones, which leads to melanin. However, different lines of investigation raise questions as to whether these views are fully correct. Here we report that hemolymph from the silkmoth, Bombyx mori, rapidly melanizes after collection from a wound site. Prior studies indicated that in vitro activated PPO hydroxylates Tyr inefficiently. Measurement of in vivo substrate titers, however, suggested that Tyr was the only PO substrate initially present in B. mori plasma and that it is rapidly metabolized by PO. Fractionation of plasma by gel filtration chromatography followed by bioassays indicated that melanization activity was primarily associated with a high mass complex (∼670 kDa) that contained PO. The prophenoloxidase-activating protease inhibitor Egf1.0 blocked formation of this complex and Tyr metabolism, but the addition of phenylthiourea to plasma before fractionation enhanced complex formation and Tyr metabolism. Mass spectrometry analysis indicated that the complex contained PO plus other proteins. Taken together, our results indicate that wounding alone activates the PO cascade in B. mori. They also suggest that complex formation is required for efficient use of Tyr as a substrate. PMID:23553628

  3. 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

  4. Torsional constraints on the formation of open promoter complexes on DNA minicircles carrying sigma 54-dependent promoters.

    PubMed

    Qureshi, M; Eydmann, T; Austin, S; Dixon, R

    1997-10-01

    A topoisomer gel retardation assay has been used to examine the topological requirements for the formation of open promoter complexes on DNA minicircles carrying sigma 54-dependent promoters. In the absence of intercalators, individual topoisomers carrying both the nifL and nifF promoters could be resolved as discrete species by electrophoresis, but exhibited anomalous electrophoretic behavior at relatively high negative superhelical density, indicative of a structural transition. In the presence of phosphorylated activator protein NTRC, ATP, and sigma 54 RNA polymerase holoenzyme, discrete topoisomer shifts were detected associated with the formation of open promoter complexes. At the nifL promoter open complexes could be formed on all negatively supercoiled topoisomers examined as well as on nicked circular DNA, but not on the DeltaLk = 0 topoisomer or positively supercoiled DNA. Minicircles carrying the sigma 54-dependent glnAp2 promoter could not be resolved in the electrophoresis system, but using a combination of potassium permanganate footprinting and topoisomerase I relaxation assays, we found in contrast to the nifL promoter, that open complexes were formed not only on negatively supercoiled topoisomers but also on relaxed minicircles and the Delta Lk = +1 topoisomer. These results indicate there is a thermodynamic barrier to the formation of open complexes on DNA minicircles carrying the nifL promoter which is not evident at glnAp2. PMID:9315870

  5. Ternary complex formation and competition quench fluorescence of ZnAF family zinc sensors.

    PubMed

    Staszewska, Anna; Kurowska, Ewa; Bal, Wojciech

    2013-11-01

    Our current understanding of the intracellular thermodynamics and kinetics of Zn(ii) ions is largely based on the application of fluorescent sensor molecules, used to study and visualize the concentration, distribution and transport of Zn(ii) ions in real time. Such agents are designed for high selectivity for zinc in respect to other biological metal ions. However, the issue of their sensitivity to physiological levels of low molecular weight Zn(ii) ligands (LMWLs) has not been addressed. We followed the effects of eight such compounds on the fluorescence of ZnAF-1 and ZnAF-2F, two representatives of the ZnAF family of fluorescein-based zinc sensors containing the N,N-bis(2-pyridylmethyl)ethylenediamine chelating unit. Fluorescence titrations of equimolar Zn(ii)-ZnAF-1 and Zn(ii)-ZnAF-2F solutions with acetate, phosphate, citrate, glycine, glutamic acid, histidine, ATP and GSH demonstrated strong fluorescence quenching. These results are interpreted in terms of an interplay of the formation of the [ZnAF-Zn(ii)-LMWL] ternary complexes and the competition for Zn(ii) between ZnAF and LMWLs. UV-vis spectroscopic titrations revealed the existence of supramolecular interactions between the fluorescein moiety of ZnAF-1 and ATP and His, which, however, did not contribute to fluorescence quenching. Therefore, the obtained results show that the ZnAF sensors, other currently used zinc sensors containing the N,N-bis(2-pyridylmethyl)ethylenediamine unit, and, in general, all sensors that do not saturate the Zn(ii) coordination sphere may co-report cellular metabolites and Zn(ii) ions, leading to misrepresentations of the concentrations and fluxes of biological zinc. PMID:23939683

