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Sample records for uranyl coordination complexes

  1. Electron transfer dissociation of dipositive uranyl and plutonyl coordination complexes.

    PubMed

    Rios, Daniel; Rutkowski, Philip X; Shuh, David K; Bray, Travis H; Gibson, John K; Van Stipdonk, Michael J

    2011-12-01

    Reported here is a comparison of electron transfer dissociation (ETD) and collision-induced dissociation (CID) of solvent-coordinated dipositive uranyl and plutonyl ions generated by electrospray ionization. Fundamental differences between the ETD and CID processes are apparent, as are differences between the intrinsic chemistries of uranyl and plutonyl. Reduction of both charge and oxidation state, which is inherent in ETD activation of [An(VI) O(2) (CH(3) COCH(3) )(4) ](2+) , [An(VI) O(2) (CH(3) CN)(4) ](2) , [U(VI) O(2) (CH(3) COCH(3) )(5) ](2+) and [U(VI) O(2) (CH(3) CN)(5) ](2+) (An = U or Pu), is accompanied by ligand loss. Resulting low-coordinate uranyl(V) complexes add O(2) , whereas plutonyl(V) complexes do not. In contrast, CID of the same complexes generates predominantly doubly-charged products through loss of coordinating ligands. Singly-charged CID products of [U(VI) O(2) (CH(3) COCH(3) )(4,5) ](2+) , [U(VI) O(2) (CH(3) CN)(4,5) ](2+) and [Pu(VI) O(2) (CH(3) CN)(4) ](2+) retain the hexavalent metal oxidation state with the addition of hydroxide or acetone enolate anion ligands. However, CID of [Pu(VI) O(2) (CH(3) COCH(3) )(4) ](2+) generates monopositive plutonyl(V) complexes, reflecting relatively more facile reduction of Pu(VI) to Pu(V). PMID:22223415

  2. Variable Denticity in Carboxylate Binding to the Uranyl Coordination Complexes

    SciTech Connect

    G. S. Groenewold; W. A. de Jong; J. Oomens; M. J. van Stipdonk

    2010-05-01

    Tris-carboxylate complexes of the uranyl [UO2]2+ cation with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transform ion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetatouranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of a symmetric and antisymmetric –CO2 stretches of both the monodentate and bidentate acetate, CH3 bending and umbrella vibrations, and a uranyl OUO asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate, and two bidentate benzoate ligand.

  3. Roles of acetone and diacetone alcohol in coordination and dissociation reactions of uranyl complexes.

    PubMed

    Rios, Daniel; Schoendorff, George; Van Stipdonk, Michael J; Gordon, Mark S; Windus, Theresa L; Gibson, John K; de Jong, Wibe A

    2012-12-01

    Combined collision-induced dissociation mass spectrometry experiments with DFT and MP2 calculations were employed to elucidate the molecular structures and energetics of dissociation reactions of uranyl species containing acetone and diacetone alcohol ligands. It is shown that solutions containing diacetone alcohol ligands can produce species with more than five oxygen atoms available for coordination. Calculations confirm that complexes with up to four diacetone alcohol ligands can be energetically stable but that the effective number of atoms coordinating with uranium in the equatorial plane does not exceed five. Water elimination reactions of diacetone alcohol ligands are shown to have two coordination-dependent reaction channels, through formation of mesityl oxide ligands or formation of alkoxide and protonated mesityl oxide species. The present results provide an explanation for the implausible observation of "[UO(2)(ACO)(6,7,8)](2+)" in and observed water-elimination reactions from purportedly uranyl-acetone complexes (Rios, D.; Rutkowski, P. X.; Van Stipdonk, M. J.; Gibson, J. K. Inorg. Chem. 2011, 50, 4781). PMID:23146003

  4. Roles of Acetone and Diacetone Alcohol in Coordination and Dissociation Reactions of Uranyl Complexes

    SciTech Connect

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

    2012-12-03

    Combined collision-induced dissociation mass-spectrometry experiments and DFT calculations were employed to elucidate the molecular structure of "hypercoordinated" species and the energetics of water-elimination reactions of uranyl acetone complexes observed in earlier work (Rios, D.; Rutkowski, P. X.; Van Stipdonk, M. J.; Gibson, J. K. Inorg. Chem. 2011, 50, 4781). It is shown that the "hypercoordinated" species contain diacetone alcohol ligands bonded in either bidentate or monodentate fashion, which are indistinguishable from (acetone)2 in mass spectrometry. Calculations confirm that four diacetone ligands can form stable complexes, but that the effective number of atoms coordinating with uranium in the equatorial plane does not exceed five. Diacetone alcohol ligands are shown to form mesityl oxide ligands and alkoxide species through the elimination of water, providing an explanation for the observed water-elimination reactions.

  5. Coordination of N-donor ligands to a uranyl(V) beta-diketiminate complex.

    PubMed

    Schettini, Michael F; Wu, Guang; Hayton, Trevor W

    2009-12-21

    Addition of 2 equiv of AgOTf to [UO(2)(Ar(2)nacnac)Cl](2) (Ar(2)nacnac = {(2,6-Pr(i)(2)C(6)H(3))NC(Me)}(2)CH) in the presence of excess pyridine, followed by addition of Cp(2)Co, generates the uranyl(V) complex UO(2)(Ar(2)nacnac)(py)(2) (2), in moderate yield. Complex 2 has proven to be an excellent precursor for the synthesis of other U(V) complexes. Thus, addition of 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), TMEDA, or 1-methylimidazole (MeIm) to 2 provides UO(2)(Ar(2)nacnac)(bipy) (3), UO(2)(Ar(2)nacnac)(phen) (4), UO(2)(Ar(2)nacnac)(TMEDA) (5), and UO(2)(Ar(2)nacnac)(MeIm)(2) (6), respectively. Complexes 2-6 have been fully characterized and their structures confirmed by X-ray crystallography. Attempts to form the analogous hexavalent uranyl complexes of bipy, phen, and TMEDA have not been successful. However, reaction of [UO(2)(Ar(2)nacnac)Cl](2) with AgOTf and 2 equiv of MeIm leads to the isolation of [UO(2)(Ar(2)nacnac)(MeIm)(2)][OTf] (7), which has been fully characterized. Attempts to ligate sulfur donor ligands to either the UO(2)(Ar(2)nacnac) or the [UO(2)(Ar(2)nacnac)](+) fragments were unsuccessful. PMID:19947577

  6. Alkali-metal ion coordination in uranyl(VI) poly-peroxo complexes in solution, inorganic analogues to crown-ethers. Part 2. Complex formation in the tetramethyl ammonium-, Li(+)-, Na(+)- and K(+)-uranyl(VI)-peroxide-carbonate systems.

    PubMed

    Zanonato, Pier Luigi; Szabó, Zoltán; Vallet, Valerie; Di Bernardo, Plinio; Grenthe, Ingmar

    2015-10-01

    The constitution and equilibrium constants of ternary uranyl(vi) peroxide carbonate complexes [(UO2)p(O2)q(CO3)r](2(p-q-r)) have been determined at 0 °C in 0.50 M MNO3, M = Li, K, and TMA (tetramethyl ammonium), ionic media using potentiometric and spectrophotometric data; (17)O NMR data were used to determine the number of complexes present. The formation of cyclic oligomers, "[(UO2)(O2)(CO3)]n", n = 4, 5, 6, with different stoichiometries depending on the ionic medium used, suggests that Li(+), Na(+), K(+) and TMA ions act as templates for the formation of uranyl peroxide rings where the uranyl-units are linked by μ-η(2)-η(2) bridged peroxide-ions. The templating effect is due to the coordination of the M(+)-ions to the uranyl oxygen atoms, where the coordination of Li(+) results in the formation of Li[(UO2)(O2)(CO3)]4(7-), Na(+) and K(+) in the formation of Na/K[(UO2)(O2)(CO3)]5(9-) complexes, while the large tetramethyl ammonium ion promotes the formation of two oligomers, TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-). The NMR spectra demonstrate that the coordination of Na(+) in the five- and six-membered oligomers is significantly stronger than that of TMA(+); these observations suggest that the templating effect is similar to the one observed in the synthesis of crown-ethers. The NMR experiments also demonstrate that the exchange between TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-) is slow on the (17)O chemical shift time-scale, while the exchange between TMA[(UO2)(O2)(CO3)]6(11-) and Na[(UO2)(O2)(CO3)]6(11-) is fast. There was no indication of the presence of large clusters of the type identified by Burns and Nyman (M. Nyman and P. C. Burns, Chem. Soc. Rev., 2012, 41, 7314-7367) and possible reasons for this and the implications for the synthesis of large clusters are briefly discussed. PMID:26331776

  7. Thermochromic properties of low-melting ionic uranyl isothiocyanate complexes.

    PubMed

    Aoyagi, Noboru; Shimojo, Kojiro; Brooks, Neil R; Nagaishi, Ryuji; Naganawa, Hirochika; Van Hecke, Kristof; Van Meervelt, Luc; Binnemans, Koen; Kimura, Takaumi

    2011-04-21

    Temperature-dependent yellow-to-red colour changes of uranyl thiocyanate complexes with 1-alkyl-3-methylimidazolium cations have been studied by different spectroscopic methods and this phenomenon is attributed to changes in the local environment of the uranyl ion, including the coordination number, as well as to cation-anion interactions. PMID:21399798

  8. Uranyl Sequestration: Synthesis and Structural Characterization of Uranyl Complexes with a Tetradentate Methylterephthalamide Ligand

    SciTech Connect

    Ni, Chengbao; Shuh, David; Raymond, Kenneth

    2011-03-07

    Uranyl complexes of a bis(methylterephthalamide) ligand (LH{sub 4}) have been synthesized and characterized by X-ray crystallography. The structure is an unexpected [Me{sub 4}N]{sub 8}[L(UO{sub 2})]{sub 4} tetramer, formed via coordination of the two MeTAM units of L to two uranyl moieties. Addition of KOH to the tetramer gave the corresponding monomeric uranyl methoxide species [Me{sub 4}N]K{sub 2}[LUO{sub 2}(OMe)].

  9. Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives

    SciTech Connect

    Schoendorff, George E.; Windus, Theresa L.; De Jong, Wibe A.

    2009-12-12

    The coordination of nitrile (acetonitrile, propionitrile, and benzonitrile) and carbonyl (formaldehyde, ethanal, and acetone) ligands to the uranyl dication (UO22+) has been examined using density functional theory (DFT) utilizing relativistic effective core potentials (RECPs). Complexes containing up to six ligands have been modeled for all ligands except formaldehyde, for which no minimum could be found. A comparison of relative binding energies indicates that five coordinate complexes are predominant while a six coordinate complex involving propionitrile ligands might be possible. Additionally, the relative binding energy and the weakening of the uranyl bond is related to the size of the ligand and, in general, nitriles bind more strongly to uranyl than carbonyls.

  10. Extraction of local coordination structure in a low-concentration uranyl system by XANES.

    PubMed

    Zhang, Linjuan; Zhou, Jing; Zhang, Jianyong; Su, Jing; Zhang, Shuo; Chen, Ning; Jia, Yunpeng; Li, Jiong; Wang, Yu; Wang, Jian Qiang

    2016-05-01

    Obtaining structural information of uranyl species at an atomic/molecular scale is a critical step to control and predict their physical and chemical properties. To obtain such information, experimental and theoretical L3-edge X-ray absorption near-edge structure (XANES) spectra of uranium were studied systematically for uranyl complexes. It was demonstrated that the bond lengths (R) in the uranyl species and relative energy positions (ΔE) of the XANES were determined as follows: ΔE1 = 168.3/R(U-Oax)(2) - 38.5 (for the axial plane) and ΔE2 = 428.4/R(U-Oeq)(2) - 37.1 (for the equatorial plane). These formulae could be used to directly extract the distances between the uranium absorber and oxygen ligand atoms in the axial and equatorial planes of uranyl ions based on the U L3-edge XANES experimental data. In addition, the relative weights were estimated for each configuration derived from the water molecule and nitrate ligand based on the obtained average equatorial coordination bond lengths in a series of uranyl nitrate complexes with progressively varied nitrate concentrations. Results obtained from XANES analysis were identical to that from extended X-ray absorption fine-structure (EXAFS) analysis. XANES analysis is applicable to ubiquitous uranyl-ligand complexes, such as the uranyl-carbonate complex. Most importantly, the XANES research method could be extended to low-concentration uranyl systems, as indicated by the results of the uranyl-amidoximate complex (∼40 p.p.m. uranium). Quantitative XANES analysis, a reliable and straightforward method, provides a simplified approach applied to the structural chemistry of actinides. PMID:27140156

  11. The gas-phase bis-uranyl nitrate complex [(UO2)(2)(NO3)(5)](-): infrared spectrum and structure

    SciTech Connect

    Gary S. Groenewold; Michael J. van Stipdonk; Jos Oomens; Wibe de Jong; Michael E. McIlwain

    2011-12-01

    The infrared spectrum of the bis-uranyl nitrate complex [(UO{sub 2}){sub 2}(NO{sub 3}){sub 5}]{sup -} was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate nu3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex [(UO{sub 2}){sub 2}(NO{sub 3}){sub 5}]{sup -} compared to the mono-complex [UO{sub 2}(NO{sub 3}){sub 3}]{sup -}, as indicated by a higher O-U-O asymmetric stretching (nu3) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the {nu}{sub 3} frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The structure was calculated using density functional theory (B3LYP functional), which produced a structure in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

  12. The gas-phase bis-uranyl nitrate complex [(UO2)2(NO3)5]-: infrared spectrum and structure

    SciTech Connect

    Groenewold, G. S.; van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; McIIwain, Michael E.

    2011-12-01

    The infrared spectrum of the bis-uranyl nitrate complex [(UO2)2(NO3)5]- was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate v3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex [(UO2)2(NO3)5]- compared to the mono-complex [UO2(NO3)3]-, as indicated by a higher O-U-O asymmetric stretching (v3) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the v3 frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The lowest energy structure predicted by density functional theory (B3LYP functional) calculations was one in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

  13. Extraction and coordination studies of a carbonyl-phosphine oxide scorpionate ligand with uranyl and lanthanide(III) nitrates: structural, spectroscopic and DFT characterization of the complexes.

    PubMed

    Matveeva, Anna G; Vologzhanina, Anna V; Goryunov, Evgenii I; Aysin, Rinat R; Pasechnik, Margarita P; Matveev, Sergey V; Godovikov, Ivan A; Safiulina, Alfiya M; Brel, Valery K

    2016-03-28

    Hybrid scorpionate ligand (OPPh2)2CHCH2C(O)Me (L) was synthesized and characterized by spectroscopic methods and X-ray diffraction. The selected coordination chemistry of L with UO2(NO3)2 and Ln(NO3)3 (Ln = La, Nd, Lu) has been evaluated. The isolated mono- and binuclear complexes, namely, [UO2(NO3)2L] (1), [{UO2(NO3)L}2(μ2-O2)]·EtOH (2), [La(NO3)3L2]·2.33MeCN (3), [Nd(NO3)3L2]·3MeCN (4), [Nd(NO3)2L2]+·(NO3)−·EtOH (5) and [Lu(NO3)3L2] (6) have been characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray structures have been determined for complexes 1-5. Intramolecular intraligand π-stacking interactions between two phenyl fragments of the coordinated ligand(s) were observed in all complexes 1-5. The π-stacking interaction energy was estimated from Bader's AIM theory calculations performed at the DFT level. Solution properties have been examined using IR and multinuclear ((1)H, (13)C, and (31)P) NMR spectroscopy in CD3CN and CDCl3. Coordination modes of L vary with the coordination polyhedron of the metal and solvent nature showing many coordination modes: P(O),P(O), P(O),P(O),C(O), P(O),C(O), and P(O). Preliminary extraction studies of U(VI) and Ln(III) (Ln = La, Nd, Ho, Yb) from 3.75 M HNO3 into CHCl3 show that scorpionate L extracts f-block elements (especially uranium) better than its unmodified prototype (OPPh2)2CH2. PMID:26888745

  14. EXAFS Study of Uranyl Complexation at Pseudomonas fluorescens Cell Surfaces

    NASA Astrophysics Data System (ADS)

    Bencheikh, R.; Bargar, J. R.; Tebo, B. M.

    2002-12-01

    Little is known about the roles of microbial biomass as a sink and source for uranium in contaminated aquifers, nor of the impact of bacterial biochemistry on uranium speciation in the subsurface. A significant role is implied by the high affinities of both Gram positive and Gram negative cells for binding uranyl (UO2{ 2+}). In the present study, Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy was used to identify membrane functional groups involved in uranyl binding to the Gram negative bacterium Pseudomonas fluorescens from pH 3 to pH 8. Throughout this pH-range, EXAFS spectra can be described primarily in terms of coordination of carboxylic groups to uranyl. U-C distances characteristic of 4-, 5- and 8- membered rings were observed, as well as the possibility of phosphato groups. Both shell-by-shell fits and principle component analyses indicate that the functional groups involved in binding of uranyl to the cell surface do not vary systematically across the pH range investigated. This result contrasts with EXAFS results of uranyl sorbed to Gram positive bacteria, and suggests an important role for long-chain carboxylate-terminated membrane functional groups in binding uranyl.

  15. Bonding and charge transfer in nitrogen-donor uranyl complexes: insights from NEXAFS spectra.

    PubMed

    Pemmaraju, C D; Copping, Roy; Wang, Shuao; Janousch, Markus; Teat, Simon J; Tyliszcak, Tolek; Canning, Andrew; Shuh, David K; Prendergast, David

    2014-11-01

    We investigate the electronic structure of three newly synthesized nitrogen-donor uranyl complexes [(UO2)(H2bbp)Cl2], [(UO)2(Hbbp)(Py)Cl], and [(UO2)(bbp)(Py)2] using a combination of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy experiments and simulations. The complexes studied feature derivatives of the tunable tridentate N-donor ligand 2,6-bis(2-benzimidazyl)pyridine (bbp) and exhibit discrete chemical differences in uranyl coordination. The sensitivity of the N K-edge X-ray absorption spectrum to local bonding and charge transfer is exploited to systematically investigate the evolution of structural as well as electronic properties across the three complexes. A thorough interpretation of the measured experimental spectra is achieved via ab initio NEXAFS simulations based on the eXcited electron and Core-Hole (XCH) approach and enables the assignment of spectral features to electronic transitions on specific absorbing sites. We find that ligand-uranyl bonding leads to a signature blue shift in the N K-edge absorption onset, resulting from charge displacement toward the uranyl, while changes in the equatorial coordination shell of the uranyl lead to more subtle modulations in the spectral features. Theoretical simulations show that the flexible local chemistry at the nonbinding imidazole-N sites of the bbp ligand is also reflected in the NEXAFS spectra and highlights potential synthesis strategies to improve selectivity. In particular, we find that interactions of the bbp ligand with solvent molecules can lead to changes in ligand-uranyl binding geometry while also modulating the K-edge absorption. Our results suggest that NEXAFS spectroscopy combined with first-principles interpretation can offer insights into the coordination chemistry of analogous functionalized conjugated ligands. PMID:25330350

  16. Surface complexation model of uranyl sorption on Georgia kaolinite

    USGS Publications Warehouse

    Payne, T.E.; Davis, J.A.; Lumpkin, G.R.; Chisari, R.; Waite, T.D.

    2004-01-01

    The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3-10), total U (1 and 10 ??mol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uranium was preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO2, its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite. ?? 2004 Elsevier B.V. All rights reserved.

  17. EXAFS determinations of uranium structures: The uranyl ion complexed with tartaric, citric, and malic acids

    SciTech Connect

    Allen, P.G.; Shuh, D.K.; Bucher, J.J.

    1996-01-31

    Studies of the coordination chemistry of uranium in aqueous solutions are increasingly important for understanding the behavior of uranium in the environment. Actinide speciation information is essential for assessing and developing long-term strategies addressing problems such as migration in nuclear waste repositories or improvements in the processing of nuclear waste and materials. Relative to the latter, one method for removing uranium contamination from soils involves extraction using a chelating agent such as Tiron, or citrate. These types of extractants are quite efficient at binding the uranyl ion and thus are suitable for removing uranium contamination when it is in the hexavalent uranyl ion form. Martell et al. and Markovits et al. have published a series of articles detailing the complexation of the uranyl ion with tartaric, malic, and citric acids as a function of pH. Using the functional dependencies of potentiometric titration results, they showed that, in the pH range 2-4, the uranyl ion forms a 2:2 dimeric species, (UO{sub 2}){sub 2-} (L){sub 2}, where L = tartrate, malate, or citrate ligands. The authors have reinvestigated the solution structures of the uranyl complexes formed in these systems with the structural technique extended X-ray absorption fine-structure (EXAFS) spectroscopy.

  18. 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

  19. 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.

  20. Gas phase uranyl activation: formation of a uranium nitrosyl complex from uranyl azide.

    PubMed

    Gong, Yu; de Jong, Wibe A; Gibson, John K

    2015-05-13

    Activation of the oxo bond of uranyl, UO2(2+), was achieved by collision induced dissociation (CID) of UO2(N3)Cl2(-) in a quadrupole ion trap mass spectrometer. The gas phase complex UO2(N3)Cl2(-) was produced by electrospray ionization of solutions of UO2Cl2 and NaN3. CID of UO2(N3)Cl2(-) resulted in the loss of N2 to form UO(NO)Cl2(-), in which the "inert" uranyl oxo bond has been activated. Formation of UO2Cl2(-) via N3 loss was also observed. Density functional theory computations predict that the UO(NO)Cl2(-) complex has nonplanar Cs symmetry and a singlet ground state. Analysis of the bonding of the UO(NO)Cl2(-) complex shows that the side-on bonded NO moiety can be considered as NO(3-), suggesting a formal oxidation state of U(VI). Activation of the uranyl oxo bond in UO2(N3)Cl2(-) to form UO(NO)Cl2(-) and N2 was computed to be endothermic by 169 kJ/mol, which is energetically more favorable than formation of NUOCl2(-) and UO2Cl2(-). The observation of UO2Cl2(-) during CID is most likely due to the absence of an energy barrier for neutral ligand loss. PMID:25906363

  1. Spectroscopic study on uranyl carboxylate complexes formed at the surface layer of Sulfolobus acidocaldarius.

    PubMed

    Reitz, Thomas; Rossberg, Andre; Barkleit, Astrid; Steudtner, Robin; Selenska-Pobell, Sonja; Merroun, Mohamed L

    2015-02-14

    The complexation of U(vi) at the proteinaceous surface layer (S-layer) of the archaeal strain Sulfolobus acidocaldarius was investigated over a pH range from pH 1.5 to 6 at the molecular scale using time-resolved laser-induced fluorescence spectroscopy (TRLFS) and U L(III)-edge extended X-ray absorption fine structure (EXAFS). The S-layer, which represents the interface between the cell and its environment, is very stable against high temperatures, proteases, and detergents. This allowed the isolation and purification of S-layer ghosts (= empty cells) that maintain the size and shape of the cells. In contrast to many other microbial cell envelope compounds the studied S-layer is not phosphorylated, enabling the investigation of uranyl carboxylate complexes formed at microbial surfaces. The latter are usually masked by preferentially formed uranyl phosphate complexes. We demonstrated that at highly acidic conditions (pH 1.5 to 3) no uranium was bound by the S-layer. In contrast to that, at moderate acidic pH conditions (pH 4.5 and 6) a complexation of U(vi) at the S-layer via deprotonated carboxylic groups was stimulated. Titration studies revealed dissociation constants for the carboxylic groups of glutamic and aspartic acid residues of pK(a) = 4.78 and 6.31. The uranyl carboxylate complexes formed at the S-layer did not show luminescence properties at room temperature, but only under cryogenic conditions. The obtained luminescence maxima are similar to those of uranyl acetate. EXAFS spectroscopy demonstrated that U(vi) in these complexes is mainly coordinated to carboxylate groups in a bidentate binding mode. The elucidation of the molecular structure of these complexes was facilitated by the absence of phosphate groups in the studied S-layer protein. PMID:25387060

  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. Predicting stability constants for uranyl complexes using density functional theory.

    PubMed

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

    2015-04-20

    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 use density functional theory (B3LYP) and the integral equation formalism polarizable continuum model (IEF-PCM) to compute aqueous stability constants for UO2(2+) 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 chelating capability to uranyl. PMID:25835578

  5. 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).

  6. Intrinsic Hydration of Uranyl-Hydroxide, -Nitrate and -Acetate Complexes

    SciTech Connect

    Winnie Chien; Dorothy Hanna; Victor Anbalagan; Garold Gresham; Gary Groenewold; Michael Van Stipdonk

    2004-06-01

    The intrinsic hydration of three monopositive uranyl-anion complexes (UO2A)+ (where A = acetate, nitrate, or hydroxide) was investigated using ion-trap mass spectrometry (IT-MS). The relative rates for the formation of the monohydrates [(UO2A)(H2O)]+, with respect to the anion, followed the trend: Acetate = nitrate >> hydroxide. This finding was rationalized in terms of the donation of electron density by the strongly basic OH- to the uranyl metal center, thereby reducing the Lewis acidity of U and its propensity to react with incoming nucleophiles, viz., H2O. An alternative explanation is that the more complex acetate and nitrate anions provide increased degrees of freedom that could accommodate excess energy from the hydration reaction. The monohydrates also reacted with water, forming dihydrates and then trihydrates. The rates for formation of the nitrate and acetate dihydrates [(UO2A)(H2O)2]+ were very similar to the rates for formation of the monohydrates; the presence of the first H2O ligand had no influence on the addition of the second. In contrast, formation of the [(UO2OH)(H2O)2]+ was nearly three times faster than the formation of the monohydrate.

  7. Tetraalkylammonium uranyl isothiocyanates.

    PubMed

    Rowland, Clare E; Kanatzidis, Mercouri G; Soderholm, L

    2012-11-01

    Three tetraalkylammonium uranyl isothiocyanates, [(CH(3))(4)N](3)UO(2)(NCS)(5) (1), [(C(2)H(5))(4)N](3)UO(2)(NCS)(5) (2), and [(C(3)H(7))(4)N](3)UO(2)(NCS)(5) (3), have been synthesized from aqueous solution and their structures determined by single-crystal X-ray diffraction. All of the compounds consist of the uranyl cation equatorially coordinated to five N-bound thiocyanate ligands, UO(2)(NCS)(5)(3-), and charge-balanced by three tetraalkylammonium cations. Raman spectroscopy data have been collected on compounds 1-3, as well as on solutions of uranyl nitrate with increasing levels of sodium thiocyanate. By tracking the Raman signatures of thiocyanate, the presence of both free and bound thiocyanate is confirmed in solution. The shift in the Raman signal of the uranyl symmetric stretching mode suggests the formation of higher-order uranyl thiocyanate complexes in solution, while the solid-state Raman data support homoleptic isothiocyanate coordination about the uranyl cation. Presented here are the syntheses and crystal structures of 1-3, pertinent Raman spectra, and a discussion regarding the relationship of these isothiocyanates to previously described uranyl halide phases, UO(2)X(4)(2-). PMID:23072277

  8. Complex nanoscale cage clusters built from uranyl polyhedra and phosphate tetrahedra

    SciTech Connect

    Unruh, Daniel K.; Ling, Jie; Qiu, Jie; Pressprich, Laura; Baranay, Melissa; Ward, Matthew; Burns, Peter C.