  6. A complex cortical reaction leads to formation of the fertilization envelope in the lobster, Homarus.

    PubMed

    Talbot, P; Goudeau, M

    1988-01-01

    We have examined the formation of the fertilization envelope in the lobsters Homarus americanus and H gammarus. Oocytes were fixed for electron microscopy either in the ovary or following extrusion from the gonopore. Mature ovarian oocytes are surrounded by a coat (envelope 1), which is comprised of small electron-dense granules and structures resembling "bottlebrushes." At least part of this coat is synthesized by the follicle cells of the ovary. The cortex of ovarian oocytes contains four types of vesicles that we refer to as high-density vesicles (HDV), low-density vesicles (LDV), moderately dense vesicles (MDV), and ring vesicles (RV). Oocytes that were electrically extruded from the gonopore and fixed immediately had an envelope identical to that of ovarian oocytes. The cortex of gonopore oocytes contained the four types of vesicles found in ovarian oocytes. When unfertilized gonopore oocytes were allowed to incubate in sea water, the oocyte cortex appeared unaltered, but envelope 1 swelled and the bottlebrushes dispersed. When recently fertilized oocytes were fixed during natural spawning or following in-vitro fertilization, each type of vesicle was released in sequence from the cortex of the oocyte. The contents of the HDV and LDV appeared first in the perivitelline space, but their fate could not be determined at later times. The ring-shaped elements of the RV and the moderately electron-dense material of the MDV were released exocytotically somewhat later; these materials coalesced in the perivitelline space to form a new coat (envelope 2). Envelope 1 subsequently condensed to its original thickness and appeared firmly attached to envelope 2. Our results show that the fertilized lobster egg is surrounded by two discrete coats. The outer coat, which is formed in the ovary, undergoes a swelling/condensation cycle at spawning. The inner coat originates from a complex cortical reaction. Together these coats comprise the fertilization envelope of the lobster egg. PMID:3198040

  7. Protection of Metal Artifacts with the Formation of Metal–Oxalates Complexes by Beauveria bassiana

    PubMed Central

    Joseph, Edith; Cario, Sylvie; Simon, Anaële; Wörle, Marie; Mazzeo, Rocco; Junier, Pilar; Job, Daniel

    2012-01-01

    Several fungi present high tolerance to toxic metals and some are able to transform metals into metal–oxalate complexes. In this study, the ability of Beauveria bassiana to produce copper oxalates was evaluated. Growth performance was tested on various copper-containing media. B. bassiana proved highly resistant to copper, tolerating concentrations of up to 20 g L−1, and precipitating copper oxalates on all media tested. Chromatographic analyses showed that this species produced oxalic acid as sole metal chelator. The production of metal–oxalates can be used in the restoration and conservation of archeological and modern metal artifacts. The production of copper oxalates was confirmed directly using metallic pieces (both archeological and modern). The conversion of corrosion products into copper oxalates was demonstrated as well. In order to assess whether the capability of B. bassiana to produce metal–oxalates could be applied to other metals, iron and silver were tested as well. Iron appears to be directly sequestered in the wall of the fungal hyphae forming oxalates. However, the formation of a homogeneous layer on the object is not yet optimal. On silver, a co-precipitation of copper and silver oxalates occurred. As this greenish patina would not be acceptable on silver objects, silver reduction was explored as a tarnishing remediation. First experiments showed the transformation of silver nitrate into nanoparticles of elemental silver by an unknown extracellular mechanism. The production of copper oxalates is immediately applicable for the conservation of copper-based artifacts. For iron and silver this is not yet the case. However, the vast ability of B. bassiana to transform toxic metals using different immobilization mechanisms seems to offer considerable possibilities for industrial applications, such as the bioremediation of contaminated soils or the green synthesis of chemicals. PMID:22291684

  8. 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.

  9. 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.

  10. Structural backgrounds for the formation of a catalytically competent complex with NADP(H) during hydride transfer in ferredoxin-NADP(+) reductases.

    PubMed

    Sánchez-Azqueta, Ana; Musumeci, Matías A; Martínez-Júlvez, Marta; Ceccarelli, Eduardo A; Medina, Milagros

    2012-07-01

    The role of the highly conserved C266 and L268 of pea ferredoxin-NADP(+) reductase (FNR) in formation of the catalytically competent complex of the enzyme with NADP(H) was investigated. Previous studies suggest that the volume of these side-chains, situated facing the side of the C-terminal Y308 catalytic residue not stacking the flavin isoalloxazine ring, may be directly involved in the fine-tuning of the catalytic efficiency of the enzyme. Wild-type pea FNR as well as single and double mutants of C266 and L268 residues were analysed by fast transient-kinetic techniques and their midpoint reduction potentials were determined. For the C266A, C266M and C266A/L268A mutants a significant reduction in the overall hydride transfer (HT) rates was observed along with the absence of charge-transfer complex formation. The HT rate constants for NADPH oxidation were lower than those for NADP(+) reduction, reaching a 30-fold decrease in the double mutant. In agreement, these variants exhibited more negative midpoint potentials with respect to the wild-type enzyme. The three-dimensional structures of C266M and L268V variants were solved. The C266M mutant shows a displacement of E306 away from the relevant residue S90 to accommodate the bulky methionine introduced. The overall findings indicate that in FNR the volume of the residue at position 266 is essential to attain the catalytic architecture between the nicotinamide and isoalloxazine rings at the active site and, therefore, for an efficient HT process. In addition, flexibility of the 268-270 loop appears to be critical for FNR to achieve catalytically competent complexes with NADP(H). PMID:22542899

  11. Crystal structure and solution species of Ce(III) and Ce(IV) formates: from mononuclear to hexanuclear complexes.

    PubMed

    Hennig, Christoph; Ikeda-Ohno, Atsushi; Kraus, Werner; Weiss, Stephan; Pattison, Philip; Emerich, Hermann; Abdala, Paula M; Scheinost, Andreas C

    2013-10-21

    Cerium(III) and cerium(IV) both form formate complexes. However, their species in aqueous solution and the solid-state structures are surprisingly different. The species in aqueous solutions were investigated with Ce K-edge EXAFS spectroscopy. Ce(III) formate shows only mononuclear complexes, which is in agreement with the predicted mononuclear species of Ce(HCOO)(2+) and Ce(HCOO)2(+). In contrast, Ce(IV) formate forms in aqueous solution a stable hexanuclear complex of [Ce6(μ3-O)4(μ3-OH)4(HCOO)x(NO3)y](12-x-y). The structural differences reflect the different influence of hydrolysis, which is weak for Ce(III) and strong for Ce(IV). Hydrolysis of Ce(IV) ions causes initial polymerization while complexation through HCOO(-) results in 12 chelate rings stabilizing the hexanuclear Ce(IV) complex. Crystals were grown from the above-mentioned solutions. Two crystal structures of Ce(IV) formate were determined. Both form a hexanuclear complex with a [Ce6(μ3-O)4(μ3-OH)4](12+) core in aqueous HNO3/HCOOH solution. The pH titration with NaOH resulted in a structure with the composition [Ce6(μ3-O)4(μ3-OH)4(HCOO)10(NO3)2(H2O)3]·(H2O)9.5, while the pH adjustment with NH3 resulted in [Ce6(μ3-O)4(μ3-OH)4(HCOO)10(NO3)4]·(NO3)3(NH4)5(H2O)5. Furthermore, the crystal structure of Ce(III) formate, Ce(HCOO)3, was determined. The coordination polyhedron is a tricapped trigonal prism which is formed exclusively by nine HCOO(-) ligands. The hexanuclear Ce(IV) formate species from aqueous solution is widely preserved in the crystal structure, whereas the mononuclear solution species of Ce(III) formate undergoes a polymerization during the crystallization process. PMID:24090406

  12. 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

  13. 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.

  14. Assessment of the CCSD and CCSD(T) Coupled-Cluster Methods in Calculating Heats of Formation for Cu Complexes

    PubMed Central

    Weaver, Michael N.; Merz, Kenneth M.