    2011-06-20

    Five cage clusters that self-assemble in alkaline aqueous solution have been isolated and characterized. Each is built from uranyl hexagonal bipyramids with two or three equatorial edges occupied by peroxide, and three also contain phosphate tetrahedra. These clusters contain 30 uranyl polyhedra; 30 uranyl polyhedra and six pyrophosphate groups; 30 uranyl polyhedra, 12 pyrophosphate groups, and one phosphate tetrahedron; 42 uranyl polyhedra; and 40 uranyl polyhedra and three pyrophosphate groups. These clusters present complex topologies as well as a range of compositions, sizes, and charges. Two adopt fullerene topologies, and the others contain combinations of topological squares, pentagons, and hexagons. An analysis of possible topologies further indicates that higher-symmetry topologies are favored.

  9. Oxidation of 2-propanol ligands during collision-induced dissociation of a gas-phase uranyl complex

    NASA Astrophysics Data System (ADS)

    van Stipdonk, Michael J.; Chien, Winnie; Anbalagan, Victor; Gresham, Garold L.; Groenewold, Gary S.

    2004-10-01

    We demonstrate, by way of multi-stage tandem mass spectrometry and extensive deuterium labeling, that 2-propanol is converted to acetone, and 2-propoxide to acetaldehyde, when monopositive 2-propanol-coordinated uranyl-ligand cations are subjected to collision-induced dissociation in the gas-phase environment of an ion trap mass spectrometer. A species with formula [(UO2OCH(CH3)2)(HOCH(CH3)2)]+, derived from dissociation of the gas-phase precursor [(UO2NO3)(HOCH(CH3)2)3]+ eliminates two H atoms and CH3 in consecutive stages to generate a monopositive complex composed of the U(V) species UO2+ coordinated by acetone and acetaldehyde, i.e. [UO2+(OC(CH3)2)(OC(H)CH3)]. Dissociation of this latter ion resulted in elimination of the two coordinating carbonyl ligands in two consecutive dissociation stages to leave UO2+. Analogous reactions were not observed for uranyl complexes containing 1-propanol or 2-methyl-2-propanol, or for cationic complexes with divalent metals such as Ni2+, Co2+, Pb2+ and Ca2+. One explanation for these reactions is bond insertion by the metal center in the bis-ligated uranyl complex, which would be expected to have an LUMO consisting of unoccupied 6d-orbitals that would confer transition metal-like behavior on the complex.

  10. Hydrothermal Crystallization of Uranyl Coordination Polymers Involving an Imidazolium Dicarboxylate Ligand: Effect of pH on the Nuclearity of Uranyl-Centered Subunits.

    PubMed

    Martin, Nicolas P; Falaise, Clément; Volkringer, Christophe; Henry, Natacha; Farger, Pierre; Falk, Camille; Delahaye, Emilie; Rabu, Pierre; Loiseau, Thierry

    2016-09-01

    Four uranyl-bearing coordination polymers (1-4) have been hydrothermally synthesized in the presence of the zwitterionic 1,3-bis(carboxymethyl)imidazolium (= imdc) anion as organic linkers after reaction at 150 °C. At low pH (0.8-3.1), the form 1 ((UO2)2(imdc)2(ox)·3H2O; ox stands for oxalate group) has been identified. Its crystal structure (XRD analysis) consists of the 8-fold-coordinated uranyl centers linked to each other through the imdc ligand together with oxalate species coming from the partial decomposition of the imdc molecule. The resulting structure is based on one-dimensional infinite ribbons intercalated by free water molecules. By adding NaOH solution, a second form 2 is observed for pH 1.9-3.9 but in a mixture with phase 1. The pure phase of 2 is obtained after a hydrothermal treatment at 120 °C. It corresponds to a double-layered network (UO2(imdc)2) composed of 7-fold-coordinated uranyl cations linked via the imdc ligands. In the same pH range, a third phase ((UO2)3O2(H2O)(imdc)·H2O, 3) is formed: it is composed of hexanuclear units of 7-fold- and 8-fold-coordinated uranyl cations, connected via the imdc molecules in a layered assembly. At higher pH, the chain-like solid (UO2)3O(OH)3(imdc)·2H2O (4) is observed and composed of the infinite edge-sharing uranyl-centered pentagonal bipyramidal polyhedra. As a function of pH, uranyl nuclearity increases from discrete 8- or 7-fold uranyl centers (1, 2) to hexanuclear bricks (3) and then infinite chains in 4 (built up from the hexameric fragments found in 3). This observation emphasized the influence of the hydrolysis reaction occurring between uranyl centers. The compounds have been further characterized by thermogravimetric analysis, infrared, and luminescence spectroscopy. PMID:27509393

  11. Complex formation between uranyl and various thiosemicarbazide derivatives

    SciTech Connect

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

    1987-01-01

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

  12. Uranyl sensitization of samarium (III) luminescence in a two-dimensional coordination polymer

    SciTech Connect

    Knope, Karah E.; de Lill, Daniel T.; Rowland, Clare E.; Cantos, Paula M.; de Bettencourt-Dias, Ana; Cahill, Christopher L.

    2012-01-02

    Heterometallic carboxyphosphonates UO₂2+/Ln3+ have been prepared from the hydrothermal reaction of uranyl nitrate, lanthanide nitrate (Ln = Sm, Tb, Er, Yb), and phosphonoacetic acid (H₃PPA). Compound 1, (UO₂)₂(PPA)(HPPA)₂Sm(H₂O)·2H₂O (1) adopts a two-dimensional structure in which the UO₂2+ metal ions bind exclusively to the phosphonate moiety, whereas the Ln3+ ions are coordinated by both phosphonate and carboxylate functionalities. Luminescence studies of 1 show very bright visible and near-IR samarium(III)-centered emission upon direct excitation of the uranyl moiety. The Sm3+ emissive state exhibits a double-exponential decay with lifetimes of 67.2 ± 6.5 and 9.0 ± 1.3 μs as measured at 594 nm, after excitation at both 365 and 420 nm. No emission is observed in the region typical of the uranyl cation, indicating that all energy is either transferred to the Sm3+ center or lost to nonradiative processes. Herein we report the synthesis, crystal structure, and luminescent behavior of 1, as well as those of the isostructural terbium, erbium, and ytterbium analogues.

  13. X-ray Absorption Spectroscopy Identifies Calcium-Uranyl-Carbonate Complexes at Environmental Concentrations

    SciTech Connect

    Kelly, Shelly D; Kemner, Kenneth M; Brooks, Scott C

    2007-01-01

    Current research on bioremediation of uranium-contaminated groundwater focuses on supplying indigenous metal-reducing bacteria with the appropriate metabolic requirements to induce microbiological reduction of soluble uranium(VI) to poorly soluble uranium(IV). Recent studies of uranium(VI) bioreduction in the presence of environmentally relevant levels of calcium revealed limited and slowed uranium(VI) reduction and the formation of a Ca-UO2-CO3 complex. However, the stoichiometry of the complex is poorly defined and may be complicated by the presence of a Na-UO2-CO3 complex. Such a complex might exist even at high calcium concentrations, as some UO2-CO3 complexes will still be present. The number of calcium and/or sodium atoms coordinated to a uranyl carbonate complex will determine the net charge of the complex. Such a change in aqueous speciation of uranium(VI) in calcareous groundwater may affect the fate and transport properties of uranium. In this paper, we present the results from X-ray absorption fine structure (XAFS) measurements of a series of solutions containing 50 lM uranium(VI) and 30 mM sodium bicarbonate, with various calcium concentrations of 0-5 mM. Use of the data series reduces the uncertainty in the number of calcium atoms bound to the UO2-CO3 complex to approximately 0.6 and enables spectroscopic identification of the Na-UO2-CO3 complex. At nearly neutral pH values, the numbers of sodium and calcium atoms bound to the uranyl triscarbonate species are found to depend on the calcium concentration, as predicted by speciation calculations.

  14. X-ray absorption spectroscopy identifies calcium-uranyl-carbonate complexes at environmental concentrations.

    SciTech Connect

    Kelly, S. D.; Kemner, K. M.; Brooks, S. C.; Biosciences Division; ORNL

    2007-01-01

    Current research on bioremediation of uranium-contaminated groundwater focuses on supplying indigenous metal-reducing bacteria with the appropriate metabolic requirements to induce microbiological reduction of soluble uranium(VI) to poorly soluble uranium(IV). Recent studies of uranium(VI) bioreduction in the presence of environmentally relevant levels of calcium revealed limited and slowed uranium(VI) reduction and the formation of a Ca-UO{sub 2}-CO{sub 3} complex. However, the stoichiometry of the complex is poorly defined and may be complicated by the presence of a Na-UO{sub 2}-CO{sub 3} complex. Such a complex might exist even at high calcium concentrations, as some UO{sub 2}-CO{sub 3} complexes will still be present. The number of calcium and/or sodium atoms coordinated to a uranyl carbonate complex will determine the net charge of the complex. Such a change in aqueous speciation of uranium(VI) in calcareous groundwater may affect the fate and transport properties of uranium. In this paper, we present the results from X-ray absorption fine structure (XAFS) measurements of a series of solutions containing 50 {micro}M uranium(VI) and 30 mM sodium bicarbonate, with various calcium concentrations of 0-5 mM. Use of the data series reduces the uncertainty in the number of calcium atoms bound to the UO{sub 2}-CO{sub 3} complex to approximately 0.6 and enables spectroscopic identification of the Na-UO{sub 2}-CO{sub 3} complex. At nearly neutral pH values, the numbers of sodium and calcium atoms bound to the uranyl triscarbonate species are found to depend on the calcium concentration, as predicted by speciation calculations.

  15. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

    SciTech Connect

    Park, Sang-Won; Leckie, J.O.; Siegel, M.D.

    1995-09-01

    Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption.

  16. Syntheses and crystal structures of two novel alkaline uranyl chromates A{sub 2}(UO{sub 2})(CrO{sub 4}){sub 2} (A=Rb, Cs) with bidentate coordination mode of uranyl ions by chromate anions

    SciTech Connect

    Siidra, Oleg I.

    2012-03-15

    Single crystals of Cs{sub 2}(UO{sub 2})(CrO{sub 4}){sub 2} and Rb{sub 2}(UO{sub 2})(CrO{sub 4}){sub 2} were prepared by solid state reactions. The structures are based upon the [(UO{sub 2})(CrO{sub 4}){sub 2}]{sup 2-} chains. Within the chains, UrO{sub 5} pentagonal bipyramids (Ur=uranyl) form Ur{sub 2}O{sub 8} dimers, which are linked via CrO{sub 4} tetrahedra into one-dimensional chains. The CrO{sub 4} tetrahedra coordinate uranyl ions in both mono- and bidentate fashion, which is unusual for uranyl chromates. The bidentate coordination has a strong influence upon geometrical parameters of both U and Cr coordination polyhedra. The conformation of the chains in 1 and 2 is different due to the different size of the Cs{sup +} and Rb{sup +} cations. - Graphical abstract: Uranyl chromate chain with monodentate and bidentate coordination mode of uranyl cations by CrO{sub 4} tetrahedra in Cs{sub 2}(UO{sub 2})(CrO{sub 4}){sub 2}. Highlights: Black-Right-Pointing-Pointer Single crystals of novel uranyl chromates were prepared by solid state reactions. Black-Right-Pointing-Pointer The CrO{sub 4} tetrahedra coordinate uranyl ions in both mono- and bidentate fashion. Black-Right-Pointing-Pointer The bidentate coordination has a strong influence upon geometrical parameters.

  17. The Influence of Linker Geometry on Uranyl Complexation by Rigidly-Linked Bis(3-hydroxy-N-methyl-pyridin-2-one)

    SciTech Connect

    Szigethy, Geza; Raymond, Kenneth

    2010-04-22

    A series of bis(3-hydroxy-N-methyl-pyridin-2-one) ligands was synthesized, and their respective uranyl complexes were characterized by single crystal X-ray diffraction analyses. These structures were inspected for high-energy conformations and evaluated using a series of metrics to measure co-planarity of chelating moieties with each other and the uranyl coordination plane, as well as to measure coordinative crowding about the uranyl dication. Both very short (ethyl, 3,4-thiophene and o-phenylene) and very long ({alpha},{alpha}{prime}-m-xylene and 1,8-fluorene) linkers provide optimal ligand geometries about the uranyl cation, resulting in planar, unstrained molecular arrangements. The planarity of the rigid linkers also suggests there is a degree of pre-organization for a planar coordination mode that is ideal for uranyl-selective ligand design. Comparison of intramolecular N{sub amide}-O{sub phenolate} distances and {sup 1}H NMR chemical shifts of amide protons supports earlier results that short linkers provide the optimal geometry for intramolecular hydrogen bonding.

  18. Designing the Ideal Uranyl Ligand: a Sterically-Induced Speciation Change in Complexes with Thiophene-Bridged Bis(3-hydroxy-N-methylpyridin-2-one)

    SciTech Connect

    Szigethy, Geza; Raymond, Kenneth N.

    2009-09-11

    Structural characterization of a mononuclear uranyl complex with a tetradentate, thiophene-linked bis(3-hydroxy-N-methylpyridin-2-one) ligand reveals the most planar coordination geometry yet observed with this ligand class. The introduction of ethylsulfanyl groups onto the thiophene linker disrupts this planar, conjugated ligand arrangement, resulting in the formation of dimeric (UO{sub 2}){sub 2}L{sub 2} species in which each ligand spans two uranyl centers. Relative energy calculations reveal that this tendency toward dimer formation is the result of steric interference between ethylsulfanyl substituents and linking amides.

  19. Designing the ideal uranyl ligand: a sterically induced speciation change in complexes with thiophene-bridged bis(3-hydroxy-n-methylpyridin-2-one).

    PubMed

    Szigethy, Géza; Raymond, Kenneth N

    2009-12-21

    Structural characterization of a mononuclear uranyl complex with a tetradentate, thiophene-linked bis(3-hydroxy-N-methylpyridin-2-one) ligand reveals the most planar coordination geometry yet observed with this ligand class. The introduction of ethylsulfanyl groups onto the thiophene linker disrupts this planar, conjugated ligand arrangement, resulting in the formation of dimeric (UO(2))(2)L(2) species in which each ligand spans two uranyl centers. Relative energy calculations reveal that this tendency toward dimer formation is the result of steric interference between ethylsulfanyl substitutents and linking amides. PMID:19928845

  20. Construction of Uranyl Selective Electrode Based on Complex of Uranyl Ion with New Ligand Carboxybenzotriazole in PVC Matrix Membrane

    NASA Astrophysics Data System (ADS)

    Abu-Dalo, M. A.; Al-Rawashdeh, N. A. F.; Al-Mheidat, I. R.; Nassory, N. S.

    2015-10-01

    In the present study uranyl selective electrodes in polyvinyl chloride (PVC) matrix membrane were prepared based on a complex of uranyl ion (UO2) with carboxybenzotriazole (CBT) as ligand. The effect of the nature of plasticizer in PVC matrix were evaluated using three different plasticizers, these are dibutyl phthalate (DBP), dioctyl phthalate (DOP) and bis(2-ethylhexyl) sebacate (BHS). The results of this study indicated that the best plasticizer could be used is the DBP, which may be attributed to its lowest viscosity value compared to DOP and BHS. The electrodes with DBP as plasticizer exhibits a Nernstian response with a slope of 28.0 mV/ decade, over a wide range of concentration from 3.0×10-5-6.0×10-2 M and a detection limit of 4.0×10-6 M. It can be used in the pH range of 4.0-10.0 with a response time of less than 10 s for DBP and 25 s for both DOP and BHS. The effects of ions interferences on the electrode response were evaluated. The di- and tri-valent cations were found to interfere less than univalent cations, which was attributed to the high diffusion and the exchange rate between the univalent ions and the uranyl ion solution. The electrodes were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron microscopy (SEM). The results of the standard addition method were satisfactory with errors less than 7%. The developed electrode was found to be fast, sensitive and reliable indicated its potential use in measuring the uranly ion concentration in the field.

  1. Binding constant determination of uranyl-citrate complex by ACE using a multi-injection method.

    PubMed

    Zhang, Yiding; Li, Linnan; Huang, Hexiang; Xu, Linnan; Li, Ze; Bai, Yu; Liu, Huwei

    2015-04-01

    The binding constant determination of uranyl with small-molecule ligands such as citric acid could provide fundamental knowledge for a better understanding of the study of uranyl complexation, which is of considerable importance for multiple purposes. In this work, the binding constant of uranyl-citrate complex was determined by ACE. Besides the common single-injection method, a multi-injection method to measure the electrophoretic mobility was also applied. The BGEs used contained HClO4 and NaClO4 , with a pH of 1.98 ± 0.02 and ionic strength of 0.050 mol/L, then citric acid was added to reach different concentrations. The electrophoretic mobilities of the uranyl-citrate complex measured by both of the two methods were consistent, and then the binding constant was calculated by nonlinear fitting assuming that the reaction had a 1:1 stoichiometry and the complex was [(UO2 )(Cit)](-) . The binding constant obtained by the multi-injection method was log K = 9.68 ± 0.07, and that obtained by the single-injection method was log K = 9.73 ± 0.02. The results provided additional knowledge of the uranyl-citrate system, and they demonstrated that compared with other methods, ACE using the multi-injection method could be an efficient, fast, and simple way to determine electrophoretic mobilities and to calculate binding constants. PMID:25598434

  2. Activation of gas-phase uranyl: from an oxo to a nitrido complex.

    PubMed

    Gong, Yu; Vallet, Valérie; Michelini, Maria del Carmen; Rios, Daniel; Gibson, John K

    2014-01-01

    The uranyl moiety, UO2(2+), is ubiquitous in the chemistry of uranium, the most prevalent actinide. Replacing the strong uranium-oxygen bonds in uranyl with other ligands is very challenging, having met with only limited success. We report here uranyl oxo bond activation in the gas phase to form a terminal nitrido complex, a previously elusive transformation. Collision induced dissociation of gas-phase UO2(NCO)Cl2(-) in an ion trap produced the nitrido oxo complex, NUOCl2(-), and CO2. NUOCl2(-) was computed by DFT to have Cs symmetry and a singlet ground state. The computed bond length and order indicate a triple U-N bond. Endothermic activation of UO2(NCO)Cl2(-) to produce NUOCl2(-) and neutral CO2 was computed to be thermodynamically more favorable than NCO ligand loss. Complete reaction pathways for the CO2 elimination process were computed at the DFT level. PMID:24354492

  3. Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium(V) cation: implications for selectivity towards uranyl.

    PubMed

    Mehio, Nada; Johnson, J Casey; Dai, Sheng; Bryantsev, Vyacheslav S

    2015-12-21

    Poly(acrylamidoxime)-based fibers bearing random mixtures of carboxylate and amidoxime groups are the most widely utilized materials for extracting uranium from seawater. However, the competition between uranyl (UO2(2+)) and vanadium ions poses a significant challenge to the industrial mining of uranium from seawater using the current generation of adsorbents. To design more selective adsorbents, a detailed understanding of how major competing ions interact with carboxylate and amidoxime ligands is required. In this work, we employ density functional theory (DFT) and wave-function methods to investigate potential binding motifs of the dioxovanadium ion, VO2(+), with water, formate, and formamidoximate ligands. Employing higher level of theory calculations (CCSD(T)) resolve the existing controversy between the experimental results and previous DFT calculations for the structure of the hydrated VO2(+) ion. Consistent with the EXAFS data, CCSD(T) calculations predict higher stability of the distorted octahedral geometry of VO2(+)(H2O)4 compared to the five-coordinate complex with a single water molecule in the second hydration shell, while all seven tested DFT methods yield the reverse stability of the two conformations. Analysis of the relative stabilities of formate-VO2(+) complexes indicates that both monodentate and bidentate forms may coexist in thermodynamic equilibrium in solution. Investigations of VO2(+) coordination with the formamidoximate anion has revealed the existence of seven possible binding motifs, four of which are within ∼4.0 kcal mol(-1) of each other. Calculations establish that the most stable binding motif entails the coordination of oxime oxygen and amide nitrogen atoms via a tautomeric rearrangement of amidoxime to imino hydroxylamine. The difference in the most stable VO2(+) and UO2(2+) binding conformation has important implications for the design of more selective UO2(2+) ligands. PMID:26559445

  4. Structural characterization of environmentally relevant ternary uranyl citrate complexes present in aqueous solutions and solid state materials.

    PubMed

    Basile, Madeline; Unruh, Daniel K; Flores, Erin; Johns, Adam; Forbes, Tori Z

    2015-02-14

    Organic acids are important metal chelators in environmental systems and tend to form soluble complexes in aqueous solutions, ultimately influencing the transport and bioavailability of contaminants in surface and subsurface waters. This is particularly true for the formation of uranyl citrate complexes, which have been utilized in advanced photo- and bioremediation strategies for soils contaminated with nuclear materials. Given the complexity of environmental systems, the formation of ternary or heterometallic uranyl species in aqueous solutions are also expected, particularly with Al(iii) and Fe(iii) cations. These ternary forms are reported to be more stable in aqueous solutions, potentially enhancing contaminant mobility and uptake by organisms, but the exact coordination geometries of these soluble molecular complexes have not been elucidated. To provide insight into the nature of these species, we have developed a series of geochemical model compounds ([(UO(2))(2)Al(2)(C(6)H(4)O(7))(4)](6-) (U(2)Al(2)), [(UO(2))(2)Fe(2)(C(6)H(4)O(7))(4)](6-) (U(2)Fe(2)-1) and [(UO(2))(2)Fe(2)(C(6)H(4)O(7))(4)(H(2)O)(2)](6-) (U(2)Fe(2)-2) and [(UO(2))(2)Fe(4)(OH)(4)(C(6)H(4)O(7))(4)](8-) (U(2)Fe(4))) that were characterized by single-crystal X-ray diffraction and vibrational spectroscopy. Mass spectroscopy was then employed to compare the model compounds to species present in aqueous solutions to provide an enhanced understanding of the ternary uranyl citrate complexes that could be relevant in natural systems. PMID:25372632

  5. Modulation of the Structure and Properties of Uranyl Ion Coordination Polymers Derived from 1,3,5-Benzenetriacetate by Incorporation of Ag(I) or Pb(II).

    PubMed

    Thuéry, Pierre; Harrowfield, Jack

    2016-07-01

    Reaction of uranyl nitrate with 1,3,5-benzenetriacetic acid (H3BTA) in the presence of additional species, either organic bases or their conjugate acids or metal cations, has provided 12 new crystalline complexes, all but one obtained under solvo-hydrothermal conditions. The complexes [C(NH2)3][UO2(BTA)]·H2O (1) and [H2NMe2][UO2(BTA)] (2) crystallize as one- or two-dimensional (1D or 2D) assemblies, respectively, both with uranyl tris-chelation by carboxylate groups and hydrogen-bonded counterions but different ligand conformations. One of the bound carboxylate units is replaced by chelating 1,10-phenanthroline (phen) or 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4phen) in the complexes [(UO2)3(BTA)2(phen)3]·4H2O (3) and [(UO2)3(BTA)2(Me4phen)3]·NMP·3H2O (4) (NMP = N-methyl-2-pyrrolidone), which are a 2D network with honeycomb topology and a 1D polymer, respectively. With silver(I) cations, [UO2Ag(BTA)] (5), a three-dimensional (3D) framework in which the ligand assumes various chelating/bridging coordination modes, and the aromatic ring is involved in Ag(I) bonding, is obtained. A series of seven heterometallic complexes results when lead(II) cations and N-chelating molecules are both present. The complexes [UO2Pb(BTA)(NO3)(bipy)] (6) and [UO2Pb2(BTA)2(bipy)2]·3H2O (7), where bipy is 2,2'-bipyridine, crystallize from the one solution, as 1D and 2D assemblies, respectively. The two 1D coordination polymers [UO2Pb(BTA)(HCOO)(phen)] (8 and 9), again obtained from the one synthesis, provide an example of coordination isomerism, with the formate anion bound either to lead(II) or to uranyl cations. Another 2D architecture is found in [(UO2)2Pb2(BTA)2(HBTA)(H2O)2(phen)2]·2H2O (10), which provides a possible example of a Pb-oxo(uranyl) "cation-cation" interaction. While [UO2Pb(BTA)(HCOO)0.5(NO3)0.5(Me2phen)] (11), where Me2phen is 5,6-dimethyl-1,10-phenanthroline, is a 1D assembly close to those in 6 and 8, [UO2Pb2(BTA)2(Me4phen)2] (12), obtained together with

  6. Density Functional Theory Study of the Complexation of the Uranyl Dication with Anionic Phosphate Ligands with and without Water Molecules

    SciTech Connect

    Jackson, Virgil E.; Gutowski, Keith E.; Dixon, David A.

    2013-08-01

    The structures, vibrational frequencies and energetics of anhydrous and hydrated complexes of UO2 2+ with the phosphate anions H2PO4 -, HPO4 2-, and PO4 3- were predicted at the density functional theory (DFT) and MP2 molecular orbital theory levels as isolated gas phase species and in aqueous solution by using self-consistent reaction field (SCRF) calculations with different solvation models. The geometries and vibrational frequencies of the major binding modes for these complexes are compared to experiment where possible and good agreement is found. The uranyl moiety is nonlinear in many of the complexes, and the coordination number (CN) 5 in the equatorial plane is the predominant binding motif. The phosphates are found to bind in both monodentate and bidentate binding modes depending on the charge and the number of water molecules. The SCRF calculations were done with a variety of approaches, and different SCRF approaches were found to be optimal for different reaction types. The acidities of HxPO4 3-x in HxPO4 3-x(H2O)4, x = 0-3 complexes were calculated with different SCRF models and compared to experiment. Phosphate anions can displace water molecules from the first solvation shell at the uranyl exothermically. The addition of water molecules can cause the bonding of H2PO4 - and HPO4 2- to change from bidentate to monodentate exothermically while maintaining CN 5. The addition of water can generate monodentate structures capable of cross-linking to other uranyl phosphates to form the types of structures found in the solid state. [UO2(HPO4)(H2O)3] is predicted to be a strong base in the gas phase and in aqueous solution. It is predicted to be a much weaker acid than H3PO4 in the gas phase and in solution.

  7. Near-infrared-induced electron transfer of an uranyl macrocyclic complex without energy transfer to dioxygen.

    PubMed

    Davis, Christina M; Ohkubo, Kei; Ho, I-Ting; Zhang, Zhan; Ishida, Masatoshi; Fang, Yuanyuan; Lynch, Vincent M; Kadish, Karl M; Sessler, Jonathan L; Fukuzumi, Shunichi

    2015-04-21

    Photoexcitation of dichloromethane solutions of an uranyl macrocyclic complex with cyclo[1]furan[1]pyridine[4]-pyrrole () at the near-infrared (NIR) band (1177 nm) in the presence of electron donors and acceptors resulted in NIR-induced electron transfer without producing singlet oxygen via energy transfer. PMID:25791126

  8. Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

    NASA Astrophysics Data System (ADS)

    Medvedkov, Ya. A.; Serezhkina, L. B.; Grigor'ev, M. S.; Serezhkin, V. N.

    2016-05-01

    Two new malonate-containing uranyl complexes with carbamide of the formulas [UO2(C3H2O4)( Urea)2] ( I) and [UO2(C3H2O4)( Urea)3] ( II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO2(C2O4)( Urea)3] ( III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO2(C3H2O4)( Urea)2]∞ belonging to the crystal-chemical group AT 11 M 2 1 ( A = UO 2 2+ , T 11 = C3H2O 4 2- , M 1 = Urea) of uranyl complexes. Crystals II and III are composed of the molecular complexes [UO2( L)( Urea)3], where L = C3H2O 4 2- or C2O 4 2- , belonging to the crystal-chemical group AB 01 M 3 1 ( A = UO 2 2+ , B 01 = C3H2O 4 2- or C2O 4 2- , M 1 = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi-Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.

  9. Coordination Complexes of Cobalt.

    ERIC Educational Resources Information Center

    Williams, Gregory M.; And Others

    1989-01-01

    Described is an experiment involving the synthesis and spectral studies of cobalt complexes that not only give general chemistry students an introduction to inorganic synthesis but allows them to conduct a systematic study on the effect of different ligands on absorption spectra. Background information, procedures, and experimental results are…

  10. Molecular Dynamics Simulations of Uranyl and Uranyl Carbonate Adsorption at Alumino-silicate Surfaces

    SciTech Connect

    Kerisit, Sebastien N.; Liu, Chongxuan

    2014-03-03

    Adsorption at mineral surfaces is a critical factor controlling the mobility of uranium(VI) in aqueous environments. Therefore, molecular dynamics (MD) simulations were performed to investigate uranyl(VI) adsorption onto two neutral alumino-silicate surfaces, namely the orthoclase (001) surface and the octahedral aluminum sheet of the kaolinite (001) surface. Although uranyl preferentially adsorbed as a bi-dentate innersphere complex on both surfaces, the free energy of adsorption at the orthoclase surface (-15 kcal mol-1) was significantly more favorable than that at the kaolinite surface (-3 kcal mol-1), which was attributed to differences in surface functional groups and to the ability of the orthoclase surface to dissolve a surface potassium ion upon uranyl adsorption. The structures of the adsorbed complexes compared favorably with X-ray absorption spectroscopy results. Simulations of the adsorption of uranyl complexes with up to three carbonate ligands revealed that uranyl complexes coordinated to up to 2 carbonate ions are stable on the orthoclase surface whereas uranyl carbonate surface complexes are unfavored at the kaolinite surface. Combining the MD-derived equilibrium adsorption constants for orthoclase with aqueous equilibrium constants for uranyl carbonate species indicates the presence of adsorbed uranium complexes with one or two carbonates in alkaline conditions, in support of current uranium(VI) surface complexation models.

  11. Structural elucidation and physicochemical properties of mononuclear Uranyl(VI) complexes incorporating dianionic units.

    PubMed

    Azam, Mohammad; Velmurugan, Gunasekaran; Wabaidur, Saikh Mohammad; Trzesowska-Kruszynska, Agata; Kruszynski, Rafal; Al-Resayes, Saud I; Al-Othman, Zeid A; Venuvanalingam, Ponnambalam

    2016-01-01

    Two derivatives of organouranyl mononuclear complexes [UO2(L)THF] (1) and [UO2(L)Alc] (2), where L = (2,2'-(1E,1'E)-(2,2-dimethylpropane-1,3-dyl)bis(azanylylidene, THF = Tetrahydrofuran, Alc = Alcohol), have been prepared. These complexes have been determined by elemental analyses, single crystal X-ray crystallography and various spectroscopic studies. Moreover, the structure of these complexes have also been studied by DFT and time dependent DFT measurements showing that both the complexes have distorted pentagonal bipyramidal environment around uranyl ion. TD-DFT results indicate that the complex 1 displays an intense band at 458.7 nm which is mainly associated to the uranyl centered LMCT, where complex 2 shows a band at 461.8 nm that have significant LMCT character. The bonding has been further analyzed by EDA and NBO. The photocatalytic activity of complexes 1 and 2 for the degradation of rhodamine-B (RhB) and methylene blue (MB) under the irradiation of 500W Xe lamp has been explored, and found more efficient in presence of complex 1 than complex 2 for both dyes. In addition, dye adsorption and photoluminescence properties have also been discussed for both complexes. PMID:27595801

  12. Structural elucidation and physicochemical properties of mononuclear Uranyl(VI) complexes incorporating dianionic units

    PubMed Central

    Azam, Mohammad; Velmurugan, Gunasekaran; Wabaidur, Saikh Mohammad; Trzesowska-Kruszynska, Agata; Kruszynski, Rafal; Al-Resayes, Saud I.; Al-Othman, Zeid A.; Venuvanalingam, Ponnambalam

    2016-01-01

    Two derivatives of organouranyl mononuclear complexes [UO2(L)THF] (1) and [UO2(L)Alc] (2), where L = (2,2′-(1E,1′E)-(2,2-dimethylpropane-1,3-dyl)bis(azanylylidene, THF = Tetrahydrofuran, Alc = Alcohol), have been prepared. These complexes have been determined by elemental analyses, single crystal X-ray crystallography and various spectroscopic studies. Moreover, the structure of these complexes have also been studied by DFT and time dependent DFT measurements showing that both the complexes have distorted pentagonal bipyramidal environment around uranyl ion. TD-DFT results indicate that the complex 1 displays an intense band at 458.7 nm which is mainly associated to the uranyl centered LMCT, where complex 2 shows a band at 461.8 nm that have significant LMCT character. The bonding has been further analyzed by EDA and NBO. The photocatalytic activity of complexes 1 and 2 for the degradation of rhodamine-B (RhB) and methylene blue (MB) under the irradiation of 500W Xe lamp has been explored, and found more efficient in presence of complex 1 than complex 2 for both dyes. In addition, dye adsorption and photoluminescence properties have also been discussed for both complexes. PMID:27595801

  13. Selective colorimetric and fluorescent quenching determination of uranyl ion via its complexation with curcumin

    NASA Astrophysics Data System (ADS)

    Zhu, Jing-Hui; Zhao, Xin; Yang, Jidong; Tan, Yu-Ting; Zhang, Lei; Liu, Shao-Pu; Liu, Zhong-Fang; Hu, Xiao-Li

    2016-04-01

    Under pH 4.0 HAc-NaAc buffer medium, curcumin alone possesses extraordinary weak fluorescence emission. Nevertheless, the introduction of Triton X-100 micelles can largely enhance the fluorescence intensity of curcumin. Uranyl ions can complex with micelles-capped curcumin, along with the slight red shift of curcumin fluorescence (about 1-7 nm), a clear decrement of absorbance (424 nm) and fluorescence (507 nm) intensities, and a distinct color change from bright yellow to orange. The fluorescence decrements (ΔF, 507 nm) are positively correlated to the amount of uranyl ions in the concentration range of 3.7 × 10- 6-1.4 × 10- 5 mol L- 1. The detection limit of this fluorescence quenching methods is 3.7 × 10- 6 mol L- 1, which is nearly 9000 times lower than the maximum allowable level in drinking water proposed by World Health Organization. Good selectivity is achieved because of a majority of co-existing substances (such as Ce4 +, La3 +, and Th4 +) do not affect the detection. The content of uranyl ions in tap water samples was determined by the proposed method with satisfactory results.

  14. Selective colorimetric and fluorescent quenching determination of uranyl ion via its complexation with curcumin.

    PubMed

    Zhu, Jing-Hui; Zhao, Xin; Yang, Jidong; Tan, Yu-Ting; Zhang, Lei; Liu, Shao-Pu; Liu, Zhong-Fang; Hu, Xiao-Li

    2016-04-15

    Under pH4.0 HAc-NaAc buffer medium, curcumin alone possesses extraordinary weak fluorescence emission. Nevertheless, the introduction of Triton X-100 micelles can largely enhance the fluorescence intensity of curcumin. Uranyl ions can complex with micelles-capped curcumin, along with the slight red shift of curcumin fluorescence (about 1-7 nm), a clear decrement of absorbance (424 nm) and fluorescence (507 nm) intensities, and a distinct color change from bright yellow to orange. The fluorescence decrements (ΔF, 507 nm) are positively correlated to the amount of uranyl ions in the concentration range of 3.7×10(-6)-1.4×10(-5) mol L(-1). The detection limit of this fluorescence quenching methods is 3.7×10(-6) mol L(-1), which is nearly 9000 times lower than the maximum allowable level in drinking water proposed by World Health Organization. Good selectivity is achieved because of a majority of co-existing substances (such as Ce(4+), La(3+), and Th(4+)) do not affect the detection. The content of uranyl ions in tap water samples was determined by the proposed method with satisfactory results. PMID:26845580

  15. Uranyl Ion Complexes with 1,1'-Biphenyl-2,2',6,6'-tetracarboxylic Acid: Structural and Spectroscopic Studies of One- to Three-Dimensional Assemblies.

    PubMed

    Thuéry, Pierre; Harrowfield, Jack

    2015-07-01

    1,1'-Biphenyl-2,2',6,6'-tetracarboxylic acid (H4L) was reacted with uranyl nitrate, either alone or in the presence of additional metal cations (Ni(2+), Cu(2+), Dy(3+)) under (solvo)-hydrothermal conditions, giving six complexes which were characterized by their crystal structure and, in all but one case, their emission spectrum in the solid state. [Ni(bipy)3][UO2(H2L)(H2O)]2(NO3)2·3H2O (1) crystallizes as a one-dimensional (1D), ribbon-like coordination polymer, while the homometallic complex [(UO2)2(L)(H2O)3]·H2O·CH3CN (2) and the heterometallic complexes [UO2Cu(L)(H2O)2]·H2O (3), [UO2Cu(L)(H2O)]·H2O (4), and [(UO2)5Cu4(HL)6(bipy)4]·2H2O (5) display two-dimensional (2D) arrangements. Lastly, the uranyl-lanthanide heterometallic complex [(UO2)8Dy(HL)6(H2O)8](I)·8H2O (6) crystallizes as a three-dimensional (3D) framework. Although these assemblies adopt different topologies, the {4(2).6} linear motif found in 1 is discernible in the structures of 2, 5, and 6, in which the higher dimensionality arises from further bridging of these subunits by uranyl (2), copper (5), or both uranyl and dysprosium (6) cations. The tetracarboxylic/ate ligands have their two aromatic rings nearly perpendicular to one another. No two of them adopt the same coordination mode in this series (except in the similar complexes 3 and 4), but chelation involving one carboxylate group from each ring is nearly ubiquitous, and the ensuing position of the cation favors the formation of planar architectures. The emission spectra of complexes 2-5 measured in the solid state show the usual uranyl vibronic fine structure, although with significant differences in the emission intensity, while complete quenching of the luminescence is observed in 1. PMID:26102315

  16. Thermodynamics of lanthanide and uranyl complexes with tetrahydrofuran-2,3,4,5-tetracarboxylic acid (THFTCA).

    SciTech Connect

    Morss, L. R.; Nash, K. L.; Tennessee Technological Univ.

    2000-01-01

    We present the results of an investigation of the thermochemistry of the complexation of La{sup 3+} Nd{sup 3+}, Eu{sup 3+}, Dy{sup 3+}, Tm{sup 3+}, and UO{sub 2}{sup 2+} by tetrahydrofuran-2,3,4,5-tetracarboxylic acid (THFTCA). This predisposed structural analog to oxydiacetic acid (ODA) has been previously shown both to exhibit greater sensitivity to lanthanide cation radius than complexes with the unconstrained ODA and to form anomalously weak complexes with UO{sub 2}{sup 2+}. Our purpose is to interpret these observations in terms of the balance between enthalpy and entropy contributions to the overall complexation thermodynamics. Enthalpies have been calculated from titration calorimetry experiments both for the protonation of the free ligand and for the formation of selected 1:1 and 1:2 complexes in pH 2-3 acidic media (I = 0.1 M). The complexation entropies for the lanthanide complexes have been calculated using the previously reported stability constants for the MH{sub 2}L{sup +}, MHL, and M(H{sub 2}L){sup 2-}. The stability constants for the uranyl complexes have been determined by potentiometric titration and these values used to calculate the thermodynamic parameters. Complexation enthalpies for the 1:1 lanthanide-THFTCA complexes (MH{sub 2}L{sup +} species) are nearly identical to those of the lanthanide ODA complexes. Therefore, the size-selectivity observed in the lanthanide-THFTCA complexes arises from the complexation entropy. The comparative weakness of the uranyl complexes with THFTCA also is accounted for thermodynamically in the entropy term. Calculations based on an electrostatic model for complexation entropy and molecular mechanics modeling are used to help interpret the experimental results.

  17. Composition for detecting uranyl

    SciTech Connect

    Baylor, L.C.; Stephens, S.M.

    1995-06-13

    A composition for detecting the presence and concentration of a substance, such as uranyl, comprises an organohalide covalently bonded to an indicator for said substance. The composition has at least one active OH site for forming a complex with the substance to be detected. The composition is made by reacting equimolar amounts of the indicator and the organohalide in a polar organic solvent. The absorbance spectrum of the composition-uranyl complex is shifted with respect to the absorbance spectrum of the indicator-uranyl complex, to provide better spectral resolution for detecting uranyl. 6 figs.

  18. Composition for detecting uranyl

    DOEpatents

    Baylor, Lewis C.; Stephens, Susan M.

    1995-01-01

    A composition for detecting the presence and concentration of a substance such as uranyl, comprising an organohalide covalently bonded to an indicator for said substance. The composition has at least one active OH site for forming a complex with the substance to be detected. The composition is made by reacting equimolar amounts of the indicator and the organohalide in a polar organic solvent. The absorbance spectrum of the composition-uranyl complex is shifted with respect to the absorbance spectrum of the indicator-uranyl complex, to provide better spectral resolution for detecting uranyl.

  19. Synthesis, structure, luminescence and photocatalytic properties of an uranyl-2,5-pyridinedicarboxylate coordination polymer

    NASA Astrophysics Data System (ADS)

    Si, Zhen-Xiu; Xu, Wei; Zheng, Yue-Qing

    2016-07-01

    An uranium coordination polymer, namely [(UO2(pydc)(H2O)]·H2O (1) (H2pydc=2,5-pyridinedicarboxylic acid), has been obtained by hydrothermal method and characterized by X-ray single crystal structure determination. Structural analysis reveals that complex 1 exhibits 1D chain coordination polymer, in which UO22+ ions are bridged by 2,5-pyridinedicarboxylate ligands and the chains are connected into a 3D supramolecular network by O-H···O hydrogen bond interactions and π-π stacking interactions. The photocatalytic properties of 1 for degradation of methylene blue (MB), Rhodamine B (RhB) and methyl orange (MO) under Hg-lamp irradiation have been performed, and the amount of the catalyst as well as Hg-lamp irradiation with different power on the photodegradation efficiency of MB have been investigated. Elemental analyses, infrared spectroscopy, TG-DTA analyses and luminescence properties were also discussed.

  20. Synthesis and structures of new uranyl malonate complexes with carbamide derivatives

    SciTech Connect

    Serezhkina, L. B.; Grigor’ev, M. S.; Medvedkov, Ya. A.; Serezhkin, V. N.

    2015-09-15

    Crystals of new malonate-containing uranyl complexes [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Imon)(H{sub 2}O)] (I) and [UO{sub 2}(C{sub 3}H{sub 2}O4)(Meur){sub 3}] (II), where Imon is imidazolidin-2-one (ethylenecarbamide) and Meur is methyl-carbamide, have been synthesized and studied by X-ray diffraction. Both compounds crystallize in the monoclinic system with the following unit-cell parameters (at 100 K): a = 11.1147(10) Å, b = 6.9900(6) Å, c = 14.4934(12) Å, β = 92.042(2)°, V = 1125.30(17) Å{sup 3}, sp. gr. P2{sub 1}/n, Z = 4, R{sub 1} = 0.0398 (I); a = 16.6613(5) Å, b = 9.5635(3) Å, c = 22.9773(6) Å, β = 103.669(2)°, V = 3557.51(18) Å{sup 3}, sp. gr. C2/c, Z = 8, R{sub 1} = 0.0207 (II). The crystals are composed of electroneutral chains [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Imon)(H{sub 2}O)] and mononuclear groups [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Meur){sub 3}] as the structural units belonging to the crystal-chemical groups AT{sup 11}M{sub 2}{sup 1} and AB{sup 01}M{sub 3}{sup 1} (A =UO{sub 2}{sup 2+}, T{sup 11} and B{sup 01} = C{sub 3}H{sub 2}, M{sup 1} = Imon, H{sub 2}O, or Meur), respectively, of uranyl complexes. The packing modes of the uranyl-containing complexes were analyzed by the method of molecular Voronoi—Dirichlet polyhedra.

  1. Gas-phase coordination complexes of dipositive plutonyl, PuO2(2+): chemical diversity across the actinyl series.

    PubMed

    Rios, Daniel; Rutkowski, Philip X; Van Stipdonk, Michael J; Gibson, John K

    2011-06-01

    We report the first transmission of solvent-coordinated dipositive plutonyl ion, Pu(VI)O(2)(2+), from solution to the gas phase by electrospray ionization (ESI) of plutonyl solutions in water/acetone and water/acetonitrile. ESI of plutonyl and uranyl solutions produced the isolable gas-phase complexes, [An(VI)O(2)(CH(3)COCH(3))(4,5,6)](2+), [An(VI)O(2)(CH(3)COCH(3))(3)(H(2)O)](2+), and [An(VI)O(2)(CH(3)CN)(4)](2+); additional complex compositions were observed for uranyl. In accord with relative actinyl stabilities, U(VI)O(2)(2+) > Pu(VI)O(2)(2+) > Np(VI)O(2)(2+), the yields of plutonyl complexes were about an order of magnitude less than those of uranyl, and dipositive neptunyl complexes were not observed. Collision-induced dissociation (CID) of the dipositive coordination complexes in a quadrupole ion trap produced doubly- and singly-charged fragment ions; the fragmentation products reveal differences in underlying chemistries of plutonyl and uranyl, including the lower stability of Pu(VI) as compared with U(VI). Particularly notable was the distinctive CID fragment ion, [Pu(IV)(OH)(3)](+) from [Pu(VI)O(2)(CH(3)COCH(3))(6)](2+), where the plutonyl structure has been disrupted and the tetravalent plutonium hydroxide produced; this process was not observed for uranyl. PMID:21517017

  2. Toward equatorial planarity about uranyl: synthesis and structure of tridentate nitrogen-donor {UO2}2+ complexes.

    PubMed

    Copping, Roy; Jeon, Byoungseon; Pemmaraju, C Das; Wang, Shuao; Teat, Simon J; Janousch, Markus; Tyliszczak, Tolek; Canning, Andrew; Grønbech-Jensen, Niels; Prendergast, David; Shuh, David K

    2014-03-01

    The reaction of UO2Cl2·3THF with the tridentate nitrogen donor ligand 2,6-bis(2-benzimidazolyl)pyridine (H2BBP) in pyridine leads to the formation of three different complexes: [(UO2)(H2BBP)Cl2] (1), [(UO)2(HBBP)(Py)Cl] (2), and [(UO2)(BBP)(Py)2] (3) after successive deprotonation of H2BBP with a strong base. Crystallographic determination of 1-3 reveals that increased charge through ligand deprotonation and displacement of chloride leads to equatorial planarity about uranyl as well as a more compact overall coordination geometry. Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectra of 1-3 at the U-4d edges have been recorded using a soft X-ray Scanning Transmission X-ray Microscope (STXM) and reveal the uranium 4d5/2 and 4d3/2 transitions at energies associated with uranium in the hexavalent oxidation state. First-principles Density Functional Theory (DFT) electronic structure calculations for the complexes have been performed to determine and validate the coordination characteristics, which correspond well to the experimental results. PMID:24528285

  3. Characterization of the Aqueous Uranyl-Silicate Complex Using X-Ray Absorption Spectroscopy and Ab Initio Modeling

    NASA Astrophysics Data System (ADS)

    Vu, M.; Massey, M.; Huang, P.

    2015-12-01

    The speciation of aqueous uranium ions is an important factor in predicting its mobility and fate in the environment. Two major controls on speciation are pH and the presence of complexing ligands. For the case of aqueous uranyl, UO22+(aq), some common complexes include uranyl-hydroxy, uranyl-carbonato, and uranyl-calcium-carbonato complexes, all of which differ in chemical reactivity and mobility. Uranyl-silicate complexes are also known but remain poorly characterized. In this work, we studied uranyl speciation in a series of aqueous solutions of 0.1 mM uranyl and 2 mM silicate with pH ranging from 4 to 7. Extended X-Ray Absorption Fine Structure (EXAFS) spectra of these samples were recorded at the Stanford Synchrotron Radiation Lightsource (SLAC National Accelerator Laboratory). Of particular note are the uranyl and silicate concentrations employed in our experiments, which are lower than conditions in previously reported EXAFS studies and approach conditions in natural groundwater systems. Preliminary analyses of EXAFS data indicate that uranyl speciation changes across the pH range, consistent with published thermodynamic data that suggest uranyl-silicate complexes may be important for pH ~ 5 and below, while uranyl-carbonato complexes become dominant at circumneutral pH. To guide the interpretation of the EXAFS data, molecular-scale simulations were carried out using density functional theory. We considered two classes of models: (i) hydrated clusters, and (ii) ab initio molecular dynamics simulations of 3D-periodic models involving uranyl and silicate in water. These calculations reveal that at pH ~ 5, the uranyl speciation is the [UO2(H2O)4H3SiO4]+ complex formed by the substitution of an equatorial uranyl water with a monodentate silicate ligand. The evidence from experiments and simulations provide a consistent picture for the uranyl-silicate complex, which may be important in the transport of uranyl in acidic, silicate-rich waters.

  4. Europium, uranyl, and thorium-phenanthroline amide complexes in acetonitrile solution: an ESI-MS and DFT combined investigation.

    PubMed

    Xiao, Cheng-Liang; Wang, Cong-Zhi; Mei, Lei; Zhang, Xin-Rui; Wall, Nathalie; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun

    2015-08-28

    The tetradentate N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen) ligand with hard-soft donor atoms has been demonstrated to be promising for the group separation of actinides from highly acidic nuclear wastes. To identify the formed complexes of this ligand with actinides and lanthanides, electrospray ionization mass spectrometry (ESI-MS) combined with density functional theory (DFT) calculations was used to probe the possible complexation processes. The 1 : 2 Eu-L species ([EuL2(NO3)](2+)) can be observed in ESI-MS at low metal-to-ligand ([M]/[L]) ratios, whereas the 1 : 1 Eu-L species ([EuL(NO3)2](+)) can be observed when the [M]/[L] ratio is higher than 1.0. However, ([UO2L(NO3)](+)) is the only detected species for the uranyl complexes. The [ThL2(NO3)2](2+) species can be observed at low [M]/[L] ratios; the 1 : 2 species ([ThL2(NO3)](3+)) and a new 1 : 1 species ([ThL(NO3)3](+)) can be detected at high [M]/[L] ratios. Collision-induced dissociation (CID) results showed that Et-Tol-DAPhen ligands can coordinate strongly with metal ions, and the coordination moieties remain intact under CID conditions. Natural bond orbital (NBO), molecular electrostatic potential (MEP), electron localization function (ELF), atoms in molecules (AIM) and molecular orbital (MO) analyses indicated that the metal-ligand bonds of the actinide complexes exhibited more covalent character than those of the lanthanide complexes. In addition, according to thermodynamic analysis, the stable cationic M-L complexes in acetonitrile are found to be in good agreement with the ESI-MS results. PMID:26200662

  5. Uranyl complexation with acetate studied by means of affinity capillary electrophoresis.

    PubMed

    Sladkov, Vladimir

    2013-05-10

    The interaction of uranyl with acetate is studied by affinity capillary electrophoresis in aqueous acid solutions at the pH values 2.0 and 2.5. The use of data on metal ion mobilities at different pHs allows to establish the ligand species interacting with metal ion and complex species formed. The formation of two complex species UO2CH3COO(+) and UO2(CH3COO)2 is observed (acetic acid concentration is up to 0.8M). In the case of uranyl-acetic acid system, the viscosity of solution is significantly changed with an increase of acid concentration. For calculation of ion mobilities the viscosity changes are taken into account. The stability constants are calculated at the ionic strengths 0.02 and 0.05 mol L(-1). The logarithms of the thermodynamic stability constants (β°) calculated with Davies equation for the activity coefficients of the ions are log β1(°)=2.94±0.08 and log β2(°)=5.50±0.15 at 25 °C. Obtained values are compared with literature data. PMID:23570853

  6. Gas-phase reactions of molecular oxygen with uranyl(V) anionic complexes-synthesis and characterization of new superoxides of uranyl(VI).

    PubMed

    Lucena, Ana F; Carretas, José M; Marçalo, Joaquim; Michelini, Maria C; Gong, Yu; Gibson, John K

    2015-04-16

    Gas-phase complexes of uranyl(V) ligated to anions X(-) (X = F, Cl, Br, I, OH, NO3, ClO4, HCO2, CH3CO2, CF3CO2, CH3COS, NCS, N3), [UO2X2](-), were produced by electrospray ionization and reacted with O2 in a quadrupole ion trap mass spectrometer to form uranyl(VI) anionic complexes, [UO2X2(O2)](-), comprising a superoxo ligand. The comparative rates for the oxidation reactions were measured, ranging from relatively fast [UO2(OH)2](-) to slow [UO2I2](-). The reaction rates of [UO2X2](-) ions containing polyatomic ligands were significantly faster than those containing the monatomic halogens, which can be attributed to the greater number of vibrational degrees of freedom in the polyatomic ligands to dissipate the energy of the initial O2-association complexes. The effect of the basicity of the X(-) ligands was also apparent in the relative rates for O2 addition, with a general correlation between increasing ligand basicity and O2-addition efficiency for polyatomic ligands. Collision-induced dissociation of the superoxo complexes showed in all cases loss of O2 to form the [UO2X2](-) anions, indicating weaker binding of the O2(-) ligand compared to the X(-) ligands. Density functional theory computations of the structures and energetics of selected species are in accord with the experimental observations. PMID:25807358

  7. Strongly coupled binuclear uranium-oxo complexes from uranyl oxo rearrangement and reductive silylation

    NASA Astrophysics Data System (ADS)

    Arnold, Polly L.; Jones, Guy M.; Odoh, Samuel O.; Schreckenbach, Georg; Magnani, Nicola; Love, Jason B.