    2010-01-01

    Heats of formation for nine complexes of the form CuXn (X = Cu, H, O, OH, S, F, F2, Cl, Cl2) were calculated using the CCSD and CCSD(T) coupled cluster methods with the 6-31G** and TZVP basis sets as well as the LANL2DZ basis set/pseudopotential on Cu with both the 6-31G** and TZVP basis sets applied to the nonmetal atoms. These values were compared with literature heat of formation values. A second order Douglas-Kroll-Hess relativistic correction was applied at the CCSD/TZVP and CCSD(T)/TZVP levels of theory. Overall, the CCSD(T)/TZVP level of theory with the relativistic correction was most suited for the heat of formation calculations possessing low absolute average error and RMSD and the ability to analyze each copper complex, except for the problematic case of copper(II) fluoride. Finally, experimental geometric parameters were compared with the calculated structures in such cases where these data were available. None of the investigated levels of theory predicted bond lengths consistently better than other methods, and it was determined that the most accurate bond length does not necessarily result in the most accurate calculated heat of formation value for a given complex. PMID:20556234

  15. Review: Formation of Peptide Radical Ions Through Dissociative Electron Transfer in Ternary Metal-Ligand-Peptide Complexes

    SciTech Connect

    Chu, Ivan K.; Laskin, Julia

    2011-12-31

    The formation and fragmentation of odd-electron ions of peptides and proteins is of interest to applications in biological mass spectrometry. Gas-phase redox chemistry occurring during collision-induced dissociation of ternary metal-ligand-peptide complexes enables the formation of a variety of peptide radicals including the canonical radical cations, M{sup +{sm_bullet}}, radical dications, [M{sup +}H]{sup 2+{sm_bullet}}, radical anions, [M-2H]{sup -{sm_bullet}}. In addition, odd-electron peptide ions with well-defined initial location of the radical site are produced through side chain losses from the radical ions. Subsequent fragmentation of these species provides information on the role of charge and the location of the radical site on the competition between radical-induced and proton-driven fragmentation of odd-electron peptide ions. This account summarizes current understanding of the factors that control the efficiency of the intramolecular electron transfer (ET) in ternary metal-ligand-peptide complexes resulting in formation of odd-electron peptide ions. Specifically, we discuss the effect of the metal center, the ligand and the peptide structure on the competition between the ET, proton transfer (PT), and loss of neutral peptide and neutral peptide fragments from the complex. Fundamental studies of the structures, stabilities, and the energetics and dynamics of fragmentation of such complexes are also important for detailed molecular-level understanding of photosynthesis and respiration in biological systems.

  16. Brazilin selectively disrupts proximal IL-1 receptor signaling complex formation by targeting an IKK-upstream signaling components.

    PubMed

    Jeon, Juhee; Lee, Ji Hoon; Park, Kyeong Ah; Byun, Hee Sun; Lee, Hyunji; Lee, Yoonjung; Zhang, Tiejun; Kang, Kidong; Seok, Jeong Ho; Kwon, Hyun-Jung; Han, Man-Deuk; Kang, Seong Wook; Hong, Jang Hee; Hur, Gang Min

    2014-06-15

    The ligation of interleukin-1 receptor (IL-1R) or tumor necrosis factor receptor 1 (TNFR1) induces the recruitment of adaptor proteins and their concomitant ubiquitination to the proximal receptor signaling complex, respectively. Such are upstream signaling events of IKK that play essential roles in NF-κB activation. Thus, the discovery of a substance that would modulate the recruitment of key proximal signaling elements at the upstream level of IKK has been impending in this field of study. Here, we propose that brazilin, an active compound of Caesalpinia sappan L. (Leguminosae), is a potent NF-κB inhibitor that selectively disrupts the formation of the upstream IL-1R signaling complex. Analysis of upstream signaling events revealed that brazilin markedly abolished the IL-1β-induced polyubiquitination of IRAK1 and its interaction with IKK-γ counterpart. Notably, pretreatment of brazilin drastically interfered the recruitment of the receptor-proximal signaling components including IRAK1/4 and TRAF6 onto MyD88 in IL-1R-triggerd NF-κB activation. Interestingly, brazilin did not affect the TNF-induced RIP1 ubiquitination and the recruitment of RIP1 and TRAF2 to TNFR1, suggesting that brazilin is effective in selectively suppressing the proximal signaling complex formation of IL-1R, but not that of TNFR1. Moreover, our findings suggest that such a disruption of IL-1R-proximal complex formation by brazilin is not mediated by affecting the heterodimerization of IL-1R and IL-1RAcP. Taken together, the results suggest that the anti-IKK activity of brazilin is induced by targeting IKK upstream signaling components and subsequently disrupting proximal IL-1 receptor signaling complex formation. PMID:24735611