    2012-03-01

    The most common motif in uranium chemistry is the d0f0 uranyl ion [UO2]2+ in which the oxo groups are rigorously linear and inert. Alternative geometries, such as the cis-uranyl, have been identified theoretically and implicated in oxo-atom transfer reactions that are relevant to environmental speciation and nuclear waste remediation. Single electron reduction is now known to impart greater oxo-group reactivity, but with retention of the linear OUO motif, and reactions of the oxo groups to form new covalent bonds remain rare. Here, we describe the synthesis, structure, reactivity and magnetic properties of a binuclear uranium-oxo complex. Formed through a combination of reduction and oxo-silylation and migration from a trans to a cis position, the new butterfly-shaped Si-OUO2UO-Si molecule shows remarkably strong UV-UV coupling and chemical inertness, suggesting that this rearranged uranium oxo motif might exist for other actinide species in the environment, and have relevance to the aggregation of actinide oxide clusters.

  8. Strongly coupled binuclear uranium-oxo complexes from uranyl oxo rearrangement and reductive silylation.

    PubMed

    Arnold, Polly L; Jones, Guy M; Odoh, Samuel O; Schreckenbach, Georg; Magnani, Nicola; Love, Jason B

    2012-03-01

    The most common motif in uranium chemistry is the d(0)f(0) uranyl ion [UO(2)](2+) in which the oxo groups are rigorously linear and inert. Alternative geometries, such as the cis-uranyl, have been identified theoretically and implicated in oxo-atom transfer reactions that are relevant to environmental speciation and nuclear waste remediation. Single electron reduction is now known to impart greater oxo-group reactivity, but with retention of the linear OUO motif, and reactions of the oxo groups to form new covalent bonds remain rare. Here, we describe the synthesis, structure, reactivity and magnetic properties of a binuclear uranium-oxo complex. Formed through a combination of reduction and oxo-silylation and migration from a trans to a cis position, the new butterfly-shaped Si-OUO(2)UO-Si molecule shows remarkably strong U(V)-U(V) coupling and chemical inertness, suggesting that this rearranged uranium oxo motif might exist for other actinide species in the environment, and have relevance to the aggregation of actinide oxide clusters. PMID:22354437

  9. Wave propagation in complex coordinates

    NASA Astrophysics Data System (ADS)

    Horsley, S. A. R.; King, C. G.; Philbin, T. G.

    2016-04-01

    We give an interpretation for the use of complex spatial coordinates in electromagnetism, in terms of a family of closely related inhomogeneous media. Using this understanding we find that the phenomenon of reflection can be related to branch cuts in the wave that originate from poles of ε (z) at complex positions. Demanding that these branch cuts disappear, we derive a new large family of inhomogeneous media that are reflectionless for a single angle of incidence. Extending this property to all angles of incidence leads us to a generalized form of the Pöschl Teller potentials that in general include regions of loss and gain. We conclude by analyzing our findings within the phase integral (WKB) method, and find another very large family of isotropic planar media that from one side have a transmission of unity and reflection of zero, for all angles of incidence.

  10. DFT Study of Uranyl Peroxo Complexes with H₂O, F⁻, OH⁻, CO₃ ²⁻, and NO₃-

    SciTech Connect

    Odoh, Samuel O.; Schreckenbach, Georg

    2013-05-06

    The structural and electronic properties of monomeric uranyl peroxo complexes with aquo, hydroxo, fluoro, carbonate, and nitrate ligands have been studied using DFT calculations with relativistic pseudopotentials. The calculated affinity of the peroxo group for the actinyl moiety far exceeds that of the other ligands tested in this work.

  11. Experimental and Theoretical Studies on the Fragmentation of Gas-Phase Uranyl-, Neptunyl- and Plutonyl-Diglycolamide Complexes

    SciTech Connect

    Gong, Yu; Hu, Han-Shi; Rao, Linfeng; Li, Jun; Gibson, John K.

    2013-10-10

    Fragmentation of actinyl(VI) complexes UVIO2(L)22+, NpVIO2(L)22+ and PuVIO2(L)22+ (L = tetramethyl-3-oxa-glutaramide, TMOGA) produced by electrospray ionization was examined in the gas phase by collision induced dissociation (CID) in a quadrupole ion trap mass spectrometer. Cleavage of the C-Oether bond was observed for all three complexes, with dominant products being UVIO2(L)(L-86)+ with charge reduction, and NpVIO2(L)(L-101)2+ and PuVIO2(L)(L-101)2+ with charge conservation. The neptunyl and plutonyl complexes also exhibited substantial L+ loss to give pentavalent complexes NpVO2(L)+ and PuVO2(L)+, whereas the uranyl complex did not, consistent with the comparative An 5f-orbital energies and the AnVIO22+/AnVO2+ (An = U, Np, Pu) reduction potentials. CID of NpVO2(L)2+ and PuVO2(L)2+ was dominated by neutral ligand loss to form NpVO2(L)+ and PuVO2(L)+, which hydrated by addition of residual water in the ion trap; UVO2(L)2+ was not observed. Theoretical calculations of the structures and bonding of the AnVIO2(L)22+ complexes using density functional theory reveal that the metal centers are coordinated by six oxygen atoms from the two TMOGA ligands. The results are compared with radiolytic decomposition of TMOGA in solution.

  12. Aqueous uranyl complexes. 3. Potentiometric measurements of the hydrolysis of uranyl(VI) ion at 25{degrees}C

    SciTech Connect

    Palmer, D.A.; Nguyen-Trung, C.

    1995-12-01

    Potentiometric titrations of uranyl(VI) solutions were conducted using a standard glass/calomel electrode combination over the pH range 3 to 12 at 0.1 mol-kg{sup {minus}1} ionic strength with tetramethylammonium trifluoromethanesulfonate as the supporting electrolyte. The electrodes were calibrated directly on the hydrogen ion concentration scale during the initial stage of each titration. The species, UO{sub 2}{sup 2+}, (UO{sub 2}){sub 2}(OH){sub 2}{sup 2+}, (UO{sub 2}){sub 3}(OH){sub 5}{sup +}, (UO{sub 2}){sub 3}(OH){sub 7}{sup {minus}}, (UO{sub 2}){sub 3}(OH){sub 8}{sup 2-}, and (UO{sub 2}){sub 3}(OH){sub 10}{sup 4-} identified in an earlier Raman study were compatible with the analysis of the titration data. Based on this analysis and application of the extended Debye-Hueckel treatment, the polynuclear species indicated above were assigned overall formation constants at 25{degrees}C and at infinite dilution of -5.51{plus_minus}0.04, -15.3{plus_minus}0.1, -27.77{plus_minus}0.09, -37.65{plus_minus}0.14, and -62.4{plus_minus}0.3, respectively. The results are discussed in reference to hydrolysis quotients reported in the literature for the first three species. Formation quotients for the last two species have not been reported previously.

  13. Copper(II) and uranyl(II) complexes with acylthiosemicarbazide: synthesis, characterization, antibacterial activity and effects on the growth of promyelocytic leukemia cells HL-60.

    PubMed

    Angelusiu, Madalina Veronica; Almajan, Gabriela Laura; Rosu, Tudor; Negoiu, Maria; Almajan, Eva-Ruxandra; Roy, Jenny

    2009-08-01

    New chelates of N(1)-[4-(4-X-phenylsulfonyl)benzoyl]-N(4)-butyl-thiosemicarbazide (X=H, Cl, Br) with Cu(2+) and UO(2)(2+) have been prepared and characterized by analytical and physico-chemical techniques such as magnetic susceptibility measurements, elemental and thermal analyses, electronic, ESR and IR spectral studies. Room temperature ESR spectra of Cu(II) complexes yield {g} values characteristic of distorted octahedral and pseudo-tetrahedral geometry. Infrared spectra indicate that complexes contain six-coordinate uranium atom with the ligand atoms arranged in an equatorial plane around the linear uranyl group. Effects of these complexes on the growth of human promyelocytic leukemia cells HL-60 and their antibacterial activity (against Staphylococcus epidermidis ATCC 14990, Bacillus subtilis ATCC 6633, Bacillus cereus ATCC 14579, Pseudomonas aeruginosa ATCC 9027 and Escherichia coli ATCC 11775 strains) were studied comparatively with that of free ligands. PMID:19356828

  14. Facile reduction of a uranyl(VI) β-ketoiminate complex to U(IV) upon oxo silylation.

    PubMed

    Brown, Jessie L; Mokhtarzadeh, Charles C; Lever, Jeremie M; Wu, Guang; Hayton, Trevor W

    2011-06-01

    Reaction of the uranyl β-ketoiminate complex UO(2)((tBu)acnac)(2) (1) ((tBu)acnac = (t)BuNC(Ph)CHC(Ph)O) with Me(3)SiI, in the presence of Ph(3)P, results in the reductive silylation of the uranyl moiety and formation of the U(V) bis-silyloxide complex [Ph(3)PI][U(OSiMe(3))(2)I(4)] (2). Subsequent reaction of 2 with Lewis bases, such as 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), and tetrahydrofuran (THF), results in a further reduction of the metal center and isolation of the U(IV) complexes U(OSiMe(3))(2)I(2)(bipy)(2) (3), U(OSiMe(3))(2)I(2)(phen)(2) (4), and [U(OSiMe(3))(2)I(THF)(4)][I(3)] (5), respectively. PMID:21545129

  15. Combining coordination and supramolecular chemistry for the formation of uranyl-organic hybrid materials

    SciTech Connect

    Deifel, N. P.; Cahill, Christopher L.

    2011-01-01

    Three hybrid compounds have been synthesized through hydrothermal reactions of UO{sub 2}(NO{sub 3}){sub 2}·6H{sub 2}O with 4-halobenzoic acid (X = Cl, Br, I). The formation of these compounds utilizes a composite synthesis methodology that explicitly employs aspects of both coordination chemistry and supramolecular chemistry (namely halogen---halogen interactions).

  16. Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3-Oxa-Glutaramide: An Extreme Red-Shift of the [O=U=O]²⁺ Asymmetric Stretch

    SciTech Connect

    Gibson, John K.; Hu, Hanshi; Van Stipdonk, Michael J.; Berden, Giel; Oomens, Jos; Li, Jun

    2015-04-09

    The gas-phase complex UO₂(TMOGA)₂²⁺ (TMOGA = tetramethyl-3-oxa-glutaramide) prepared by electrospray ionization was characterized by infrared multiphoton dissociation (IRMPD) spectroscopy. The IRMPD spectrum from 700–1800 cm⁻¹ was interpreted using a computational study based on density functional theory. The predicted vibrational frequencies are in good agreement with the measured values, with an average deviation of only 8 cm⁻¹ (<1%) and a maximum deviation of 21 cm⁻¹ (<2%). The only IR peak assigned to the linear uranyl moiety was the asymmetric ν₃ mode, which appeared at 965 cm⁻¹ and was predicted by DFT as 953 cm⁻¹. This ν₃ frequency is red-shifted relative to bare uranyl, UO₂²⁺, by ca. 150 cm⁻¹ due to electron donation from the TMOGA ligands. Based on the degree of red-shifting, it is inferred that two TMOGA oxygen-donor ligands have a greater effective gas basicity than the four monodentate acetone ligands in UO₂(acetone)₄²⁺. The uranyl ν₃ frequency was also computed for uranyl coordinated by two TMGA ligands, in which the central Oether of TMOGA has been replaced by CH₂. The computed ν₃ for UO₂(TMGA)₂²⁺, 950 cm⁻¹, is essentially the same as that for UO₂(TMOGA)₂²⁺, suggesting that electron donation to uranyl from the Oether of TMOGA is minor. The computed ν₃ asymmetric stretching frequencies for the three actinyl complexes, UO₂(TMOGA)₂²⁺, NpO₂(TMOGA)₂²⁺ and PuO₂(TMOGA)₂²⁺, are comparable. This similarity is discussed in the context of the relationship between ν₃ and intrinsic actinide-oxygen bond energies in actinyl complexes.

  17. Infrared multiphoton dissociation spectroscopy of a gas-phase complex of uranyl and 3-oxa-glutaramide: an extreme red-shift of the [O═U═O](2+) asymmetric stretch.

    PubMed

    Gibson, John K; Hu, Han-Shi; Van Stipdonk, Michael J; Berden, Giel; Oomens, Jos; Li, Jun

    2015-04-01

    The gas-phase complex UO2(TMOGA)2(2+) (TMOGA = tetramethyl-3-oxa-glutaramide) prepared by electrospray ionization was characterized by infrared multiphoton dissociation (IRMPD) spectroscopy. The IRMPD spectrum from 700-1800 cm(-1) was interpreted using a computational study based on density functional theory. The predicted vibrational frequencies are in good agreement with the measured values, with an average deviation of only 8 cm(-1) (<1%) and a maximum deviation of 21 cm(-1) (<2%). The only IR peak assigned to the linear uranyl moiety was the asymmetric ν3 mode, which appeared at 965 cm(-1) and was predicted by DFT as 953 cm(-1). This ν3 frequency is red-shifted relative to bare uranyl, UO2(2+), by ca. 150 cm(-1) due to electron donation from the TMOGA ligands. Based on the degree of red-shifting, it is inferred that two TMOGA oxygen-donor ligands have a greater effective gas basicity than the four monodentate acetone ligands in UO2(acetone)4(2+). The uranyl ν3 frequency was also computed for uranyl coordinated by two TMGA ligands, in which the central Oether of TMOGA has been replaced by CH2. The computed ν3 for UO2(TMGA)2(2+), 950 cm(-1), is essentially the same as that for UO2(TMOGA)2(2+), suggesting that electron donation to uranyl from the Oether of TMOGA is minor. The computed ν3 asymmetric stretching frequencies for the three actinyl complexes, UO2(TMOGA)2(2+), NpO2(TMOGA)2(2+) and PuO2(TMOGA)2(2+), are comparable. This similarity is discussed in the context of the relationship between ν3 and intrinsic actinide-oxygen bond energies in actinyl complexes. PMID:25785482

  18. Scale-Dependent Rates of Uranyl Surface Complexation Reaction in Sediments

    SciTech Connect

    Liu, Chongxuan; Shang, Jianying; Kerisit, Sebastien N.; Zachara, John M.; Zhu, Weihuang

    2013-03-15

    Scale-dependency of uranyl[U(VI)] surface complexation rates was investigated in stirred flow-cell and column systems using a U(VI)-contaminated sediment from the US Department of Energy, Hanford site, WA. The experimental results were used to estimate the apparent rate of U(VI) surface complexation at the grain-scale and in porous media. Numerical simulations using molecular, pore-scale, and continuum models were performed to provide insights into and to estimate the rate constants of U(VI) surface complexation at the different scales. The results showed that the grain-scale rate constant of U(VI) surface complexation was over 3 to 10 orders of magnitude smaller, dependent on the temporal scale, than the rate constant calculated using the molecular simulations. The grain-scale rate was faster initially and slower with time, showing the temporal scale-dependency. The largest rate constant at the grain-scale decreased additional 2 orders of magnitude when the rate was scaled to the porous media in the column. The scaling effect from the grain-scale to the porous media became less important for the slower sorption sites. Pore-scale simulations revealed the importance of coupled mass transport and reactions in both intragranular and inter-granular domains, which caused both spatial and temporal dependence of U(VI) surface complexation rates in the sediment. Pore-scale simulations also revealed a new rate-limiting mechanism in the intragranular porous domains that the rate of coupled diffusion and surface complexation reaction was slower than either process alone. The results provided important implications for developing models to scale geochemical/biogeochemical reactions.

  19. 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

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

    SciTech Connect

    Rothe, Robert Emil; Briggs, Joseph Blair

    1999-06-01

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

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

    SciTech Connect

    J. B. Briggs; R. E. Rothe

    1999-06-14

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

  2. Assessing covalency in equatorial U-N bonds: density based measures of bonding in BTP and isoamethyrin complexes of uranyl.

    PubMed

    Di Pietro, Poppy; Kerridge, Andrew

    2016-06-22

    Calculations performed at the density functional level of theory have been used to investigate complexes of uranyl with the expanded porphyrin isoamethyrin and the bis-triazinyl-pyridine (BTP) ligands, the latter of which is well-known to be effective in the separation of trivalent lanthanides and actinides. Analysis has been performed using a range of density-based techniques, including the Quantum Theory of Atoms in Molecules (QTAIM), the Electron Localisation Function (ELF) and the reduced density gradient (RDG). The effects of peripheral alkyl substituents on UO2-isoamethyrin, known to be vital for proper replication of the experimental geometry, are considered. Evidence for comparable amounts of covalent character has been found in the largely ionic U-N bonds of UO2-isoamethyrin and [UO2(BTP)2](2+) and examination of the variation in the electronic characteristics of the uranyl unit upon complexation in both of these cases reveal striking similarities in the nature of the U-N bonding and the effect of this bonding on the U-Oyl interaction, as well as evidence of donation into the U-N bonding region from the uranyl unit itself. PMID:27279271

  3. Passage of TBP-uranyl complexes from aqueous-organic interface to the organic phase: insights from molecular dynamics simulation.

    PubMed

    Sahu, Pooja; Ali, Sk Musharaf; Shenoy, Kalasanka Trivikram

    2016-08-24

    The present study reports molecular dynamics simulations for biphasic systems comprising tributyl phosphate (TBP) in dodecane and uranyl nitrate in the aqueous phase, which are key chemical species in the well-known Pu-U extraction (PUREX) process. An attempt has been made to understand the nature of interface and mechanism of 'TBP associated uranyl' crossing under neutral and acidic conditions. Results show that the solvent density undergoes large fluctuation near the interface depending on the nature of the aqueous-organic phase. The study provides compelling evidence of experimentally observed reorganization of interfacial complexes at the interface and their structural reformation during extraction. It has been observed that the surface active nature of TBP and their interfacial coverage is modulated by the nature of incorporated solute species and their location with respect to the interface. Also, the TBP structuring near the interface is destroyed when an acidic interface is considered rather than a neutral one which favors the uranyl extraction. With an acidic interface, the water humidity of organic phase was observed to be increased in the experiments. Furthermore, the acid/water solubility in the organic phase was observed to be influenced by selection of acid models and their concentration. Simulations with high acid concentration show water pocket formation in the organic phase. However, in the case of dissociated ions or a mixture of both, no such water pool is observed and the extracted water remains dispersed in the organic phase, having the tendency to be replaced by HNO3 because of preferred TBP·HNO3 complexation over TBP·H2O. Most remarkably, the present study makes evident the TBP-induced charge redistribution of uranyl complexes during migration from the interface to the bulk organic phase, which contributes to drive uranyl complexes such as UO2·NO3·4TBP, UO2·5TBP and UO2·NO3·3TBP·HNO3 in the organic phase, and this was reestablished by

  4. Polymer complexes. LX. Supramolecular coordination and structures of N(4-(acrylamido)-2-hydroxybenzoic acid) polymer complexes

    NASA Astrophysics Data System (ADS)

    Ghoneim, M. M.; El-Sonbati, A. Z.; El-Bindary, A. A.; Diab, M. A.; Serag, L. S.

    2015-04-01

    A number of novel polymer complexes of various anions of copper(II), cobalt(II), nickel(II) and uranyl(II) with N(4-(acrylamido)-2-hydroxy benzoic acid) (ABH) have been synthesized and characterized by elemental analysis, IR, 1H NMR, magnetic susceptibility measurements, electronic spin resonance, vibrational spectra and thermal analysis. The molecular structures of the ligand are optimized theoretically and the quantum chemical parameters are calculated. Tentative structures for the polymeric metal complexes due to their potential application are also suggested. The IR data exhibit the coordination of ONO2/OAc/SO4 with the metal ions in the polymeric metal complex. Vibrational spectra indicate coordination of carboxylate oxygen and phenolic OH of the ligand giving a MO4 square planar chromophore. Ligand field ESR spectra support square planar geometry around Cu(II). The thermal decomposition of the polymer complexes were discussed in relation to structure, and the thermodynamic parameters of the decomposition stages were evaluated applying Coast-Redfern and Horowitz-Metzger methods.

  5. Influence of Acidity on Uranyl Nitrate Association in Aqueous Solutions: A Molecular Dynamics Simulation Study

    SciTech Connect

    de Almeida, Valmor F; Cui, Shengting; Khomami, Bamin; Ye, Xianggui; Smith, Rodney Bryan

    2010-01-01

    Uranyl ion complexation with water and nitrate is a key aspect of the uranium/plutonium extraction process. We have carried out a molecular dynamics simulation study to investigate this complexation process, including the molecular composition of the various complex species, the corresponding structure, and the equilibrium distribution of the complexes. The observed structures of the complexes suggest that in aqueous solution, uranyls are generally hydrated by 5 water molecules in the equatorial plane. When associating with nitrate ions, a water molecule is replaced by a nitrate ion, preserving the five-fold coordination and planar symmetry. Analysis of the pair correlation function between uranyl and nitrate suggests that nitrates bind to uranyl in aqueous solution mainly in a monodentate mode, although a small portion of bidentates occur. Dynamic association and dissociation between uranyls and nitrates take place in aqueous solution with a substantial amount of fluctuation in the number of various uranyl nitrate species. The average number of the uranyl mononitrate complexes shows a dependence on acid concentration consistent with equilibrium-constant analysis, namely, the concentration of [UO2NO3]+ increases with nitric acid concentration.

  6. Discussion on the complexing ability of the uranyl ion with several crown ethers and cryptands in water and in propylene carbonate

    SciTech Connect

    Brighli, M.; Fux, P.; Lagrange, J.; Lagrange, P.

    1985-01-02

    Interactions of the uranyl ion (UO/sub 2//sup 2 +/) with some common crown ethers (12C4, 15C5, 18C6, DB-18C6) and cryptands (22,222) are investigated in aqueous and propylene carbonate (PC) solutions, I = 0.1 M ((TEA)ClO/sub 4/). Stability constants of the complexes formed are determined by potentiometric and spectrophotometric measurements. Discussions on the stability constants of the complexes allow us to postulate whether or not direct uranyl-macrocycle bonds are obtained. In PC solution, uranyl inner-sphere complexes with 18C6, DB-18C6, 22, and 222 are formed with the uranyl ion probably inside or partially enclosed in the ligand cavity. In aqueous media, complexation occurs only with crown ethers by formation of hydrogen bonds between hydrogen of water molecules of the hydrate shell of the uranyl ion and oxygen atoms of the crown ether (UO/sub 2//sup 2 +/ outer-sphere complexes). 31 references, 5 figures, 3 tables.

  7. Role of citrate as a complexing ligand which permits enzymically-mediated uranyl ion bioaccumulation

    SciTech Connect

    Yong, P.; Macaskie, L.E.

    1995-06-01

    Microorganisms can be used to remove toxic heavy metals from liquid industrial wastes. One potentially useful system utilizes the enzymically-mediated biomineralization of heavy metals at the surface of bacterial cells. This well-documented system harnesses a metal-resistant phosphatase enzyme overproduced by a Citrobacter sp.; metal uptake is mediated by the activity of this enzyme, which persists in non-growing cells, to liberate HPO{sub 4}{sup 2-} from glycerol 2-phosphate with stoichiometric deposition of heavy metals(M) as cell-bound MHPO{sub 4}. Recent attention has focused on the treatment of wastes from nuclear power and nuclear fuel reprocessing activities, together with discharges of native uranium in mining wastes. Previous investigations using the Citrobacter sp. demonstrated removal of uranium and the transuranic elements, plutonium and americium. Although uranium is inhibitory to the growth of the Citrobacter strain, and the activity of the cellular phosphatase, uranyl phosphate accumulates as polycrystalline HUO{sub 2}PO{sub 4} at the cell surface. The rate of uranyl removal into the growing crystal is primarily dependent on the rate of phosphate release by the enzyme catalysed reaction. This is inconsistent with the reported toxicity of uranyl ion to the mediating phosphatase; however, in the presence of an excess of substrate, the rapid rate of phosphate release facilitated metal precipitation without toxic effect. Under substrate-limiting conditions uranyl toxicity was seen. The present investigation shows the inhibition of Citrobacter sp. phosphatase is related to the concentration of uranyl ion, and that citrate buffer can protect against this toxicity, and permit metal bioaccumulation. The toxicity pattern is dependent upon the substrate used; possible reasons for these effects, and environmental implications are discussed. 18 refs., 5 figs.

  8. Chemical controls on uranyl citrate speciation and the self-assembly of nanoscale macrocycles and sandwich complexes in aqueous solutions.

    PubMed

    Basile, M; Unruh, D K; Gojdas, K; Flores, E; Streicher, L; Forbes, T Z

    2015-03-28

    Uranyl citrate forms trimeric species at pH > 5.5, but exact structural characteristics of these important oligomers have not previously been reported. Crystallization and structural characterization of the trimers suggests the self-assembly of the 3 : 3 and 3 : 2 U : Cit complexes into larger sandwich and macrocyclic molecules. Raman spectroscopy and ESI-MS have been utilized to investigate the relative abundance of these species in solution under varying pH and citrate concentrations. Additional dynamic light scattering experiments indicate that self-assembly of the larger molecules does occur in aqueous solution. PMID:25469487

  9. Strong anticipation: complexity matching in interpersonal coordination.

    PubMed

    Marmelat, Vivien; Delignières, Didier

    2012-10-01

    A subtle coordination occurs within complex systems, between multiple nested sub-systems. This intra-system coordination can be detected by the presence of 1/f fluctuations produced by the system. But coordination can occur also between systems. Interpersonal coordination has been studied from a local point of view until now, focusing on macroscopic interactions. But the recent concept of strong anticipation introduced by Dubois (Lect Notes Comput Sci 2684:110-132, 2003) suggests that interactions could occur on multiple levels between complex systems. The hypothesis is that time series in interpersonal synchronization present a matching of the complexity index (fractal exponent). Moreover, it is argued that this matching is not a consequence of short-term adaptations but reveals a global coordination between participants. Eleven pairs of participants oscillated a hand-held pendulum in the in-phase pattern for 11 min, in three conditions where the coupling strength was manipulated by the perceptual feedbacks. The results show a high correlation between fractal exponents irrespective of the coupling strength, and a very low percentage of local cross-correlations between time series appear at lag 0 and lag 1. These results suggest that interpersonal coordination, and more globally synchronization of participants with natural environments, is based on non-local time scales. PMID:22865163

  10. Self-assembly of a 3d-5f trinuclear single-molecule magnet from a pentavalent uranyl complex.

    PubMed

    Chatelain, Lucile; Walsh, James P S; Pécaut, Jacques; Tuna, Floriana; Mazzanti, Marinella

    2014-12-01

    Mixed-metal uranium compounds are very attractive candidates in the design of single-molecule magnets (SMMs), but only one 3d-5f hetero-polymetallic SMM containing a uranium center is known. Herein, we report two trimeric heterodimetallic 3d-5f complexes self-assembled by cation-cation interactions between a uranyl(V) complex and a TPA-capped M(II)  complex (M=Mn (1), Cd (2); TPA=tris(2-pyridylmethyl)amine). The metal centers were strategically chosen to promote the formation of discrete molecules rather than extended chains. Compound 1, which contains an almost linear {MnOUOMn} core, exhibits SMM behavior with a relaxation barrier of 81±0.5 K-the highest reported for a mono-uranium system-arising from intramolecular Mn-U exchange interactions combined with the high Ising anisotropy of the uranyl(V) moiety. Compound 1 also exhibits an open magnetic hysteresis loop at temperatures less than 3 K, with a significant coercive field of 1.9 T at 1.8 K. PMID:25284018

  11. Sequestering uranium from seawater: binding strength and modes of uranyl complexes with glutarimidedioxime.

    PubMed

    Tian, Guoxin; Teat, Simon J; Zhang, Zhiyong; Rao, Linfeng

    2012-10-14

    Glutarimidedioxime (H(2)A), a cyclic imide dioxime ligand that has implications in sequestering uranium from seawater, forms strong tridentate complexes with UO(2)(2+). The stability constants and the enthalpies of complexation for five U(VI) complexes were measured by potentiometry and microcalorimetry. The crystal structure of the 1 : 2 metal-ligand complex, UO(2)(HA)(2)·H(2)O, was determined. The re-arrangement of the protons of the oxime groups (-CH=N-OH) and the deprotonation of the imide group (-CH-NH-CH-) results in a conjugated system with delocalized electron density on the ligand (-O-N-C-N-C-N-O-) that coordinates to UO(2)(2+)via its equatorial plane. PMID:22801978

  12. COMPLEXANTS FOR ACTINIDE ELEMENT COORDINATION AND IMMOBILIZATION

    EPA Science Inventory

    We propose that inorganic clusters known as polyoxoanions (POAs) can be exploited as complexants for actinide (An) ion coordination and immobilization. Our objective is to develop rugged, stoichiometrically well-defined POAs that act as molecular containers of An elements. Poly...

  13. Synthesis of New Bis(3-hydroxy-4-pyridinone) Ligands as Chelating Agents for Uranyl Complexation.

    PubMed

    Jin, Bo; Zheng, Rongzong; Peng, Rufang; Chu, Shijin

    2016-01-01

    Five new bis(3-hydroxy-4-pyridinone) tetradentate chelators were synthesized in this study. The structures of these tetradentate chelators were characterized by ¹H-NMR, (13)C-NMR, FT-IR, UV-vis, and mass spectral analyses. The binding abilities of these tetradentate chelators for uranyl ion at pH 7.4 were also determined by UV spectrophotometry in aqueous media. Results showed that the efficiencies of these chelating agents are dependent on the linker length. Ligand 4b is the best chelator and suitable for further studies. PMID:27005598

  14. The Complexes of Bisphosphonate and Magnetite Nanoparticles to Remove Uranyl Ions from Aqueous Phase

    SciTech Connect

    Wang, L.; Yang, Z.; Gao, J.; Xu, K.; Gu, H.; Xu, B.; Zhang, B.; Zhang, X.

    2007-03-20

    Using tetraethyl-3-amino-propane-1,1-bisphosphonate (BP) as the functional molecule, we functionalized Fe3O4 magnetic nanoparticles via dopamine (DA) linkage to create a system with an Fe3O4-DA-BP nanostructure, which possesses high specificity for removing uranyl ions from water or blood. This work demonstrates that magnetic nanoparticles, combined with specific receptor-ligand interactions, promise a sensitive and rapid platform for the detection, recovery, and decorporation of radioactive metal toxins from biological environment.

  15. Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions.

    PubMed

    Thuéry, Pierre; Harrowfield, Jack

    2016-03-01

    Twelve new complexes were obtained from reaction of uranyl ions with the aliphatic dicarboxylic acids HOOC-(CH2)n-2-COOH (H2Cn; n = 7-10 and 12) under solvo-hydrothermal conditions, in the presence of 3d-block metal ions (Mn(2+), Fe(3+), Co(2+), Ni(2+), and Cu(2+)) and 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen). In contrast to previously reported triple-stranded helicates obtained with C9(2-) and C12(2-), all these complexes crystallize as polymeric one-dimensional (1D) or two-dimensional (2D) species. [Fe(bipy)3][(UO2)2(C7)3]·3H2O (1), [Cu(phen)2]2[(UO2)3(C7)4(H2O)2]·2H2O (2), and [Cu(bipy)2]2[(UO2)2(C9)3] (6), in which the 3d cation was reduced in situ, are 1D ladderlike polymers displaying tetra- or hexanuclear rings, of sufficient width to encompass two counterions in 2 and 6. The three complexes [Co(phen)3][(UO2)3(C8)3(O)]·H2O (3), [Ni(phen)3][(UO2)3(C8)3(O)]·H2O (4) and [Co(phen)3][(UO2)3(C9)3(O)]·H2O (5) contain bis(μ3-oxo)-bridged tetranuclear secondary building units, and they crystallize as deeply furrowed 2D assemblies. Depending on the nature of the counterion, C10(2-) gives [Ni(bipy)3][(UO2)2(C10)3]·2H2O (7), a 2D network displaying elongated decanuclear rings containing the counterions, or [Mn(phen)3][(UO2)2(C10)3]·6H2O (8), [Co(phen)3][(UO2)2(C10)3]·7H2O (9), and [Ni(phen)3][(UO2)2(C10)3]·7H2O (10), which consist of 2D assemblies with honeycomb topology; the hexanuclear rings in 8-10 are chairlike and occupied by one counterion and two uranyl groups from neighboring layers. Two complexes of the ligand with the longest chain, C12(2-), are reported. [UO2(C12)(bipy)] (11) is a neutral 1D species in which bipy chelates the uranyl ion and plays an important role in the packing through π-stacking interactions. Two polymeric units, 1D and 2D, coexist in the complex [Ni(bipy)3][(UO2)2(C12)3][UO2(C12)(H2O)2]·H2O (12); the 2D network has the honeycomb topology, but the hexanuclear rings are markedly convoluted, with local features akin to

  16. Uranyl mediated photofootprinting reveals strong E. coli RNA polymerase--DNA backbone contacts in the +10 region of the DeoP1 promoter open complex.

    PubMed Central

    Jeppesen, C; Nielsen, P E

    1989-01-01

    Employing a newly developed uranyl photofootprinting technique (Nielsen et al. (1988) FEBS Lett. 235, 122), we have analyzed the structure of the E. coli RNA polymerase deoP1 promoter open complex. The results show strong polymerase DNA backbone contacts in the -40, -10, and most notably in the +10 region. These results suggest that unwinding of the -12 to +3 region of the promoter in the open complex is mediated through polymerase DNA backbone contacts on both sides of this region. The pattern of bases that are hyperreactive towards KMnO4 or uranyl within the -12 to +3 region furthermore argues against a model in which this region is simply unwound and/or single stranded. The results indicate specific protein contacts and/or a fixed DNA conformation within the -12 to +3 region. Images PMID:2503811

  17. Uranyl adsorption at solvated edge surfaces of 2 : 1 smectites. A density functional study.

    PubMed

    Kremleva, Alena; Krüger, Sven; Rösch, Notker

    2015-05-28

    We systematically studied the adsorption of uranyl(vi) on two common edge surfaces, (010) and (110), of 2 : 1 smectite clay minerals, using standard periodic DFT models. To describe various types of permanently charged clay minerals, we introduced charged defects into the initially neutral layer of pyrophyllite, cation substitutions in tetrahedral (beidellitic) and octahedral (montmorillonitic) sheets. Comparing uranyl(vi) species at various sites of these two types of surfaces, we found that structural parameters of such adsorption complexes are essentially determined by the surface chemical groups forming the adsorption site, not by the type of the clay mineral. Even for sites involving a substituted cation we noticed only a weak effect of the substitution on the geometric parameters. Geometry optimization resulted in adsorbed uranyl or uranyl hydroxide, with coordination numbers of 4 or 5. However, in most cases the same species was determined on the same type of site, independent of the substitutions. Optimization of adsorbed uranyl leads to hydrolysis at sites close to a AlOH(-1/2) surface group, resulting in uranyl monohydroxide as adsorbate and protonation of the AlOH(-1/2) group. While most species are equatorially five-coordinated, coordination 4 is preferred when uranyl adsorbs on mixed AlO(H)-SiO(H) sites. Calculated formation energies of surface complexes do not single out a preferred species or site, but point to an equilibrium of several species. Comparison to experiment and consideration of pH conditions suggests AlOHOH and AlOH-SiO sites of (010) surfaces and AlOmOH, SiOOm, and AlOH-SiO sites of (110) surfaces as most probable for uranyl adsorption. PMID:25941904

  18. Extraordinary aluminum coordination in a novel homometallic double complex salt.

    PubMed

    Mandai, Toshihiko; Masu, Hyuma; Johansson, Patrik

    2015-07-01

    We have characterized a novel aluminum-based homometallic double complex salt, incorporating discrete octa-coordinated cationic [Al(G3)2](3+) and hexa-coordinated anionic [Al(TfO)4(OH)2](3-) complexes (G3 = triglyme, TfO = trifluoromethanesulfonate). X-ray crystallography, Raman spectra, and DFT calculations demonstrate extraordinary weak Al(3+) coordination in [Al(G3)2](3+). PMID:26024493

  19. Perturbation of the O-U-O Angle in Uranyl by Coordination to a 12-Membered Macrocycle.

    PubMed

    Pedrick, Elizabeth A; Schultz, Jason W; Wu, Guang; Mirica, Liviu M; Hayton, Trevor W

    2016-06-01

    Reaction of [UO2Cl2(THF)2]2 (THF = tetrahydrofuran) with 2 equiv of (H)N4 ((H)N4 = 2,11-diaza[3,3](2,6) pyridinophane) or (Me)N4 ((Me)N4 = N,N'-dimethyl-2,11-diaza[3,3](2,6) pyridinophane), in MeCN, results in the formation of UO2Cl2((R)N4) (R = H; 1; Me, 2), which were isolated as yellow-orange solids in good yields. Similarly, reaction of UO2(OTf)2(THF)3 with (H)N4 in MeCN results in the formation of UO2(OTf)2((H)N4) (3), as an orange powder in 76% yield. Finally, reaction of UO2(OTf)2(THF)3 with (Me)N4 in THF results in the formation of [UO2(OTf)(THF)((H)N4)][OTf] (4), as an orange powder in 73% yield. Complexes 1-4 were fully characterized, including characterization by X-ray crystallography. These complexes exhibit the smallest O-U-O bond angles measured to date, ranging from 168.2(3)° (for 2) to 161.7(5)° (for 4), a consequence of an unfavorable steric interaction between the oxo ligands and the macrocycle backbone. A Raman spectroscopic study of 1-4 reveals no correlation between O-U-O angle and the U═O νsym mode. However, complexes 1 and 2 do feature lower U═O νsym modes than complexes 3 and 4, which can be rationalized by the stronger donor strength of Cl(-) versus OTf(-). This observation suggests that the identity of the equatorial ligands has a greater effect on the U═O νsym frequency than does a change in O-U-O angle, at least when the changes in the O-U-O angles are small. PMID:27177203

  20. Gas-Phase Coordination Complexes of UVIO{2/2+}, NpVIO{2/2+}, and PuVIO{2/2+} with Dimethylformamide

    NASA Astrophysics Data System (ADS)

    Rutkowski, Philip X.; Rios, Daniel; Gibson, John K.; van Stipdonk, Michael J.

    2011-11-01

    Electrospray ionization of actinyl perchlorate solutions in H2O with 5% by volume of dimethylformamide (DMF) produced the isolatable gas-phase complexes, [AnVIO2(DMF)3(H2O)]2+ and [AnVIO2(DMF)4]2+, where An = U, Np, and Pu. Collision-induced dissociation confirmed the composition of the dipositive coordination complexes, and produced doubly- and singly-charged fragment ions. The fragmentation products reveal differences in underlying chemistries of uranyl, neptunyl, and plutonyl, including the lower stability of Np(VI) and Pu(VI) compared with U(VI).

  1. SYNTHESIS, CHARACTERIZATION, AND STRUCTURE OF A URANYL COMPLEX WITH A DISULFIDE LIGAND, BIS(DI-n-PROPYLAMMONIUM) DISULFIDOBIS (DI-n-PROPYLMONOTHIOCARBAMATO) DIOXOURANATE(VI)

    SciTech Connect

    Perry, Dale L.; Zalkin, Allan; Ruben, Helena; Templeton, David H.

    1981-05-01

    Olive-green crystals of the title compound, [({underline n}-C{sub 3}H{sub 7}){sub 2}NH{sub 2}{sup +}]{sub 2} [UO(({underline n}-C{sub 3}H{sub 7}){sub 2}NCOS){sub 2}(S{sub 2}){sup -2}, are orthorhombic, space group Pcan, with {underline a}= 15.326(6) {Angstrom}, {underline b} = 17.474(6) {Angstrom}, {underline C} = 14.728(6) {Angstrom}, and Z = 4, (d{sub X} = 1.45 g/cm{sup 3}). For 1833 data, I >{sigma}, R = 0.052, and R{sub w} = 0.069. The structure was revealed by single-crystal x-ray diffraction studies to consist of [(n-C{sub 3}H{sub 7}){sub 2}NH{sub 2}]+ cations and [UO{sub 2}(({underline n|-C{sub 3}H{sub 7}){sub 2}NCOS){sub 2}(S{sub 2}){sup -2} anions with the uranium atom at the center of an irregular hexagonal bipyramid. The uranyl oxygen atoms occupy the axial positions. The equatorial coordination plane contains the disulfide (S{sub 2}{sup -2}) group bonded in a "side-on" fashion, and two oxygen and two sulfur donor atoms from the monothiocarbamate ligands. Interatomic distances are S-S = 2.05(1) {Angstrom}, U-S= 2.714(3) {Angstrom} (disulfide); U-S= 2.871(3) {Angstrom} and U-O = 2.46(1) {Angstrom} (thiocarbamate); U-O = 1.81(1) {Angstrom} (uranyl), The nitrogen atom in the dipropylammonium cation is hydrogen bonded to the uranyl oxgyen atoms,

  2. Development and application of an assay for uranyl complexation by fungal metabolites, including siderophores.

    PubMed

    Renshaw, Joanna C; Halliday, Verity; Robson, Geoffrey D; Trinci, Anthony P J; Wiebe, Marilyn G; Livens, Francis R; Collison, David; Taylor, Robin J

    2003-06-01

    An assay to detect UO(2)(2+) complexation was developed based on the chrome azurol S (CAS) assay for siderophores (B. Schwyn and J. B. Neilands, Anal. Biochem. 160:47-56, 1987) and was used to investigate the ability of fungal metabolites to complex actinides. In this assay the discoloration of two dyed agars (one containing a CAS-Fe(3+) dye and the other containing a CAS-UO(2)(2+) dye) caused by ligands was quantified. The assay was tested by using the siderophore desferrioxamine B (DFO), and the results showed that there was a regular, reproducible relationship between discoloration and the amount of siderophore added. The ratio of the discoloration on the CAS-UO(2)(2+) agar to the discoloration on the CAS-Fe(3+) agar was independent of the amount of siderophore added. A total of 113 fungi and yeasts were isolated from three soil samples taken from the Peak District National Park. The fungi were screened for the production of UO(2)(2+) chelators by using the CAS-based assay and were also tested specifically for hydroxamate siderophore production by using the hydroxamate siderophore auxotroph Aureobacterium flavescens JG-9. This organism is highly sensitive to the presence of hydroxamate siderophores. However, the CAS-based assay was found to be less sensitive than the A. flavescens JG-9 assay. No significant difference between the results for each site for the two tests was found. Three isolates were selected for further study and were identified as two Pencillium species and a Mucor species. Our results show that the new assay can be effectively used to screen fungi for the production of UO(2)(2+) chelating ligands. We suggest that hydroxamate siderophores can be produced by mucoraceous fungi. PMID:12788768

  3. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    SciTech Connect

    Arnold, John

    2015-01-21

    The uranyl cation (UO₂²⁺) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  4. Impact of uranyl-calcium-carbonato complexes on uranium(VI) adsorption to synthetic and natural sediments.

    PubMed

    Stewart, Brandy D; Mayes, Melanie A; Fendorf, Scott

    2010-02-01

    Adsorption on soil and sediment solids may decrease aqueous uranium concentrations and limit its propensity for migration in natural and contaminated settings. Uranium adsorption will be controlled in large part by its aqueous speciation, with a particular dependence on the presence of dissolved calcium and carbonate. Here we quantify the impact of uranyl speciation on adsorption to both goethite and sediments from the Hanford Clastic Dike and Oak Ridge Melton Branch Ridgetop formations. Hanford sediments were preconditioned with sodium acetate and acetic acid to remove carbonate grains, and Ca and carbonate were reintroduced at defined levels to provide a range of aqueous uranyl species. U(VI) adsorption is directly linked to UO(2)(2+) speciation, with the extent of retention decreasing with formation of ternary uranyl-calcium-carbonato species. Adsorption isotherms under the conditions studied are linear, and K(d) values decrease from 48 to 17 L kg(-1) for goethite, from 64 to 29 L kg (-1) for Hanford sediments, and from 95 to 51 L kg(-1) for Melton Branch sediments as the Ca concentration increases from 0 to 1 mM at pH 7. Our observations reveal that, in carbonate-bearing waters, neutral to slightly acidic pH values ( approximately 5) and limited dissolved calcium are optimal for uranium adsorption. PMID:20058915

  5. The synthesis and characterization of new iron coordination complexes utilizing an asymmetric coordinating chelate ligand

    SciTech Connect

    Watkins, B.E.; Satcher, J.H.

    1995-07-01

    A binuclear, unsymmetric coordinating ligand that is an effective metal chelator has been designed and synthesized. The new ligand has been shown to react readily with iron(II)/(III) forming a variety of coordination complexes. The binuclear complexes are of significant interest since they represent proof-of-principle for the development of coordinatively asymmetric, binuclear metal chelate compounds. Although this structural type of chelator now appears to be common in biological systems, it has not been previously described for inorganic coordination chemistry. The isolation of oxidation products will be helpful in establishing reaction mechanism(s) of these complexes with molecular oxygen. It is expected that this ligand and derivatives of it will play an important role in the development of bioinorganic complexes that aim to mimic enzyme active sites that function by substrate interaction at only one metal site of a multimetal active site.

  6. Synthesis of uranyl(II), vanadyl(II) and zirconyl urate complexes, spectral, thermal and biological studies

    NASA Astrophysics Data System (ADS)

    El-Megharbel, Samy M.; El-Metwaly, Nashwa M.; Refat, Moamen S.

    2015-10-01

    Three urate chelations were obtained when uric acid was reacted with UO2(CH3COO)2H2O, VOSO4·XH2O and ZrOCl2·XH2O salts with neutralized with 0.1 M NaOH aqueous media. The 1:2 metal-to-ligand complexes [(UO2)2(C5H2N4O3)2](H2O), [(ZrO)2(H2O)2(C5H2N4O3)2] and [VO((C5H3N4O3)2] were characterized by elemental analyses, molar conductivity, (infrared, Raman and UV-vis) spectra, effective magnetic moment in Bohr magnetons, and thermal analysis (TG/DTG). The urate ligand coordinates as mononegative bidentate donor towards the mononuclear central vanadium atom and coordinated as binegative tetradentate mode towards the binuclear dioxouranium and zirconyl centers. The antibacterial activity of the metal complexes were tested against some kind of bacteria and fungi strains and compared with uric acid. The ligand, ZrO(II) and UO2(II) complex showed a week potential degradation on calf thymus DNA, whereas VO(II) complex slightly degraded the DNA.

  7. Umbellate distortions of the uranyl coordination environment result in a stable and porous polycatenated framework that can effectively remove cesium from aqueous solutions.

    PubMed

    Wang, Yanlong; Liu, Zhiyong; Li, Yuxiang; Bai, Zhuanling; Liu, Wei; Wang, Yaxing; Xu, Xiaomei; Xiao, Chengliang; Sheng, Daopeng; Diwu, Juan; Su, Jing; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2015-05-20

    Searching for new chemically durable and radiation-resistant absorbent materials for actinides and their fission products generated in the nuclear fuel cycle remain highly desirable, for both waste management and contamination remediation. Here we present a rare case of 3D uranyl organic framework material built through polycatenating of three sets of graphene-like layers, which exhibits significant umbellate distortions in the uranyl equatorial planes studied thoroughly by linear transit calculations. This unique structural arrangement leads to high β and γ radiation-resistance and chemical stability in aqueous solutions within a wide pH range from 3 to 12. Being equipped with the highest surface area among all actinide compounds known to date and completely exchangeable [(CH3)2NH2](+) cations in the structure, this material is able to selectively remove cesium from aqueous solutions while retaining the polycatenated framework structure. PMID:25939750

  8. Structural features of two polymorphs of ammonium uranyl crotonate

    NASA Astrophysics Data System (ADS)

    Savchenkov, A. V.; Peresypkina, E. V.; Pushkin, D. V.; Virovets, A. V.; Serezhkina, L. B.; Serezhkin, V. N.

    2014-09-01

    X-ray crystallography, FTIR spectroscopy and thermal analysis were conducted for crystals of two polymorphs of NH4UO2(C3H5COO)3, which are the first examples of uranyl tricarboxylate complexes with ions of unsaturated aliphatic monocarboxylic acid. The main structural units of both polymorphs are anionic complexes [UO2(C3H5COO)3]-. Uranium atoms adopt hexagonal bipyramidal coordination polyhedron, and crotonate ions realize bidentate cyclic type of coordination. Due to different packing of ammonium ions and [UO2(C3H5COO)3]- complexes triclinic crystals of α-polymorph have layer structure and cubic crystals of β-polymorph have three dimensional structure. Features of three dimensional packing of R+ ions and [UO2L3]- complexes in structures of 25 known R[UO2L3] compounds are discussed.

  9. Colloidal Nanocrystals Fluoresced by Surface Coordination Complexes

    PubMed Central

    Wang, Guan; Ji, Jianwei; Zhang, Xinwen; Zhang, Yan; Wang, Qiangbin; You, Xiaozeng; Xu, Xiangxing

    2014-01-01

    Colloidal Nanocrystals (NCs) with fluorescence originating from surface complexes are successfully prepared. The components of these NCs range from insulator, semiconductor to metal, with either pure phase, doped or core/shell structures. The photoluminescence of these NCs can be reversibly tuned across the visible to infrared spectrum, and even allow multi-color emission. A light emitting device is fabricated and a new in vivo cell imaging method is performed to demonstrate the power of this technology for emerging applications. PMID:24970242

  10. Energy Landscape of Chelated Uranyl: Antibody Interactions by Dynamic Force Spectroscopy

    PubMed Central

    Odorico, Michael; Teulon, Jean-Marie; Bessou, Thérèse; Vidaud, Claude; Bellanger, Laurent; Chen, Shu-wen W.; Quéméneur, Éric; Parot, Pierre; Pellequer, Jean-Luc

    2007-01-01

    We used dynamic force spectroscopy (DFS) to explore the energy landscape of interactions between a chelated uranyl compound and a monoclonal antibody raised against the uranyl-dicarboxy-phenanthroline complex. We estimated the potential energy barrier widths and the relevant thermodynamic rate constants along the dissociation coordinate. Using atomic force microscopy, four different experimental setups with or without the uranyl ion in the chelate ligand, we have distinguished specific and nonspecific binding in the binding affinity of the uranyl compound to the antibody. The force loading rates for our system were measured from 15 to 26,400 pN/s. The results showed two regimes in the plot of the most probable unbinding force versus the logarithm of the loading rate, revealing the presence of two (at least) activation barriers. Analyses of DFS suggest parallel multivalent binding present in either regime. We have also built a molecular model for the variable fragment of the antibody and used computational graphics to dock the chelated uranyl ion into the binding pocket. The structural analysis led us to hypothesize that the two regimes originate from two interaction modes: the first one corresponds to an energy barrier with a very narrow width of 0.5 ± 0.2 Å, inferring dissociation of the uranyl ion from its first coordination shell (Asp residue); the second one with a broader energy barrier width (3.9 ± 0.3 Å) infers the entire chelate compound dissociated from the antibody. Our study highlights the sensitivity of DFS experiments to dissect protein-metal compound interactions. PMID:17449661

  11. Synthesis of Coordinatively Unsaturated Tetravalent Actinide Complexes with η(5) Coordination of Pyrrole.

    PubMed

    Batrice, Rami J; Fridman, Natalia; Eisen, Moris S

    2016-03-21

    The synthesis of new actinide complexes utilizing bridged α-alkyl-pyrrolyl ligands is presented. Lithiation of the ligands followed by treatment with 1 equiv of actinide tetrachloride (uranium or thorium) produces the desired complex in good yield. X-ray diffraction studies reveal unique η(5):η(5) coordination of the pyrrolyl moieties; when the nonsterically demanding methylated ligand is used, rapid addition of the lithiated ligand solution to the metal precursor forms a bis-ligated complex that reveals η(5):η(1) coordination as determined by crystallographic analysis. PMID:26950463

  12. Quantifying the binding strength of salicylaldoxime-uranyl complexes relative to competing salicylaldoxime-transition metal ion complexes in aqueous solution: a combined experimental and computational study.

    PubMed

    Mehio, Nada; Ivanov, Alexander S; Williams, Neil J; Mayes, Richard T; Bryantsev, Vyacheslav S; Hancock, Robert D; Dai, Sheng

    2016-05-31

    The design of new ligands and investigation of UO2(2+) complexations are an essential aspect of reducing the cost of extracting uranium from seawater, improving the sorption efficiency for uranium and the selectivity for uranium over competing ions (such as the transition metal cations). The binding strengths of salicylaldoxime-UO2(2+) complexes were quantified for the first time and compared with the binding strengths of salicylic acid-UO2(2+) and representative amidoxime-UO2(2+) complexes. We found that the binding strengths of salicylaldoxime-UO2(2+) complexes are ∼2-4 log β2 units greater in magnitude than their corresponding salicylic acid-UO2(2+) and representative amidoxime-UO2(2+) complexes; moreover, the selectivity of salicylaldoxime towards the UO2(2+) cation over competing Cu(2+) and Fe(3+) cations is far greater than those reported for salicylic acid and glutarimidedioxime in the literature. The higher UO2(2+) selectivity can likely be attributed to the different coordination modes observed for salicylaldoxime-UO2(2+) and salicylaldoxime-transition metal complexes. Density functional theory calculations indicate that salicylaldoxime can coordinate with UO2(2+) as a dianion species formed by η(2) coordination of the aldoximate and monodentate binding of the phenolate group. In contrast, salicylaldoxime coordinates with transition metal cations as a monoanion species via a chelate formed between phenolate and the oxime N; the complexes are stabilized via hydrogen bonding interactions between the oxime OH group and phenolate. By coupling the experimentally determined thermodynamic constants and the results of theoretical computations, we are able to derive a number of ligand design principles to further improve the UO2(2+) cation affinity, and thus further increase the selectivity of salicylaldoxime derivatives. PMID:26979403

  13. The phi complex as a neuromarker of human social coordination

    PubMed Central

    Tognoli, Emmanuelle; Lagarde, Julien; DeGuzman, Gonzalo C.; Kelso, J. A. Scott

    2007-01-01

    Many social interactions rely upon mutual information exchange: one member of a pair changes in response to the other while at the same time producing actions that alter the behavior of the other. However, little is known about how such social processes are integrated in the brain. Here, we used a specially designed dual-electroencephalogram system and the conceptual framework of coordination dynamics to identify neural signatures of effective, real-time coordination between people and its breakdown or absence. High-resolution spectral analysis of electrical brain activity before and during visually mediated social coordination revealed a marked depression in occipital alpha and rolandic mu rhythms during social interaction that was independent of whether behavior was coordinated or not. In contrast, a pair of oscillatory components (phi1 and phi2) located above right centro-parietal cortex distinguished effective from ineffective coordination: increase of phi1 favored independent behavior and increase of phi2 favored coordinated behavior. The topography of the phi complex is consistent with neuroanatomical sources within the human mirror neuron system. A plausible mechanism is that the phi complex reflects the influence of the other on a person's ongoing behavior, with phi1 expressing the inhibition of the human mirror neuron system and phi2 its enhancement. PMID:17470821

  14. Microporous coordination complex and method of making the same

    DOEpatents

    Matzger, Adam J.; Koh, Kyoungmoo

    2016-05-31

    Disclosed herein is a three-dimensional coordination complex that includes a plurality of inorganic centers; a plurality of a first bis(bidentate) linker; and a plurality of a second bis(bidentate) linker, where the first and the second bis(bidentate) linkers are have different lengths, and the bidentate binding sites on each linker face in opposite directions on an axis.