  17. Experimental determination of the solubility constant for magnesium chloride hydroxide hydrate (Mg 3Cl(OH) 5·4H 2O, phase 5) at room temperature, and its importance to nuclear waste isolation in geological repositories in salt formations

    NASA Astrophysics Data System (ADS)

    Xiong, Yongliang; Deng, Haoran; Nemer, Martin; Johnsen, Shelly

    2010-08-01

    In this study, the solubility constant of magnesium chloride hydroxide hydrate, Mg 3Cl(OH) 5·4H 2O, termed as phase 5, is determined from a series of solubility experiments in MgCl 2-NaCl solutions. The solubility constant in logarithmic units at 25 °C for the following reaction, MgCl(OH)·4HO+5H=3Mg+9HO(l)+Cl is calculated as 43.21 ± 0.33 (2 σ) based on the specific interaction theory (SIT) model for extrapolation to infinite dilution. The Gibbs free energy and enthalpy of formation for phase 5 at 25 °C are derived as -3384 ± 2 (2 σ) kJ mol -1 and -3896 ± 6 (2 σ) kJ mol -1, respectively. MgO (bulk, pure MgO corresponding to the mineral periclase) is the only engineered barrier certified by the Environmental Protection Agency (EPA) for emplacement in the Waste Isolation Pilot Plant (WIPP) in the US, and an Mg(OH) 2-based engineered barrier (bulk, pure Mg(OH) 2 corresponding to brucite) is to be employed in the Asse repository in Germany. Phase 5, and its similar phase, phase 3 (Mg 2Cl(OH) 3·4H 2O), could have a significant role in influencing the geochemical conditions in geological repositories for nuclear waste in salt formations where MgO or brucite is employed as engineered barriers. Based on our solubility constant for phase 5 in combination with the literature value for phase 3, we predict that the composition for the invariant point of phase 5 and phase 3 would be mMg = 1.70 and pmH = 8.94 in the Mg-Cl binary system. The recent WIPP Compliance Recertification Application Performance Assessment Baseline Calculations indicate that phase 5, instead of phase 3, is indeed a stable phase when the WIPP Generic Weep Brine (GWB), a Na-Mg-Cl-dominated brine associated with the Salado Formation, equilibrates with actinide-source-term phases, brucite, magnesium carbonates, halite and anhydrite. Therefore, phase 5 is important to the WIPP, and potentially important to other repositories in salt formations.

  18. Designing ancillary ligands for heteroleptic/homoleptic zinc complex formation: synthesis, structures and application in ROP of lactides.

    PubMed

    Jędrzkiewicz, D; Ejfler, J; Gulia, N; John, Ł; Szafert, S

    2015-08-14

    Synthesis and characterization of a series of new amino-phenol/naphthol ligands (L(1,2)-H) have been developed and their respective zinc complexes ( 1 and 2-Zn ) have been synthesized. The molecular structures of L(1)-H and 1, 2-Zn were explored in detail by NMR, single-crystal X-ray studies and DFT calculations, which confirmed the existence of complexes as stabile dimers both in a solution and in the solid state. All complexes mediate the ring-opening polymerization (ROP) of lactide highly efficiently, at room temperature, in a controlled fashion. The influence of the architecture of the ligand on the desired homo/heteroleptic complex formation, as well as the relationship between the initiator design and the catalytic activity have been investigated. PMID:26150026

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

    NASA Astrophysics Data System (ADS)

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

    2008-09-01

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

  20. Complexities of Identity Formation: A Narrative Inquiry of an EFL Teacher

    ERIC Educational Resources Information Center

    Tsui, Amy B. M.