  15. Extended structures and physicochemical properties of uranyl-organic compounds.

    PubMed

    Wang, Kai-Xue; Chen, Jie-Sheng

    2011-07-19

    The ability of uranium to undergo nuclear fission has been exploited primarily to manufacture nuclear weapons and to generate nuclear power. Outside of its nuclear physics, uranium also exhibits rich chemistry, and it forms various compounds with other elements. Among the uranium-bearing compounds, those with a uranium oxidation state of +6 are most common and a particular structural unit, uranyl UO(2)(2+) is usually involved in these hexavalent uranium compounds. Apart from forming solids with inorganic ions, the uranyl unit also bonds to organic molecules to generate uranyl-organic coordination materials. If appropriate reaction conditions are employed, uranyl-organic extended structures (1-D chains, 2-D layers, and 3-D frameworks) can be obtained. Research on uranyl-organic compounds with extended structures allows for the exploration of their rich structural chemistry, and such studies also point to potential applications such as in materials that could facilitate nuclear waste disposal. In this Account, we describe the structural features of uranyl-organic compounds and efforts to synthesize uranyl-organic compounds with desired structures. We address strategies to construct 3-D uranyl-organic frameworks through rational selection of organic ligands and the incorporation of heteroatoms. The UO(2)(2+) species with inactive U═O double bonds usually form bipyramidal polyhedral structures with ligands coordinated at the equatorial positions, and these polyhedra act as primary building units (PBUs) for the construction of uranyl-organic compounds. The geometry of the uranyl ions and the steric arrangements and functionalities of organic ligands can be exploited in the the design of uranyl--organic extended structures, We also focus on the investigation of the promising physicochemical properties of uranyl-organic compounds. Uranyl-organic materials with an extended structure may exhibit attractive properties, such as photoluminescence, photocatalysis

  16. Molecular Simulation of the Diffusion of Uranyl Carbonate Species in Aqueous Solution

    SciTech Connect

    Kerisit, Sebastien N.; Liu, Chongxuan

    2010-09-01

    Molecular dynamics simulations of aqueous uranyl carbonate species were carried out with two different potential models to gain molecular-level insight into the hydration properties of these species and evaluate the ability of the two models to reproduce published ab initio and experimental data. The simulation results were used to estimate the self-diffusion coefficients of uranyl carbonate species that often dominate uranyl speciation in groundwater systems. The first potential model was based on a series of shell models developed by Parker and co-workers (including (DE LEEUW and PARKER, 1998; KERISIT and PARKER, 2004; PAVESE et al., 1996). The second potential model was a rigid-ion model based on the flexible SPC water model (TELEMAN et al., 1987), the uranyl model of Guilbaud and Wipff (GUILBAUD and WIPFF, 1996), and the parameters for the carbonate ion given by Greathouse and co-workers (GREATHOUSE and CYGAN, 2005; GREATHOUSE et al., 2002). Analysis of structural (mean interatomic distances and coordination numbers) and dynamical (water residence times in hydration shell and self-diffusion coefficients) properties showed that, overall, the first potential model performed best when compared to published data, although the only major discrepancy with the second model was a misrepresentation of the configuration adopted by the alkaline-earth uranyl carbonate ions. The diffusion coefficients obtained for the alkaline-earth cations and the uranyl ion were compared with three variants of the Stokes-Einstein (SE) equation and it was found that none of the three SE models were able to reproduce both the absolute values and the overall trend determined from the molecular dynamics simulations. However, as would be expected based on the SE equation, a plot of the diffusion coefficients of the uranyl carbonate complexes as a function of the inverse of the equivalent spherical radius showed a general linear dependence with the two models yielding almost identical gradients

  17. Coordinating complex problem-solving among distributed intelligent agents

    NASA Technical Reports Server (NTRS)

    Adler, Richard M.

    1992-01-01

    A process-oriented control model is described for distributed problem solving. The model coordinates the transfer and manipulation of information across independent networked applications, both intelligent and conventional. The model was implemented using SOCIAL, a set of object-oriented tools for distributing computing. Complex sequences of distributed tasks are specified in terms of high level scripts. Scripts are executed by SOCIAL objects called Manager Agents, which realize an intelligent coordination model that routes individual tasks to suitable server applications across the network. These tools are illustrated in a prototype distributed system for decision support of ground operations for NASA's Space Shuttle fleet.

  18. The synthesis and characterization of new iron coordination complexes utilizing an asymmetric coordinating chelate ligand

    SciTech Connect

    Watkins, B.E.; Satcher, J.H.

    1995-03-01

    We are investigating the structure/activity relationships of the bacterial enzyme methane monooxygenase, which catalyzes the specific oxidation of methane to methanol. We then utilize this information to design and synthesize inorganic coordination complexes that mimic the function of the native enzyme but are more robust and have higher catalytic site density. We envision these catalysts to be useful in process catalytic reactors in the conversion of methane in natural gas to liquid ethanol.

  19. The synthesis and characterization of new iron coordination complexes utilizing an asymmetric coordinating chelate ligand

    SciTech Connect

    Baldwin, D.; Watkins, B.E.; Satcher, J.H.

    1993-12-31

    The authors are investigating the structure/activity relationships of the bacterial enzyme, methane monooxygenase, which catalyzes the specific oxidation of methane to methanol. They then utilize this information to design and synthesize inorganic coordination complexes that mimic the function of the native enzyme but are more robust and have higher catalytic site density. They envision these catalysts to be useful in process catalytic reactors in the conversion of methane in natural gas to liquid methanol.

  20. Energetic lanthanide complexes: coordination chemistry and explosives applications

    NASA Astrophysics Data System (ADS)

    Manner, V. W.; Barker, B. J.; Sanders, V. E.; Laintz, K. E.; Scott, B. L.; Preston, D. N.; Sandstrom, M.; Reardon, B. L.

    2014-05-01

    Metals are generally added to organic molecular explosives in a heterogeneous composite to improve overall heat and energy release. In order to avoid creating a mixture that can vary in homogeneity, energetic organic molecules can be directly bonded to high molecular weight metals, forming a single metal complex with Angstrom-scale separation between the metal and the explosive. To probe the relationship between the structural properties of metal complexes and explosive performance, a new series of energetic lanthanide complexes has been prepared using energetic ligands such as NTO (5-nitro-2,4-dihydro-1,2,4-triazole-3-one). These are the first examples of lanthanide NTO complexes where no water is coordinated to the metal, demonstrating novel control of the coordination environment. The complexes have been characterized by X-ray crystallography, NMR and IR spectroscopies, photoluminescence, and sensitivity testing. The structural and energetic properties are discussed in the context of enhanced blast effects and detection. Cheetah calculations have been performed to fine-tune physical properties, creating a systematic method for producing explosives with 'tailor made' characteristics. These new complexes will be benchmarks for further study in the field of metalized high explosives.

  1. Energetic Lanthanide Complexes: Coordination Chemistry and Explosives Applications

    NASA Astrophysics Data System (ADS)

    Manner, Virginia; Barker, Beau; Sanders, Eric; Laintz, Kenneth; Scott, Brian; Preston, Daniel; Sandstrom, Mary; Reardon, Bettina

    2013-06-01

    Metals are generally added to organic molecular explosives in a heterogeneous composite to improve overall heat and energy release. In order to avoid creating a mixture that can vary in homogeneity, energetic organic molecules can be directly bonded to high molecular weight metals, forming a single metal complex with Angstrom-scale separation between the metal and the explosive. To probe the relationship between the structural properties of metal complexes and explosive performance, a new series of energetic lanthanide complexes has been prepared using energetic ligands such as NTO (5-nitro-2,4-dihydro-1,2,4-triazole-3-one). These are the first examples of lanthanide NTO complexes where no water is coordinated to the metal, demonstrating novel control of the coordination environment. The complexes have been characterized by X-ray crystallography, NMR and IR spectroscopies, photoluminescence, and sensitivity testing. The structural and energetic properties are discussed in the context of enhanced blast effects and detection. Cheetah calculations have been performed to fine-tune physical properties, creating a systematic method for producing explosives with ``tailor made'' characteristics. These new complexes will be benchmarks for further study in the field of metalized high explosives.

  2. Gas-phase coordination complexes of U(VI)O2(2+), Np(VI)O2(2+), and Pu(VI)O2(2+) with dimethylformamide.

    PubMed

    Rutkowski, Philip X; Rios, Daniel; Gibson, John K; Van Stipdonk, Michael J

    2011-11-01

    Electrospray ionization of actinyl perchlorate solutions in H(2)O with 5% by volume of dimethylformamide (DMF) produced the isolatable gas-phase complexes, [An(VI)O(2)(DMF)(3)(H(2)O)](2+) and [An(VI)O(2)(DMF)(4)](2+), where An = U, Np, and Pu. Collision-induced dissociation confirmed the composition of the dipositive coordination complexes, and produced doubly- and singly-charged fragment ions. The fragmentation products reveal differences in underlying chemistries of uranyl, neptunyl, and plutonyl, including the lower stability of Np(VI) and Pu(VI) compared with U(VI). PMID:21952769

  3. Structure sensitive normal coordinate analysis of metal-diethyldithiocarbamate - complexes

    NASA Astrophysics Data System (ADS)

    Mikosch, H.; Bauer, G.; Kellner, R.; Trendafilova, N. S.; St. Nikolov, G.

    1986-03-01

    Symmetry changes in the course of dissolution are assumed to produce frequency shifts in molecular spectra of N, N-Disubstituted Dithiocarbamates. Using (mass-weighted) cartesian coordinates it is possible to calculate eigenvalues both for the site- and the molecular symmetry. Calculated shifts for Cu- and Zn- complexes are of the same order of magnitude as experimental results and calculation of frequencies even for assumed structures is possible.

  4. Charge transfer vibronic transitions in uranyl tetrachloride compounds;

    SciTech Connect

    Liu, G. K.; Deifel, N. P.; Cahill, C. L.

    2012-01-01

    The electronic and vibronic interactions of uranyl (UO{sub 2}){sup 2+} in three tetrachloride crystals have been investigated with spectroscopic experiments and theoretical modeling. Analysis and simulation of the absorption and photoluminescence spectra have resulted in a quantitative understanding of the charge transfer vibronic transitions of uranyl in the crystals. The spectra obtained at liquid helium temperature consist of extremely narrow zero-phonon lines (ZPL) and vibronic bands. The observed ZPLs are assigned to the first group of the excited states formed by electronic excitation from the 3{sigma} ground state into the f{sub {delta}{phi}}, orbitals of uranyl. The Huang-Rhys theory of vibronic coupling is modified successfully for simulating both the absorption and luminescence spectra. It is shown that only vibronic coupling to the axially symmetric stretching mode is Franck-Condon allowed, whereas other modes are involved through coupling with the symmetric stretching mode. The energies of electronic transitions, vibration frequencies of various local modes, and changes in the O=U=O bond length of uranyl in different electronic states and in different coordination geometries are evaluated in empirical simulations of the optical spectra. Multiple uranyl sites derived from the resolution of a superlattice at low temperature are resolved by crystallographic characterization and time- and energy-resolved spectroscopic studies. The present empirical simulation provides insights into fundamental understanding of uranyl electronic interactions and is useful for quantitative characterization of uranyl coordination.

  5. Charge transfer vibronic transitions in uranyl tetrachloride compounds

    SciTech Connect

    Liu, Guokui; Deifel, Nicholas P.; Cahill, Christopher L.; Zhurov, Vladimir V.; Pinkerton, A. Alan

    2012-01-01

    The electronic and vibronic interactions of uranyl (UO₂)2+ in three tetrachloride crystals have been investigated with spectroscopic experiments and theoretical modeling. Analysis and simulation of the absorption and photoluminescence spectra have resulted in a quantitative understanding of the charge transfer vibronic transitions of uranyl in the crystals. The spectra obtained at liquid helium temperature consist of extremely narrow zero-phonon lines (ZPL) and vibronic bands. The observed ZPLs are assigned to the first group of the excited states formed by electronic excitation from the 3σ ground state into the fδ,Φ orbitals of uranyl. The Huang–Rhys theory of vibronic coupling is modified successfully for simulating both the absorption and luminescence spectra. It is shown that only vibronic coupling to the axially symmetric stretching mode is Franck–Condon allowed, whereas other modes are involved through coupling with the symmetric stretching mode. The energies of electronic transitions, vibration frequencies of various local modes, and changes in the O=U=O bond length of uranyl in different electronic states and in different coordination geometries are evaluated in empirical simulations of the optical spectra. Multiple uranyl sites derived from the resolution of a superlattice at low temperature are resolved by crystallographic characterization and time- and energy-resolved spectroscopic studies. The present empirical simulation provides insights into fundamental understanding of uranyl electronic interactions and is useful for quantitative characterization of uranyl coordination.

  6. Giant regular polyhedra from calixarene carboxylates and uranyl

    PubMed Central

    Pasquale, Sara; Sattin, Sara; Escudero-Adán, Eduardo C.; Martínez-Belmonte, Marta; de Mendoza, Javier

    2012-01-01

    Self-assembly of large multi-component systems is a common strategy for the bottom-up construction of discrete, well-defined, nanoscopic-sized cages. Icosahedral or pseudospherical viral capsids, built up from hundreds of identical proteins, constitute typical examples of the complexity attained by biological self-assembly. Chemical versions of the so-called 5 Platonic regular or 13 Archimedean semi-regular polyhedra are usually assembled combining molecular platforms with metals with commensurate coordination spheres. Here we report novel, self-assembled cages, using the conical-shaped carboxylic acid derivatives of calix[4]arene and calix[5]arene as ligands, and the uranyl cation UO22+ as a metallic counterpart, which coordinates with three carboxylates at the equatorial plane, giving rise to hexagonal bipyramidal architectures. As a result, octahedral and icosahedral anionic metallocages of nanoscopic dimensions are formed with an unusually small number of components. PMID:22510690

  7. Tuning Coordination in s-Block Carbazol-9-yl Complexes

    PubMed Central

    Ortu, Fabrizio; Moxey, Graeme J; Blake, Alexander J; Lewis, William; Kays, Deborah L

    2015-01-01

    1,3,6,8-Tetra-tert-butylcarbazol-9-yl and 1,8-diaryl-3,6-di(tert-butyl)carbazol-9-yl ligands have been utilized in the synthesis of potassium and magnesium complexes. The potassium complexes (1,3,6,8-tBu4carb)K(THF)4 (1; carb=C12H4N), [(1,8-Xyl2-3,6-tBu2carb)K(THF)]2 (2; Xyl=3,5-Me2C6H3) and (1,8-Mes2-3,6-tBu2carb)K(THF)2 (3; Mes=2,4,6-Me3C6H2) were reacted with MgI2 to give the Hauser bases 1,3,6,8-tBu4carbMgI(THF)2 (4) and 1,8-Ar2-3,6-tBu2carbMgI(THF) (Ar=Xyl 5, Ar=Mes 6). Structural investigations of the potassium and magnesium derivatives highlight significant differences in the coordination motifs, which depend on the nature of the 1- and 8-substituents: 1,8-di(tert-butyl)-substituted ligands gave π-type compounds (1 and 4), in which the carbazolyl ligand acts as a multi-hapto donor, with the metal cations positioned below the coordination plane in a half-sandwich conformation, whereas the use of 1,8-diaryl substituted ligands gave σ-type complexes (2 and 6). Space-filling diagrams and percent buried volume calculations indicated that aryl-substituted carbazolyl ligands offer a steric cleft better suited to stabilization of low-coordinate magnesium complexes. PMID:25783772

  8. Complex-coordinate non-Hermitian transformation optics

    NASA Astrophysics Data System (ADS)

    Savoia, S.; Castaldi, G.; Galdi, V.

    2016-04-01

    Transformation optics (TO) is conventionally based on real-valued coordinate transformations and, therefore, cannot naturally handle metamaterials featuring gain and/or losses. Motivated by the growing interest in non-Hermitian optical scenarios featuring spatial modulation of gain and loss, and building upon our previous studies, we explore here possible extensions of the TO framework relying on complex-valued coordinate transformations. We show that such extensions can be naturally combined with well-established powerful tools and formalisms in electromagnetics and optics, based on the ‘complexification’ of spatial and spectral quantities. This enables us to deal with rather general non-Hermitian optical scenarios, while retaining the attractive characteristics of conventional (real-valued) TO in terms of physically incisive modeling and geometry-driven intuitive design. As representative examples, we illustrate the manipulation of beam-like wave-objects (modeled in terms of ‘complex source points’) as well as radiating states (‘leaky waves’, modeled in terms of complex-valued propagation constants). Our analytical results, validated against full-wave numerical simulations, provide useful insight into the wave propagation in non-Hermitian scenarios, and may indicate new directions in the synthesis of active optical devices and antennas.

  9. Structure and dynamics of complexes of the uranyl ion with nonamethylimidodiphosphoramide (NIPA). 2. NMR studies of complexes (UO/sub 2/(NIPA)/sub 2/X)(CIO/sub 4/)/sub 2/ with X = H/sub 2/O, MeOH, EtOH, or Me/sub 2/CO

    SciTech Connect

    Rodehueser, L.; Rubini, P.R.; Bokolo, K.; Delpuech, J.J.

    1982-03-01

    The /sup 31/P and /sup 1/H spectra at -90/sup 0/C of the title uranyl complex ions (prepared as solutions of the solid perchlorates in inert anhydrous organic solvents (CH/sub 3/NO/sub 2/, CH/sub 2/Cl/sub 2/)) reveal a pentacoordinated arrangement of two symmetrically doubly bonded NIPA molecules and one solvent molecule about the uranyl group. In the case of (UO/sub 2/(NIPA)/sub 2/(EtOH))(ClO/sub 4/)/sub 2/, an intermolecular exchange between bound and free ethanol molecules is observed above -75/sup 0/C upon addition of ethanol to a solution of the complex. The observed rate law, k/sub inter/ = kK(EtOH)/(1 + K(EtOH) is accounted for by the existence of an outer-sphere complex (UO/sub 2//sup 2 +/(NIPA)/sub 2/(EtOH))EtOH in fast equilibrium (K) with the initial complex and free ethanol. The rate-determining step (k) consists of an outer-sphere to inner-sphere interchange of ethanol molecules. The thermodynamic and kinetic parameters are K(25/sup 0/C) = 15.8 dm/sup 3/ mol/sup -1/, k(25/sup 0/C) = 1.0 x 10/sup 4/s/sup -1/, ..delta..H and ..delta..H/sub inter//sup + +/ = -4.8 and 7.6 kcal mol/sup -1/, and ..delta..S and ..delta..S/sub inter//sup + +/ = 10.7 and -14.7 eu. A second exchange takes place at higher temperatures (above -30/sup 0/C) yielding full dynamic equivalence of the phosphorus nuclei of the coordinated NIPA molecules. The observed rate law k/sub intra/ = k/sub ex/(1 + K(EtOH)) reveals that the internal rearrangement of NIPA molecules occurs on the complex ion (UO/sub 2/(NIPA)/sub 2/(EtOH))/sup 2 +/ but not on the outer-sphere complex: k/sub ex/(25/sup 0/C) = 0.91 x 10/sup 3/s/sup -1/, ..delta..H/sub intra//sup + +/ = 10.6 kcal mol/sup -1/ and ..delta..S/sub intra//sup + +/ = -9.4 eu. Possible mechanisms for this exchange are discussed. 5 figures, 2 tables.

  10. Uranyl peroxide closed clusters containing topological squares

    SciTech Connect

    Unruh, Daniel K.; Burtner, Alicia; Pressprich, Laura; Sigmon, Ginger E.; Burns, Peter C

    2010-01-01

    Four self-assembling clusters of uranyl peroxide polyhedra have been formed in alkaline aqueous solutions and structurally characterized. These clusters consist of 28, 30, 36 and 44 uranyl polyhedra and exhibit complex new topologies. Each has a structure that contains topological squares, pentagons and hexagons. Analysis of possible topologies within boundary constraints indicates a tendency for adoption of higher symmetry topologies in these cases. Small angle X-ray scattering data demonstrated that crystals of one of these clusters can be dissolved in ultrapure water and that the clusters remain intact for at least several days.

  11. {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.

  12. Expanding the crystal chemistry of uranyl peroxides: four hybrid uranyl-peroxide structures containing EDTA.

    PubMed

    Qiu, Jie; Ling, Jie; Sieradzki, Claire; Nguyen, Kevin; Wylie, Ernest M; Szymanowski, Jennifer E S; Burns, Peter C

    2014-11-17

    The first four uranyl peroxide compounds containing ethylenediaminetetra-acetate (EDTA) were synthesized and characterized from aqueous uranyl peroxide nitrate solutions with a pH range of 5-7. Raman spectra demonstrated that reaction solutions that crystallized [NaK15[(UO2)8(O2)8(C10H12O10N2)2(C2O4)4]·(H2O)14] (1) and [Li4K6[(UO2)8(O2)6(C10H12O10N2)2(NO3)6]·(H2O)26] (2) contained excess peroxide, and their structures contained oxidized ethylenediaminetetraacetate, EDTAO2(4-). The solutions from which [K4[(UO2)4(O2)2(C10H13O8N2)2(IO3)2]·(H2O)16] (3) and LiK3[(UO2)4(O2)2(C10H12O8N2)2(H2O)2]·(H2O)18 (4) crystallized contained no free peroxide, and the structures incorporated intact EDTA(4-). In contrast to the large family of uranyl peroxide cage clusters, coordination of uranyl peroxide units in 1-4 by EDTA(4-) or EDTAO2(4-) results in isolated tetramers or dimers of uranyl ions that are bridged by bidentate peroxide groups. Two tetramers are bridged by EDTAO2(4-) to form octamers in 1 and 2, and dimers of uranyl polyhedra are linked through iodate groups in 3 and EDTA(4-) in 4, forming chains in both cases. In each structure the U-O2-U dihedral angle is strongly bent, at ∼140°, consistent with the configuration of this linkage in cage clusters and other recently reported uranyl peroxides. PMID:25350361

  13. Coordination Chemistry of Homoleptic Actinide(IV)-Thiocyanate Complexes.

    PubMed

    Carter, Tyler J; Wilson, Richard E

    2015-10-26

    The synthesis, X-ray crystal structure, vibrational and optical spectroscopy for the eight-coordinate thiocyanate compounds, [Et4 N]4 [Pu(IV) (NCS)8 ], [Et4 N]4 [Th(IV) (NCS)8 ], and [Et4 N]4 [Ce(III) (NCS)7 (H2 O)] are reported. Thiocyanate was found to rapidly reduce plutonium to Pu(III) in acidic solutions (pH<1) in the presence of NCS(-) . The optical spectrum of [Et4 N][SCN] containing Pu(III) solution was indistinguishable from that of aquated Pu(III) suggesting that inner-sphere complexation with [Et4 N][SCN] does not occur in water. However, upon concentration, the homoleptic thiocyanate complex [Et4 N]4 [Pu(IV) (NCS)8 ] was crystallized when a large excess of [Et4 N][NCS] was present. This compound, along with its U(IV) analogue, maintains inner-sphere thiocyanate coordination in acetonitrile based on the observation of intense ligand-to-metal charge-transfer bands. Spectroscopic and crystallographic data do not support the interaction of the metal orbitals with the ligand π system, but support an enhanced An(IV) -NCS interaction, as the Lewis acidity of the metal ion increases from Th to Pu. PMID:26493880

  14. Similarities between GCS and human motor cortex: complex movement coordination

    NASA Astrophysics Data System (ADS)

    Rodríguez, Jose A.; Macias, Rosa; Molgo, Jordi; Guerra, Dailos

    2014-07-01

    The "Gran Telescopio de Canarias" (GTC1) is an optical-infrared 10-meter segmented mirror telescope at the ORM observatory in Canary Islands (Spain). The GTC control system (GCS), the brain of the telescope, is is a distributed object & component oriented system based on RT-CORBA and it is responsible for the management and operation of the telescope, including its instrumentation. On the other hand, the Human motor cortex (HMC) is a region of the cerebrum responsible for the coordination of planning, control, and executing voluntary movements. If we analyze both systems, as far as the movement control of their mechanisms and body parts is concerned, we can find extraordinary similarities in their architectures. Both are structured in layers, and their functionalities are comparable from the movement conception until the movement action itself: In the GCS we can enumerate the Sequencer high level components, the Coordination libraries, the Control Kit library and the Device Driver library as the subsystems involved in the telescope movement control. If we look at the motor cortex, we can also enumerate the primary motor cortex, the secondary motor cortices, which include the posterior parietal cortex, the premotor cortex, and the supplementary motor area (SMA), the motor units, the sensory organs and the basal ganglia. From all these components/areas we will analyze in depth the several subcortical regions, of the the motor cortex, that are involved in organizing motor programs for complex movements and the GCS coordination framework, which is composed by a set of classes that allow to the high level components to transparently control a group of mechanisms simultaneously.

  15. Coordination Programming of Two-Dimensional Metal Complex Frameworks.

    PubMed

    Maeda, Hiroaki; Sakamoto, Ryota; Nishihara, Hiroshi

    2016-03-22

    Since the discovery of graphene, two-dimensional materials with atomic thickness have attracted much attention because of their characteristic physical and chemical properties. Recently, coordination nanosheets (CONASHs) came into the world as new series of two-dimensional frameworks, which can show various functions based on metal complexes formed by numerous combinations of metal ions and ligands. This Feature Article provides an overview of recent progress in synthesizing CONASHs and in elucidating their intriguing electrical, sensing, and catalytic properties. We also review recent theoretical studies on the prediction of the unique electronic structures, magnetism, and catalytic ability of materials based on CONASHs. Future prospects for applying CONASHs to novel applications are also discussed. PMID:26915925

  16. Micro practices of coordination based on complex adaptive systems: user needs and strategies for coordinating public health in Denmark

    PubMed Central

    Wittrup, Inge; Burau, Viola

    2015-01-01

    Introduction Many highly formalised approaches to coordination poorly fit public health and recent studies call for coordination based on complex adaptive systems. Our contribution is two-fold. Empirically, we focus on public health, and theoretically we build on the patient perspective and treat coordination as a process of contingent, two-level negotiations of user needs. Theory and Methods The paper draws on the concept of user needs-based coordination and sees coordination as a process, whereby needs emerging from the life world of the user are made amenable to the health system through negotiations. The analysis is based on an explorative case study of a health promotion initiative in Denmark. It adopts an anthropological qualitative approach and uses a range of qualitative data. Results The analysis identifies four strategies of coordination: the coordinator focusing on the individual user or on relations with other professionals; and the manager coaching the coordinator or providing structural support. Crucially, the coordination strategies by management remain weak as they do not directly relate to specific user needs. Discussion In process of bottom-up negotiations user needs become blurred and this is especially a challenge for management. The study therefore calls for an increased focus on the level nature of negotiations to bridge the gap that currently weakens coordination strategies by management. PMID:26528097

  17. Cytotoxicity of Cyclometalated Platinum Complexes Based on Tridentate NCN and CNN-coordinating ligands: Remarkable Coordination Dependence

    PubMed Central

    Vezzu, Dileep A. k.; Lu, Qun; Chen, Yan-Hua; Huo, Shouquan

    2014-01-01

    A series of cyclometalated platinum complexes with diverse coordination patterns and geometries were screened for their anticancer activity. It was discovered that the NʌCʌN-coordinated platinum complex based on 1,3-di(pyridyl)benzene displayed much higher cytotoxicity against human lung cancer cells NCI-H522, HCC827, and NCI-H1299, and human prostate cancer cell RV1 than cisplatin. In a sharp contrast, the CʌNʌN-coordinated platinum complex based on 6-phenyl-2,2′-bipyridine was ineffective on these cancer cells. This remarkable difference in cytotoxicity displayed by NʌCʌN- and CʌNʌN-coordinated platinum complexes was related to the trans effect of the carbon donor in the cyclometalated platinum complexes, which played a crucial role in facilitating the dissociation of the chloride ligand to create an active binding site. The DNA binding was studied for the NʌCʌN-coordinated platinum complex using electrophoresis and emission titration. The cellular uptake observed by fluorescent microscope showed the complex is largely concentrated in the cytoplasm. The possible pathways for the cell apoptosis was studied by western blot analysis and the activation of PARP via caspase 7 was observed. PMID:24531534

  18. Cytotoxicity of cyclometalated platinum complexes based on tridentate NCN and CNN-coordinating ligands: remarkable coordination dependence.

    PubMed

    Vezzu, Dileep A K; Lu, Qun; Chen, Yan-Hua; Huo, Shouquan

    2014-05-01

    A series of cyclometalated platinum complexes with diverse coordination patterns and geometries were screened for their anticancer activity. It was discovered that the N^C^N-coordinated platinum complex based on 1,3-di(pyridyl)benzene displayed much higher cytotoxicity against human lung cancer cells NCI-H522, HCC827, and NCI-H1299, and human prostate cancer cell RV1 than cisplatin. In a sharp contrast, the C^N^N-coordinated platinum complex based on 6-phenyl-2,2'-bipyridine was ineffective on these cancer cells. This remarkable difference in cytotoxicity displayed by N^C^N- and C^N^N-coordinated platinum complexes was related to the trans effect of the carbon donor in the cyclometalated platinum complexes, which played a crucial role in facilitating the dissociation of the chloride ligand to create an active binding site. The DNA binding was studied for the N^C^N-coordinated platinum complex using electrophoresis and emission titration. The cellular uptake observed by fluorescent microscope showed that the complex is largely concentrated in the cytoplasm. The possible pathways for the cell apoptosis were studied by western blot analysis and the activation of PARP via caspase 7 was observed. PMID:24531534

  19. Structure determination of a complex tubular uranyl phenylphosphonate, (UO{sub 2}){sub 3}(HO{sub 3}PC{sub 6}H{sub 5}){sub 2}(O{sub 3}PC{sub 6}H{sub 5}){sub 2}{center_dot}H{sub 2}O, from conventional x-ray powder diffraction data

    SciTech Connect

    Poojary, D.M.; Cabeza, A.; Aranda, A.G.

    1996-03-13

    The three-dimensional structure of a complex tubular uranyl phosphonate, (UO{sub 2}){sub 3}(HO{sub 3}PC{sub 6}H{sub 5}){sub 2}(O{sub 3}PC{sub 6}H{sub 5}){sub 2}(O{sub 3}PC{sub 6}H{sub 5}){sub 2} {center_dot} H{sub 2}O, was determined ab initio from laboratory X-ray powder diffraction data and refined by the Rietveld method. The crystals belong to the space group P2{sub 1}2{sub 1}2{sub 1}, with {alpha} = 17.1966(2) {Angstrom}, b = 7.2125(2) {Angstrom}, c = 27.8282(4) {Angstrom}, and Z = 4. The structure consists of three independent uranium atoms, among which two are seven-coordinated and the third is eight-coordinated. These metal atoms are connected by four different phosphonate groups to form a one-dimensional channel structure along the b axis. The phenyl groups are arranged on the outer periphery of the channels, and their stacking forces keep the channels intact in the lattice. The determination of this structure which contains 50 non-hydrogen atoms in the asymmetric unit, from conventional X-ray powder data, represents significant progress in the application of powder techniques to structure of complex inorganic compounds, including organometallic compounds.

  20. Silver Ion-Mediated Heterometallic Three-Fold Interpenetrating Uranyl-Organic Framework.

    PubMed

    Mei, Lei; Wu, Qun-yan; An, Shu-wen; Gao, Zeng-qiang; Chai, Zhi-fang; Shi, Wei-qun

    2015-11-16

    A unique case of a uranyl-silver heterometallic 3-fold interpenetrating network (U-Ag-2,6-DCPCA) from a multifunctionalized organic ligand, 2,6-dichloroisonicotinic acid, in the presence of uranyl and silver ions is reported. It is the first report of a heterometallic uranyl-organic interpenetrating network or framework. Notably, a (4,4)-connected uranyl building unit in U-Ag-2,6-DCPCA, which is available through combined influences of structural halogenation and silver ion additive on uranyl coordination, plays a vital role in the formation of a 3-fold interpenetrating network. Halogen substitution effectively changes structural features and coordination behaviors of isonicotinate ligand and contributes to the control of uranyl coordination. Meanwhile, it exerts influence on the stabilization of 3-fold interpenetrating networks by halogen-halogen interactions. Theoretical calculation suggests that the silver ion should mainly serve as an inductive factor of uranyl species through strong Ag-N binding affinity, directly leading to the formation of a (4,4)-connected uranyl building unit and finally a heterometallic 3-fold interpenetrating network. Related experimental results, especially an interesting postsynthetic metalation, afford further evidence of this induction effect. PMID:26491817

  1. Chemical equilibria in the uranyl(VI)-peroxide-carbonate system; identification of precursors for the formation of poly-peroxometallates.

    PubMed

    Zanonato, Pier Luigi; Di Bernardo, Plinio; Szabó, Zoltán; Grenthe, Ingmar

    2012-10-14

    The focus of this study is on the identification of precursors in solution that might act as building blocks when solid uranyl(VI) poly-peroxometallate clusters containing peroxide and hydroxide bridges are formed. The precursors could be identified by using carbonate as an auxiliary ligand that prevented the formation of large clusters, such as the ones found in solids of fullerene type. Using data from potentiometric and NMR ((17)O and (13)C) experiments we identified the following complexes and determined their equilibrium constants: (UO(2))(2)(O(2))(CO(3))(4)(6-), UO(2)(O(2))CO(3)(2-), UO(2)(O(2))(CO(3))(2)(4-), (UO(2))(2)(O(2))(CO(3))(2)(2-), (UO(2))(2)(O(2))(2)(CO(3))(2-) and [UO(2)(O(2))(CO(3))](5)(10-). The NMR spectra of the pentamer show that all uranyl and carbonate sites are equivalent, which is only consistent with a ring structure built from uranyl units linked by peroxide bridges with the carbonate coordinated "outside" the ring; this proposed structure is very similar to [UO(2)(O(2))(oxalate)](5)(10-) identified by Burns et al. (J. Am. Chem. Soc., 2009, 131, 16648; Inorg. Chem., 2012, 51, 2403) in K(10)[UO(2)(O(2))(oxalate)](5)·(H(2)O)(13); similar ring structures where oxalate or carbonate has been replaced by hydroxide are important structure elements in solid poly-peroxometallate complexes. The equivalent uranyl sites in (UO(2))(2)(O(2))(2)(CO(3))(2-) suggest that the uranyl-units are linked by the carbonate ion and not by peroxide. PMID:22858588

  2. Binding of oxime group to uranyl ion.

    PubMed

    Tsantis, Sokratis T; Zagoraiou, Eirini; Savvidou, Aikaterini; Raptopoulou, Catherine P; Psycharis, Vassilis; Szyrwiel, Lukasz; Hołyńska, Małgorzata; Perlepes, Spyros P

    2016-05-31

    Currently, the leading approach for extraction of uranium from seawater is selective sorption of UO2(2+) ions onto a poly(acrylamidoxime) fiber. Amidoxime functional groups are the most studied extractant moieties for this application, but are not perfectly selective, and understanding how these groups (and more generally the oxime groups) interact with UO2(2+) and competing ions in seawater is an important step in designing better extractants. We have started a new research programme aiming at in-depth studies of the uranyl-oxime/amidoxime interactions and we report here our first results which cover aspects of the coordination chemistry of 2-pyridyl ketoximes towards UO2(2+). Detailed synthetic investigations of various UO2(2+)/mepaoH and UO2(2+)/phpaoH reaction systems (mepaoH is methyl 2-pyridyl ketoxime and phpaoH is phenyl 2-pyridyl ketoxime) have provided access to the complexes [UO2(mepao)2(MeOH)2]{[UO2(NO3)(mepao)(MeOH)2]}2 (), [UO2(mepao)2(MeOH)2] (), [(UO2)2(O2)(O2CMe)2(mepaoH)2] () and [UO2(phpao)2(MeOH)2] (). The peroxido group in , which was isolated without the addition of external peroxide sources, probably arises from a bis(aquo)- and/or bis(hydroxido)-bridged diuranyl precursor in solution followed by photochemical oxidation of the bridging groups. The U(VI) atom in the [UO2(NO3)(mepao)(MeOH)2] molecules of () is surrounded by one nitrogen and seven oxygen atoms in a very distorted hexagonal bipyramidal geometry; two oxygen atoms from the terminal MeOH ligands, two oxygen atoms from the bidentate chelating nitrato group, and the oxygen and nitrogen atoms from the η(2) oximate group of the 1.110 (Harris notation) mepao(-) ligand define the equatorial plane. This plane consists of two terminal MeOH ligands and two η(2) oximate groups in the [UO2(mepao)2(MeOH)2] molecule () of . The structure of the [UO2(mepao)2(MeOH)2] molecule that is present in is very similar to the structure of the corresponding molecule in . The structure of the dinuclear

  3. Ionothermal synthesis of uranyl compounds that incorporate imidazole derivatives

    NASA Astrophysics Data System (ADS)

    Wylie, Ernest M.; Dustin, Megan K.; Smith, Jeremy S.; Burns, Peter C.

    2013-01-01

    Ionothermal reactions of uranyl nitrate with various salts in methylimidazolium-based ionic liquids have produced single crystals of three uranyl compounds that incorporate imidazole derivatives as charge-balancing cations. (C4H7N2)[(UO2)(PO3F)(F)] (1) crystallizes in space group C2, a=17.952(1) Å, b=6.9646(6) Å, c=8.5062(7) Å, β=112.301(1)°, (C6H11N2)2[(UO2)(SO4)2] (2) crystallizes in space group C2/c, a=31.90(1) Å, b=9.383(5) Å, c=13.770(7) Å, β=93.999(7)° and (C6H11N2)[(UO2)2(PO4)(HPO4) (3) crystallizes in space group P21/n, a=9.307(2), b=18.067(4), c=9.765(2), β=93.171(2). The U6+ cations are present as (UO2)2+ uranyl ions coordinated by three O atoms and two F atoms in 1 and five O atoms in 2 and 3 to give pentagonal bipyramids. The structural unit in 1 is composed of F-sharing dimers of uranyl pentagonal bipyramids linked into sheets through corner-sharing fluorophosphate tetrahedra. The structural unit in 2 is composed of uranyl pentagonal bipyramids with one chelating sulfate tetrahedron linked into chains by three other corner-sharing sulfate tetrahedra. In 3, the structural unit is composed of chains of uranyl pentagonal bipyramids linked into sheets through edge- and corner-sharing phosphate and hydrogen phosphate tetrahedra. N-methylimidazolium cations occupy the interstitial space between the uranyl fluorophosphate sheets in 1, whereas 1-ethyl-3-methylimidazolium cations link the uranyl sulfate and phosphate units in 2 and 3 into extended structures.

  4. Coordinated disassembly of the divisome complex in Escherichia coli.

    PubMed

    Söderström, Bill; Mirzadeh, Kiavash; Toddo, Stephen; von Heijne, Gunnar; Skoglund, Ulf; Daley, Daniel O

    2016-08-01

    The divisome is the macromolecular complex that carries out cell division in Escherichia coli. Every generation it must be assembled, and then disassembled so that the sequestered proteins can be recycled. Whilst the assembly process has been well studied, virtually nothing is known about the disassembly process. In this study, we have used super-resolution SIM imaging to monitor pairs of fluorescently tagged divisome proteins as they depart from the division septum. These simple binary comparisons indicated that disassembly occurs in a coordinated process that consists of at least five steps: [FtsZ, ZapA] ⇒ [ZipA, FtsA] ⇒ [FtsL, FtsQ] ⇒ [FtsI, FtsN] ⇒ [FtsN]. This sequence of events is remarkably similar to the assembly process, indicating that disassembly follows a first-in, first-out principle. A secondary observation from these binary comparisons was that FtsZ and FtsN formed division rings that were spatially separated throughout the division process. Thus the data indicate that the divisome structure can be visualized as two concentric rings; a proto-ring containing FtsZ and an FtsN-ring. PMID:27096604

  5. Ligand sensitized luminescence of uranyl by benzoic acid in acetonitrile medium: A new luminescent uranyl benzoate specie

    NASA Astrophysics Data System (ADS)

    Kumar, Satendra; Maji, S.; Joseph, M.; Sankaran, K.

    2015-03-01

    Benzoic acid (BA) is shown to sensitize and enhance the luminescence of uranyl ion in acetonitrile medium. Luminescence spectra and especially UV-Vis spectroscopy studies reveal the formation of tri benzoate complex of uranyl i.e. [UO2(C6H5COO)3]- which is highly luminescent. In particular, three sharp bands at 431, 443, 461 nm of absorption spectra provides evidence for tri benzoate specie of uranyl in acetonitrile medium. The luminescence lifetime of uranyl in this complex is 68 μs which is much more compared to the lifetime of uncomplexed uranyl (20 μs) in acetonitrile medium. In contrary to aqueous medium where uranyl benzoate forms 1:1 and 1:2 species, spectroscopic data reveal formation of 1:3 complex in acetonitrile medium. Addition of water to acetonitrile results in decrease of luminescence intensity of this specie and the luminescence features implode at 20% (v/v) of water content. For the first time, to the best of our knowledge, the existence of [UO2(C6H5COO)3]- specie in acetonitrile is reported. Mechanism of luminescence enhancement is discussed.

  6. Ligand sensitized luminescence of uranyl by benzoic acid in acetonitrile medium: a new luminescent uranyl benzoate specie.

    PubMed

    Kumar, Satendra; Maji, S; Joseph, M; Sankaran, K

    2015-03-01

    Benzoic acid (BA) is shown to sensitize and enhance the luminescence of uranyl ion in acetonitrile medium. Luminescence spectra and especially UV-Vis spectroscopy studies reveal the formation of tri benzoate complex of uranyl i.e. [UO2(C6H5COO)3](-) which is highly luminescent. In particular, three sharp bands at 431, 443, 461nm of absorption spectra provides evidence for tri benzoate specie of uranyl in acetonitrile medium. The luminescence lifetime of uranyl in this complex is 68μs which is much more compared to the lifetime of uncomplexed uranyl (20μs) in acetonitrile medium. In contrary to aqueous medium where uranyl benzoate forms 1:1 and 1:2 species, spectroscopic data reveal formation of 1:3 complex in acetonitrile medium. Addition of water to acetonitrile results in decrease of luminescence intensity of this specie and the luminescence features implode at 20% (v/v) of water content. For the first time, to the best of our knowledge, the existence of [UO2(C6H5COO)3](-) specie in acetonitrile is reported. Mechanism of luminescence enhancement is discussed. PMID:25528510

  7. Reactivity of the "yl"-bond in uranyl(VI) complexes. 1. Rates and mechanisms for the exchange between the trans-dioxo oxygen atoms in (UO2)2(OH)2 2+ and mononuclear UO2(OH)n 2-n complexes with solvent water.

    PubMed

    Szabó, Zoltan; Grenthe, Ingmar

    2007-10-29

    The stoichiometric mechanism, rate constant, and activation parameters for the exchange of the "yl"-oxygen atoms in the dioxo uranium(VI) ion with solvent water have been studied using 17O NMR spectroscopy. The experimental rate equation, (-->)v= k(2obs)[UO2(2+)]tot2/[H+]2, is consistent with a mechanism where the first step is a rapid equilibrium 2U(17)O2(2+) + 2H2O<==>(U(17)O2)2(OH)2(2+) + 2H+, followed by the rate-determining step (U(17)O2)2(OH)2(2+) + H2O<==>(UO2)2*(OH)2(2+) + H2(17)O, where the back reaction can be neglected because the (17)O enrichment in the water is much lower than in the uranyl ion. This mechanism results in the following rate equation (-->)v= d[(UO2)2(OH)2(2+)]/dt = k(2,2)[(UO2)2(OH)2(2+)] = k(2,2*)beta(2,2)[UO2(2+)]2/[H + ]2; with k(2,2) = (1.88 +/- 0.22) x 10(4) h(-1), corresponding to a half-life of 0.13 s, and the activation parameters DeltaH++ = 119 +/- 13 kJ mol-1 and DeltaS++ = 81 +/- 44 J mol(-1) K(-1). *Beta(2,)2 is the equilibrium constant for the reaction 2UO2(2+) + 2H2O<==>(UO2)2(OH)2(2+) + 2H+. The experimental data show that there is no measurable exchange of the "yl"-oxygen in UO2(2+), UO2(OH)+, and UO2(OH)4(2-)/ UO2(OH)5(3-), indicating that "yl"-exchange only takes place in polynuclear hydroxide complexes. There is no "yl"-exchange in the ternary complex (UO2)2(mu-OH)2(F)2(oxalate)2(4-), indicating that it is also necessary to have coordinated water in the first coordination sphere of the binuclear complex, for exchange to take place. The very large increase in lability of the "yl"-bonds in (UO2)2(OH)2(2+) as compared to those of the other species is presumably a result of proton transfer from coordinated water to the "yl"-oxygen, followed by a rapid exchange of the resulting OH group with the water solvent. "Yl"-exchange through photochemical mediation is well-known for the uranyl(VI) aquo ion. We noted that there was no photochemical exchange in UO2(CO3)3(4-), whereas there was a slow exchange or photo reduction in the

  8. SERS detection of uranyl using functionalized gold nanostars promoted by nanoparticle shape and size.

    PubMed

    Lu, Grace; Forbes, Tori Z; Haes, Amanda J

    2016-08-15

    The radius of curvature of gold (Au) nanostar tips but not the overall particle dimensions can be used for understanding the large and quantitative surface-enhanced Raman scattering (SERS) signal of the uranyl (UO2)(2+) moiety. The engineered roughness of the Au nanostar architecture and the distance between the gold surface and uranyl cations are promoted using carboxylic acid terminated alkanethiols containing 2, 5, and 10 methylene groups. By systematically varying the self-assembled monolayer (SAM) thickness with these molecules, the localized surface plasmon resonance (LSPR) spectral properties are used to quantify the SAM layer thickness and to promote uranyl coordination to the Au nanostars in neutral aqueous solutions. Successful uranyl detection is demonstrated for all three functionalized Au nanostar samples as indicated by enhanced signals and red-shifts in the symmetric U(vi)-O stretch. Quantitative uranyl detection is achieved by evaluating the integrated area of these bands in the uranyl fingerprint window. By varying the concentration of uranyl, similar free energies of adsorption are observed for the three carboxylic acid terminated functionalized Au nanostar samples indicating similar coordination to uranyl, but the SERS signals scale inversely with the alkanethiol layer thickness. This distance dependence follows previously established models assuming that roughness features associated with the radius of curvature of the tips are considered. These results indicate that SERS signals using functionalized Au nanostar substrates can provide quantitative detection of small molecules and that the tip architecture plays an important role in understanding the resulting SERS intensities. PMID:27326897

  9. Uranyl incorporation in natural calcite.

    SciTech Connect

    Kelly, S. D.; Newville, M. G.; Cheng, L.; Kemner, K. M.; Sutton, S. R.; Fenter, P.; Sturchio, N. C.; Spotl, C.; Environmental Research; Univ. of Chicago; Univ. of Illiois at Chicago; Univ. of Innsbruck

    2003-01-01

    The occurrence of trace amounts of uranyl in natural calcite has posed a long-standing problem in crystal chemistry because of speculation that the size and shape of the uranyl ion may preclude its incorporation in a stable lattice position in calcite. This also defines an important environmental problem because of its bearing on the transport and sequestration of uranyl released from nuclear facilities and uranium mining operations. Calcite is a nearly ubiquitous mineral in soils and groundwater aquifers. X-ray absorption spectroscopy and X-ray fluorescence microprobe studies of uranium in relatively U-rich {approx}13700-year-old calcite from a speleothem in northernmost Italy indicate substitution of uranyl for a calcium and two adjacent carbonate ions in calcite. These new data imply that uranyl has a stable lattice position in natural calcite, indicating that it may be reliably sequestered in calcite over long time scales.

  10. Recent advances in nanoparticle carriers for coordination complexes.

    PubMed

    Sato, Mariana Rillo; da Silva, Patricia Bento; de Souza, Rodrigo Alves; dos Santos, Karen Cristina; Chorilli, Marlus

    2015-01-01

    Coordination compounds are substances in which a central metal atom is bonded to nonmetal atoms, or groups of atoms, called ligands. Examples include vitamin B12, hemoglobin, chlorophyll, dyes and pigments, as well as catalysts used in organic synthesis. Coordination compounds have received much attention in recent years. This interest was prompted by the discovery that several coordination compounds exhibit activity against bacteria, fungi and cancer. Some coordination compounds are not in clinical use, because of poor water solubility. Because they are unable to cross the lipid membranes of cells, bioavailability and efficacy are low. Some researchers have applied nanotechnology to coordination compounds, hoping to reduce the number of doses required and the severity of side effects, and also to improve biological activity. Nanotechnology can deliver active components in sufficient concentrations throughout treatment, guiding it to the desired location of action; conventional treatments do not meet these requirements. In this study we review some drug delivery systems based on nanotechnology, such as microemulsions (MEs), cyclodextrin (CD), polymeric nanoparticles (PN), solid lipid nanoparticles (SLNs), nanostructured lipid carriers (NLCs), magnetic and gold nanoparticles (MNPs / AuNPs) and liquid crystalline systems (LC), and coordination compounds. PMID:25579344

  11. Uranyl extraction by N,N-dialkylamide ligands studied using static and dynamic DFT simulations.

    PubMed

    Sieffert, Nicolas; Wipff, Georges

    2015-02-14

    We report DFT static and dynamic studies on uranyl complexes [UO(2)(NO(3))x(H(2)O)(y)L(z)](2-x) involved in the uranyl extraction from water to an "oil" phase (hexane) by an amide ligand L (N,N-dimethylacetamide). Static DFT results "in solution" (continuum SMD models for water and hexane) predict that the stepwise formation of [UO(2)(NO(3))(2)L(2)] from the UO(2)(H(2)O)(5)(2+) species is energetically favourable, and allow us to compare cis/trans isomers of penta- and hexa-coordinated complexes and key intermediates in the two solvents. DFT-MD simulations of [UO(2)(NO(3))(2)L(2)], [UO(2)(NO(3))(2)(H(2)O)L(2)], and [UO(2)(NO(3))(H(2)O)L(2)](+) species in explicit solvent environments (water, hexane, or the water/hexane interface) represented at the MM or full-DFT level reveal a versatile solvent dependent binding mode of nitrates, also evidenced by metadynamics simulations. In water and at the interface, the latter exchange from bi- to monodentate, via in plane rotational motions in some cases. Remarkably, structures of complexes at the interface are more "water-like" than gas phase- or hexane-like. Thus, the order of U-O(NO(3))/U-O(L) bond distances observed in the gas phase (U-O(nit) < U-OL) is inverted at the interface and in water. Overall, the results are consistent with the experimental observation of uranyl extraction from nitric acid solutions by amide analogues (bearing "fatty" substituents), and allow us to propose possible extraction mechanisms, involving complexation of L "right at the interface". They also point to the importance of the solvent environment and the dynamics on the structure and stability of the complexes. PMID:25412447

  12. Tetranuclear Uranyl Polyrotaxanes: Preferred Selectivity toward Uranyl Tetramer for Stabilizing a Flexible Polyrotaxane Chain Exhibiting Weakened Supramolecular Inclusion.

    PubMed

    Mei, Lei; Wang, Lin; Liu, Cai-ming; Zhao, Yu-liang; Chai, Zhi-fang; Shi, Wei-qun

    2015-07-01

    Introduction of mechanically interlocked components into actinide-based metal-organic materials such as polyrotaxanes will generate an entirely new type of inorganic-organic hybrid materials showing more supramolecular encapsulation-based dynamics. In this work, tetranuclear uranyl-directed polyrotaxanes (UO2 )4 O2 -C5A3-CB6 (1) and (UO2 )4 O2 -C6A3-CB6 (2), which are the first actinide pseudorotaxanes with high-nuclearity uranium centers, were obtained through systematic extension of the string spacer in pseudorotaxane ligands from 1,4-butylene (C4) to 1,5-pentylene (C5) and 1,6-hexylene (C6). Both of the as-synthesized tetranuclear uranyl polyrotaxanes were structurally characterized and analyzed. Considering the structure of UO2 -C4A3-CB6 and the 1,4-butylene string spacer, the preference for the uranyl tetramer may be related to the configurational inversion of the pseudorotaxane ligands from trans mode to cis mode on coordination to the uranyl center. Detailed structural analysis suggests that the length of the stretched string molecules for CB6-encapsulated pseudorotaxanes has remarkable effect on the supramolecular inclusion interactions and the configurations of pseudorotaxanes, and should be responsible for the configurational inversion of pseudorotaxane spacers and subsequent distinct changes of the uranyl building units and geometric structures. PMID:26036243

  13. Barium uranyl diphosphonates

    SciTech Connect

    Nelson, Anna-Gay D.; Alekseev, Evgeny V.; Ewing, Rodney C.; Albrecht-Schmitt, Thomas E.