    2007-01-01

    This article explores teachers' identity formation through a narrative inquiry of the professional identity of an EFL teacher, Minfang, in the People's Republic of China. Drawing on Wenger's (1998) social theory of identity formation as a dual process of identification and negotiation of meanings, it examines the lived experience of Minfang as an…

  1. 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 (ΔG(0), ΔH(0) and ΔS(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 hν(CT) of the charge-transfer complexes were compared with the theoretical values of hν(CT) of the complexes obtained from HOMO and LUMO of the donor and the acceptors. The reasons for the differences in hνCT values were explained. Density function theory was used for calculation. hν(CT) (experimental) values of the transition energies of the complexes in acetonitrile differed from hν(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

  2. Unusual dimer formation of cyclometalated ruthenium NHC p-cymene complexes.

    PubMed

    Schleicher, David; Tronnier, Alexander; Leopold, Hendrik; Borrmann, Horst; Strassner, Thomas

    2016-02-16

    We present the synthesis and structural characterization of novel ruthenium complexes containing C^C* cyclometalated N-heterocyclic carbene ligands, η(6)-arene (p-cymene) ligands and one bridging chlorine ion. Complexes of the general formula [Ru(p-cymene)(C^C*)Cl] were prepared via a one-pot synthesis using in situ transmetalation from the correspondent silver NHC complexes. These complexes react with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBAr(F)4) to form dinuclear complexes of the general structure [Ru(p-cymene)(C^C*)-μ-Cl-(p-cymene)(C^C*)Ru](+)[BAr(F)4](-). Solid-state structures confirm that the pseudo-tetrahedral coordination around the metal center with the η(6)-ligand aligned perpendicularly to the C^C* ligand and the i-Pr group "atop" is retained in the bimetallic complexes. PMID:26839062

  3. Imine-functionalised protic NHC complexes of Ir: direct formation by C-H activation.

    PubMed

    He, Fan; Braunstein, Pierre; Wesolek, Marcel; Danopoulos, Andreas A

    2015-02-18

    N-Arylimine-functionalised protic NHC (pNHC) Ir(i) and Ir(iii) complexes are obtained directly from neutral or cationic Ir(i) imidazole complexes using excess [Ir(cod)(μ-Cl)]2 or TlPF6, respectively. N-Arylimine-functionalised imidazolium salts lead to imidazole or pNHC complexes by competing N-H or C-H bond activation depending on the type of imidazolium counterion. PMID:25586232

  4. Three-color single molecule imaging shows WASP detachment from Arp2/3 complex triggers actin filament branch formation

    PubMed Central

    Smith, Benjamin A; Padrick, Shae B; Doolittle, Lynda K; Daugherty-Clarke, Karen; Corrêa, Ivan R; Xu, Ming-Qun; Goode, Bruce L; Rosen, Michael K; Gelles, Jeff

    2013-01-01

    During cell locomotion and endocytosis, membrane-tethered WASP proteins stimulate actin filament nucleation by the Arp2/3 complex. This process generates highly branched arrays of filaments that grow toward the membrane to which they are tethered, a conflict that seemingly would restrict filament growth. Using three-color single-molecule imaging in vitro we revealed how the dynamic associations of Arp2/3 complex with mother filament and WASP are temporally coordinated with initiation of daughter filament growth. We found that WASP proteins dissociated from filament-bound Arp2/3 complex prior to new filament growth. Further, mutations that accelerated release of WASP from filament-bound Arp2/3 complex proportionally accelerated branch formation. These data suggest that while WASP promotes formation of pre-nucleation complexes, filament growth cannot occur until it is triggered by WASP release. This provides a mechanism by which membrane-bound WASP proteins can stimulate network growth without restraining it. DOI: http://dx.doi.org/10.7554/eLife.01008.001 PMID:24015360

  5. Discovery of a Strongly-Interrelated Gene Network in Corals under Constant Darkness by Correlation Analysis after Wavelet Transform on Complex Network Model

    PubMed Central

    Zhou, Xilong; Liu, Xuefeng; Zhang, Zhaobao; Wang, Xumin; Liu, Tao; Liu, Guiming

    2014-01-01

    Coral reefs occupy a relatively small portion of sea area, yet serve as a crucial source of biodiversity by establishing harmonious ecosystems with marine plants and animals. Previous researches mainly focused on screening several key genes induced by stress. Here we proposed a novel methodcorrelation analysis after wavelet transform of complex network model, to explore the effect of light on gene expression in the coral Acropora millepora based on microarr