    2012-08-15

    Three Ba{sup 2+}/UO{sub 2}{sup 2+} methylenediphosphonates have been prepared from mild hydrothermal treatment of uranium trioxide, methylendiphosphonic acid (C1P2) with barium hydroxide octahydrate, barium iodate monohydrate, and small aliquots of HF at 200 Degree-Sign C. These compounds, Ba[UO{sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{center_dot}1.4H{sub 2}O (Ba-1), Ba{sub 3}[(UO{sub 2}){sub 4}(CH{sub 2}(PO{sub 3}){sub 2}){sub 2}F{sub 6}]{center_dot}6H{sub 2}O (Ba-2), and Ba{sub 2}[(UO{sub 2}){sub 2}(CH{sub 2}(PO{sub 3}){sub 2})F{sub 4}]{center_dot}5.75H{sub 2}O (Ba-3) all adopt layered structures based upon linear uranyl groups and disphosphonate molecules. Ba-2 and Ba-3 are similar in that they both have UO{sub 5}F{sub 2} pentagonal bipyramids that are bridged and chelated by the diphosphonate moiety into a two-dimensional zigzag anionic sheet (Ba-2) and a one-dimensional ribbon anionic chain (Ba-3). Ba-1, has a single crystallographically unique uranium metal center where the C1P2 ligand solely bridges to form [UO{sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{sup 2-} sheets. The interlayer space of the structures is occupied by Ba{sup 2+}, which, along with the fluoride ion, mediates the structure formed and maintains overall charge balance. - Graphical abstract: Illustration of the stacking of the layers in Ba{sub 3}[(UO{sub 2}){sub 4}(CH{sub 2}(PO{sub 3}){sub 2}){sub 2})F{sub 6}]{center_dot}6H{sub 2}O viewed along the c-axis. The structure is constructed from UO{sub 7} pentagonal bipyramidal units, U(1)O{sub 7}=gray, U(2)O{sub 7}=yellow, barium=blue, phosphorus=magenta, fluorine=green, oxygen=red, carbon=black, and hydrogen=light peach. Highlights: Black-Right-Pointing-Pointer The polymerization of the UO{sub 2}{sup 2+} sites to form uranyl dimers leads to structural variations in compounds. Black-Right-Pointing-Pointer Barium cations stitch uranyl diphosphonate anionic layers together, and help mediate structure formation. Black-Right-Pointing-Pointer HF acts as both a

  14. Distributed detection of communities in complex networks using synthetic coordinates

    NASA Astrophysics Data System (ADS)

    Papadakis, H.; Panagiotakis, C.; Fragopoulou, P.

    2014-03-01

    Various applications like finding Web communities, detecting the structure of social networks, and even analyzing a graph’s structure to uncover Internet attacks are just some of the applications for which community detection is important. In this paper, we propose an algorithm that finds the entire community structure of a network, on the basis of local interactions between neighboring nodes and an unsupervised distributed hierarchical clustering algorithm. The novelty of the proposed approach, named SCCD (standing for synthetic coordinate community detection), lies in the fact that the algorithm is based on the use of Vivaldi synthetic network coordinates computed by a distributed algorithm. The current paper not only presents an efficient distributed community finding algorithm, but also demonstrates that synthetic network coordinates could be used to derive efficient solutions to a variety of problems. Experimental results and comparisons with other methods from the literature are presented for a variety of benchmark graphs with known community structure, derived from varying a number of graph parameters and real data set graphs. The experimental results and comparisons to existing methods with similar computation cost on real and synthetic data sets demonstrate the high performance and robustness of the proposed scheme.

  15. Coordinating complex decision support activities across distributed applications

    NASA Technical Reports Server (NTRS)

    Adler, Richard M.

    1994-01-01

    Knowledge-based technologies have been applied successfully to automate planning and scheduling in many problem domains. Automation of decision support can be increased further by integrating task-specific applications with supporting database systems, and by coordinating interactions between such tools to facilitate collaborative activities. Unfortunately, the technical obstacles that must be overcome to achieve this vision of transparent, cooperative problem-solving are daunting. Intelligent decision support tools are typically developed for standalone use, rely on incompatible, task-specific representational models and application programming interfaces (API's), and run on heterogeneous computing platforms. Getting such applications to interact freely calls for platform independent capabilities for distributed communication, as well as tools for mapping information across disparate representations. Symbiotics is developing a layered set of software tools (called NetWorks! for integrating and coordinating heterogeneous distributed applications. he top layer of tools consists of an extensible set of generic, programmable coordination services. Developers access these services via high-level API's to implement the desired interactions between distributed applications.

  16. Composition for detecting uranyl

    DOEpatents

    Baylor, L.C.; Stephens, S.M.

    1994-01-01

    The present invention relates to an indicator composition for use in spectrophotometric detection of a substance in a solution, and a method for making the composition. Useful indicators are sensitive to the particular substance being measured, but are unaffected by the fluid and other chemical species that may be present in the fluid. Optical indicators are used to measure the uranium concentration of process solutions in facilities for extracting uranium from ores, production of nuclear fuels, and reprocessing of irradiated fuels. The composition comprises an organohalide covalently bonded to an indicator for the substance, in such a manner that the product is itself an indicator that provides increased spectral resolution for detecting the substance. The indicator is preferably arsenazo III and the organohalide is preferably cyanuric chloride. These form a composition that is ideally suited for detecting uranyl.

  17. Role of the sodium-dependent phosphate co-transporters and of the phosphate complexes of uranyl in the cytotoxicity of uranium in LLC-PK{sub 1} cells

    SciTech Connect

    Muller, D. . E-mail: dany.muller@kcl.ac.uk; Houpert, P. . E-mail: pascale.houpert@irsn.fr; Cambar, J. . E-mail: marie-helene.napoli@cea.fr

    2006-07-15

    Although uranium is a well-characterized nephrotoxic agent, very little is known at the cellular and molecular level about the mechanisms underlying the uptake and toxicity of this element in proximal tubule cells. The aim of this study was thus to characterize the species of uranium that are responsible for its cytotoxicity and define the mechanism which is involved in the uptake of the cytotoxic fraction of uranium using two cell lines derived from kidney proximal (LLC-PK{sub 1}) and distal (MDCK) tubule as in vitro models. Treatment of LLC-PK{sub 1} cells with colchicine, cytochalasin D, concanavalin A and PMA increased the sodium-dependent phosphate co-transport and the cytotoxicity of uranium. On the contrary, replacement of the extra-cellular sodium with N-methyl-D-glucamine highly reduced the transport of phosphate and the cytotoxic effect of uranium. Uranium cytotoxicity was also dependent upon the extra-cellular concentration of phosphate and decreased in a concentration-dependent manner by 0.1-10 mM phosphonoformic acid, a competitive inhibitor of phosphate uptake. Consistent with these observations, over-expression of the rat proximal tubule sodium-dependent phosphate co-transporter NaPi-IIa in stably transfected MDCK cells significantly increased the cytotoxicity of uranium, and computer modeling of uranium speciation showed that uranium cytotoxicity was directly dependent on the presence of the phosphate complexes of uranyl UO{sub 2}(PO{sub 4}){sup -} and UO{sub 2}(HPO{sub 4}){sub aq}. Taken together, these data suggest that the cytotoxic fraction of uranium is a phosphate complex of uranyl whose uptake is mediated by a sodium-dependent phosphate co-transporter system.

  18. Equilibrium between Different Coordination Geometries in Oxidovanadium(IV) Complexes

    ERIC Educational Resources Information Center

    Ugone, Valeria; Garribba, Eugenio; Micera, Giovanni; Sanna, Daniele

    2015-01-01

    In this laboratory activity, the equilibrium between square pyramidal and octahedral V(IV)O[superscript 2+] complexes is described. We propose a set of experiments to synthesize and characterize two types of V(IV)O[superscript 2+] complexes. The experiment allows great flexibility and may be effectively used at a variety of levels and the activity…

  19. Novel uranyl(VI) complexes incorporating propylene-bridged salen-type N2O2-ligands: a structural and computational approach.

    PubMed

    Azam, Mohammad; Al-Resayes, Saud I; Velmurugan, Gunasekaran; Venuvanalingam, Ponnambalam; Wagler, Jörg; Kroke, Edwin

    2015-01-14

    The synthesis of the tetradentate dianionic ligand, H2L (2,2'-(1E,1'E)-(2,2-dimethylpropane-1,3-dyl)bis(azanylylidene)bis(methanylylidene)diphenol), from 2,2-dimethyl-1,3-diaminopropane and its reaction with UO2(CH3COO)2·2H2O in a 1:1 molar ratio in methanol to produce the complex [UO2(L)(CH3OH)] are reported. The isolated compounds have been characterized by elemental analysis, ionization mass spectrometry (ESI-MS), UV/Vis, FT-IR, (1)H- and (13)C-NMR, DEPT-135 spectroscopy, TGA and single-crystal X-ray diffraction. As shown by X-ray crystallography, the coordination geometry around the uranium centre is distorted pentagonal bipyramidal with two imine nitrogen atoms, two phenolic oxygen atoms and one methanol O atom occupying equatorial sites, together with two axial oxo groups. To obtain insights into the structure and spectral properties of the studied complex, density functional theory (DFT) and time dependent density functional theory (TD-DFT) calculations have been carried out. The computed results show that LUMO of the complex is featured with uranium f orbital character. TD-DFT results indicate that the complex displays two intense bands and one weak charge transfer band. The charge transfer band is primarily due to HOMO → LUMO (53%). Two intense bands have main contributions from HOMO-2 → LUMO (81%) and HOMO-3 → LUMO (77%) transitions, respectively. TD-DFT results indicate that the complex displays the charge transfer band primarily due to HOMO → LUMO (53%) and other two charge transfer bands have main contributions from HOMO-2 → LUMO (81%), HOMO-3 → LUMO (77%) transitions, respectively. NBO analysis reveals that the ground state of the complex is mainly stabilized by n→n* interaction. EDA analysis reveals that the interaction existing between the ligand and other parts of the complex is mainly electrostatic in nature. PMID:25380389

  20. Emergent complexity matching in interpersonal coordination: Local dynamics and global variability.

    PubMed

    Fine, Justin M; Likens, Aaron D; Amazeen, Eric L; Amazeen, Polemnia G

    2015-06-01

    Rhythmic coordination with stimuli and other people's movements containing variable or unpredictable fluctuations might involve distinct processes: detecting the fluctuation structure and tuning to or matching the structure's temporal complexity. This framework predicts that global tuning and local parameter adjustments (e.g., position, velocity or phase) can operate independently during coordination (Marmelat & Delignières, 2012). Alternatively, we propose that complexity matching is a result of local phase adjustments during coordination (Delignières & Marmelat, 2014; Torre, Varlet, & Marmelat, 2013). The current study examined this relationship in a rhythmic interpersonal coordination task. Dyads coordinated swinging pendulums that differed in their uncoupled frequencies (detuning). We predicted that frequency detuning would require increased local corrections to maintain the intended phase pattern (in phase). This was expected to yield a relative phase shift accompanied by a change in period complexity and matching. Experimental data and numerical modeling of the pendulum dynamics confirmed our predictions. Increased relative phase shifts occurred simultaneously with increased dissociation between individuals' movement period complexity. This provided evidence that global complexity matching is intricately linked to local movement adjustments and is not a distinct coordination mechanism. These findings are considered with respect to dynamical and computational approaches to interpersonal coordination. PMID:25798782

  1. Human Balance System: A Complex Coordination of Central and Peripheral Systems

    MedlinePlus

    ... 8428 · INFO @ VESTIBULAR . ORG · WWW . VESTIBULAR . ORG The Human Balance System — A Complex Coordination of Central and ... support. 1 A properly functioning balance system allows humans to see clearly while moving, identify orientation with ...

  2. Proton exchange in acid-base complexes induced by reaction coordinates with heavy atom motions

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Taghikhani, Mahdi

    2012-06-01

    We extend previous work on nitric acid-ammonia and nitric acid-alkylamine complexes to illustrate that proton exchange reaction coordinates involve the rocking motion of the base moiety in many double hydrogen-bonded gas phase strong acid-strong base complexes. The complexes studied involve the biologically and atmospherically relevant glycine, formic, acetic, propionic, and sulfuric acids with ammonia/alkylamine bases. In these complexes, the magnitude of the imaginary frequencies associated with the proton exchange transition states are <400 cm-1. This contrasts with widely studied proton exchange reactions between symmetric carboxylic acid dimers or asymmetric DNA base pair and their analogs where the reaction coordinate is localized in proton motions and the magnitude of the imaginary frequencies for the transition states are >1100 cm-1. Calculations on complexes of these acids with water are performed for comparison. Variations of normal vibration modes along the reaction coordinate in the complexes are described.

  3. Facile Synthesis of Functionalized Carbene Metal Complexes from Coordinated Isonitriles.

    PubMed

    Lothschütz, Christian; Wurm, Thomas; Zeiler, Anna; Freiherr V Falkenhausen, Alexander; Rudolph, Matthias; Rominger, Frank; Hashmi, A Stephen K

    2016-02-01

    The scope and limitations of the isonitrile-based NHC template synthesis were investigated with a series of precursors containing a nucleophilic amine in combination with tethered electrophiles. In the case of alkynes and phosphonic esters as electrophiles no ring closure was observed and new functionalized NAC gold complexes were obtained. By the use of unsaturated esters and phosphonic esters as Michael acceptors in the amine precursors, ester-modified gold and palladium NHC complexes were accessible in high efficiency. PMID:26033484

  4. Synthesis and Characterization of Templated Ion Exchange Resins for the Selective Complexation of Actinide Ions

    SciTech Connect

    Uy, O. Manual

    2001-03-01

    The purpose of this research is to develop a polymeric extractant for the selective complexation of uranyl ions (and subsequently other actinyl and actinide ions) from aqueous solutions (lakes, streams, waste tanks and even body fluids). Chemical insights into what makes a good complexation site will be used to synthesize reagents tailor-made for the complexation of uranyl and other actinide ions. These insights, derived from studies of molecular recognition include ion coordination number and geometry, ionic size and ionic shape, as well as ion to ligand thermodynamic affinity. Selectivity for a specific actinide ion will be obtained by providing the polymers with cavities lined with complexing ligands so arranged as to match the charge, coordination number, coordination geometry, and size of the actinide metal ion. These cavity-containing polymers will be produced by using a specific ion (or surrogate) as a template around which monomeric complexing ligands will be polymerized. The complexing ligands will be ones containing functional groups known to form stable complexes with a specific ion and less stable complexes with other cations. Prior investigator's approaches for making templated resins for metal ions have had marginal success. We have extended and amended these methodologies in our work with Pb(II) and uranyl ion, by changing the order of the steps, by the inclusion of sonication, by using higher complex loading, and the selection of functional groups with better complexation constants. This has resulted in significant improvements to selectivity. The unusual shape of the uranyl ion suggests that this approach will result in even greater selectivities than already observed for Pb(II). Preliminary data obtained for uranyl templated polymers shows unprecedented selectivity and has resulted in the first ion selective electrode for uranyl ion.

  5. Understanding the bonding nature of uranyl ion and functionalized graphene: a theoretical study.

    PubMed

    Wu, Qun-Yan; Lan, Jian-Hui; Wang, Cong-Zhi; Xiao, Cheng-Liang; Zhao, Yu-Liang; Wei, Yue-Zhou; Chai, Zhi-Fang; Shi, Wei-Qun

    2014-03-20

    Studying the bonding nature of uranyl ion and graphene oxide (GO) is very important for understanding the mechanism of the removal of uranium from radioactive wastewater with GO-based materials. We have optimized 22 complexes between uranyl ion and GO applying density functional theory (DFT) combined with quasi-relativistic small-core pseudopotentials. The studied oxygen-containing functional groups include hydroxyl, carboxyl, amido, and dimethylformamide. It is observed that the distances between uranium atoms and oxygen atoms of GO (U-OG) are shorter in the anionic GO complexes (uranyl/GO(-/2-)) compared to the neutral GO ones (uranyl/GO). The formation of hydrogen bonds in the uranyl/GO(-/2-) complexes can enhance the binding ability of anionic GO toward uranyl ions. Furthermore, the thermodynamic calculations show that the changes of the Gibbs free energies in solution are relatively more negative for complexation reactions concerning the hydroxyl and carboxyl functionalized anionic GO complexes. Therefore, both the geometries and thermodynamic energies indicate that the binding abilities of uranyl ions toward GO modified by hydroxyl and carboxyl groups are much stronger compared to those by amido and dimethylformamide groups. This study can provide insights for designing new nanomaterials that can efficiently remove radionuclides from radioactive wastewater. PMID:24592814

  6. Two-coordinate Fe⁰ and Co⁰ complexes supported by cyclic (alkyl)(amino)carbenes.

    PubMed

    Ung, Gaël; Rittle, Jonathan; Soleilhavoup, Michele; Bertrand, Guy; Peters, Jonas C

    2014-08-01

    The CAAC [CAAC=cyclic (alkyl)(amino)carbene] family of carbene ligands have shown promise in stabilizing unusually low-coordination number transition-metal complexes in low formal oxidation states. Here we extend this narrative by demonstrating their utility in affording access to the first examples of two-coordinate formal Fe(0) and Co(0) [(CAAC)2M] complexes, prepared by reduction of their corresponding two-coordinate cationic Fe(I) and Co(I) precursors. The stability of these species arises from the strong σ-donating and π-accepting properties of the supporting CAAC ligands, in addition to steric protection. PMID:24953342

  7. An Extensible Space-Based Coordination Approach for Modeling Complex Patterns in Large Systems

    NASA Astrophysics Data System (ADS)

    Kühn, Eva; Mordinyi, Richard; Schreiber, Christian

    Coordination is frequently associated with shared data spaces employing Linda coordination. But in practice, communication between parallel and distributed processes is carried out with message exchange patterns. What, actually, do shared data spaces contribute beyond these? In this paper we present a formal representation for a definition of shared spaces by introducing an "extensible tuple model", based on existing research on Linda coordination, some Linda extensions, and virtual shared memory. The main enhancements of the extensible tuple model comprise: means for structuring of spaces, Internet- compatible addressing of resources, more powerful coordination capabilities, a clear separation of user data and coordination information, support of symmetric peer application architectures, and extensibility through programmable aspects. The advantages of the extensible tuple model (XTM) are that it allows for a specification of complex coordination patterns.

  8. The coordination and atom transfer chemistry of titanium porphyrin complexes

    SciTech Connect

    Hays, J.A.

    1993-11-05

    Preparation, characterization, and reactivity of ({eta}{sup 2}- alkyne)(meso-tetratolylpoprphrinato)titanium(II) complexes are described, along with inetermetal oxygen atom transfer reactions involving Ti(IV) and Ti(III) porphyrin complexes. The {eta}{sup 2}- alkyne complexes are prepared by reaction of (TTP)TiCl{sub 2} with LiAlH{sub 4} in presence of alkyne. Structure of (OEP)Ti({eta}{sup 2}-Ph-C{triple_bond}C-Ph) (OEP=octaethylporphryin) was determined by XRD. The compounds undergo simple substitution to displace the alkyne and produce doubly substituted complexes. Structure of (TTP)Ti(4-picoline){sub 2} was also determined by XRD. Reaction of (TTP)Ti{double_bond}O with (OEP)Ti-Cl yields intermetal O/Cl exchange, which is a one-electron redox process mediated by O atom transfer. Also a zero-electron redox process mediated by atom transfer is observed when (TTP)TiCl{sub 2} is reacted with (OEP)Ti{double_bond}O.

  9. Supramolecular coordination and antimicrobial activities of constructed mixed ligand complexes

    NASA Astrophysics Data System (ADS)

    El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Abou-Dobara, M. I.; Seyam, H. A.

    2013-03-01

    A novel series of copper(II) and palladium(II) with 4-derivatives benzaldehyde pyrazolone (Ln) were synthesized. The mixed ligand complexes were prepared by using 1,10-phenanthroline (Phen) as second ligand. The structure of these complexes was identified and confirm by elemental analysis, molar conductivity, UV-Vis, IR and 1H NMR spectroscopy and magnetic moment measurements as well as thermal analysis. The ligand behaves as a neutral bidentate ligand through ON donor sites. ESR spectra show the simultaneous presence of a planar trans and a nearly planar cis isomers in the 1:2 ratio for all N,O complexes [Cu(Ln)2]Cl2ṡ2H2O. Schiff bases (Ln) were tested against bacterial species; namely two Gram positive bacteria (Staphylococcus aureus and Bacillus cereus) and two Gram negative bacteria (Escherichia coli and Klebsiella pneumoniae) and fungal species (Aspergillus niger, Fusarium oxysporium, Penicillium italicum and Alternaria alternata). The tested compounds have antibacterial activity against S. aureus, B. cereus and K. pneumoniae.

  10. Solid state and aqueous behavior of uranyl peroxide cage clusters

    NASA Astrophysics Data System (ADS)

    Pellegrini, Kristi Lynn

    Uranyl peroxide cage clusters include a large family of more than 50 published clusters of a variety of sizes, which can incorporate various ligands including pyrophosphate and oxalate. Previous studies have reported that uranyl clusters can be used as a method to separate uranium from a solid matrix, with potential applications in reprocessing of irradiated nuclear fuel. Because of the potential applications of these novel structures in an advanced nuclear fuel cycle and their likely presence in areas of contamination, it is important to understand their behavior in both solid state and aqueous systems, including complex environments where other ions are present. In this thesis, I examine the aqueous behavior of U24Pp 12, as well as aqueous cluster systems with added mono-, di-, and trivalent cations. The resulting solutions were analyzed using dynamic light scattering and ultra-small angle X-ray scattering to evaluate the species in solution. Precipitates of these systems were analyzed using powder X-ray diffraction, X-ray fluorescence spectrometry, and Raman spectroscopy. The results of these analyses demonstrate the importance of cation size, charge, and concentration of added cations on the aqueous behavior of uranium macroions. Specifically, aggregates of various sizes and shapes form rapidly upon addition of cations, and in some cases these aggregates appear to precipitate into an X-ray amorphous material that still contains U24Pp12 clusters. In addition, I probe aggregation of U24Pp12 and U60, another uranyl peroxide cage cluster, in mixed solvent water-alcohol systems. The aggregation of uranyl clusters in water-alcohol systems is a result of hydrogen bonding with polar organic molecules and the reduction of the dielectric constant of the system. Studies of aggregation of uranyl clusters also allow for comparison between the newer uranyl polyoxometalate family and century-old transition metal polyoxometalates. To complement the solution studies of uranyl

  11. Barium uranyl diphosphonates

    NASA Astrophysics Data System (ADS)

    Nelson, Anna-Gay D.; Alekseev, Evgeny V.; Ewing, Rodney C.; Albrecht-Schmitt, Thomas E.

    2012-08-01

    Three Ba2+/UO22+ methylenediphosphonates have been prepared from mild hydrothermal treatment of uranium trioxide, methylendiphosphonic acid (C1P2) with barium hydroxide octahydrate, barium iodate monohydrate, and small aliquots of HF at 200 °C. These compounds, Ba[UO2[CH2(PO3)2]·1.4H2O (Ba-1), Ba3[(UO2)4(CH2(PO3)2)2F6]·6H2O (Ba-2), and Ba2[(UO2)2(CH2(PO3)2)F4]·5.75H2O (Ba-3) all adopt layered structures based upon linear uranyl groups and disphosphonate molecules. Ba-2 and Ba-3 are similar in that they both have UO5F2 pentagonal bipyramids that are bridged and chelated by the diphosphonate moiety into a two-dimensional zigzag anionic sheet (Ba-2) and a one-dimensional ribbon anionic chain (Ba-3). Ba-1, has a single crystallographically unique uranium metal center where the C1P2 ligand solely bridges to form [UO2[CH2(PO3)2]2- sheets. The interlayer space of the structures is occupied by Ba2+, which, along with the fluoride ion, mediates the structure formed and maintains overall charge balance.

  12. Insertion of Trivalent Lanthanides into Uranyl Vanadate Layers and Frameworks.

    PubMed

    Wang, Yaxing; Yin, Xuemiao; Zhao, Yanyan; Gao, Yang; Chen, Lanhua; Liu, Zhiyong; Sheng, Daopeng; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2015-09-01

    Two new uranyl vanadates have been prepared from hydrothermal reactions and structurally characterized by single-crystal X-ray diffraction. The structure of (H3O)UO2VO4 (UVO-1) consists of anionic layers containing UO2(2+) pentagonal bipyramids coordinated by edge-sharing VO5 square pyramids, with the charge balanced by interlaminar H3O(+) cations. Vanadium in (UO2)3(VO4)2(H2O)3 (UVO-2) exists as monomeric VO4 tetrahedra coordinating to UO2(2+) pentagonal bipyramids, forming a 3D uranyl(VI) vanadate framework. Similar reactions with the addition of Ln(NO3)3 (Ln = Nd, Eu) afford the three heterobimetallic lanthanide uranyl vanadate frameworks Nd(UO2)3(VO4)3(H2O)11 (NdUVO-1), Eu(UO2)3(VO4)3(H2O)10 (EuUVO-1), and Eu2(UO2)12(VO4)10(H2O)24 (EuUVO-2). In NdUVO-1 and EuUVO-1, Ln(3+) cations are inserted into the interlayer space of UVO-1 substituting for H3O(+) and further bridging adjacent layers into 3D frameworks. Similarly, EuUVO-2 adopts the same sheet topology as UVO-2, with Eu(3+) ions replacing some of the interlayer uranyl ions in UVO-2. Our work has demonstrated that uranyl vanadate extended structures are excellent hosts for further incorporation of trivalent lanthanide/actinide cations and has provided a new way to create new heterobimetallic 4f-5f and 5f-5f compounds. PMID:26292148

  13. Synthesis, characterization, and crystal structures of uranyl compounds containing mixed chromium oxidation states

    SciTech Connect

    Unruh, Daniel K.; Quicksall, Andrew; Pressprich, Laura; Stoffer, Megan; Qiu, Jie; Nuzhdin, Kirill; Wu, Weiqiang; Vyushkova, Mariya; Burns, Peter C.

    2012-07-15

    The mixed-valence chromium uranyl compounds Li{sub 5}[(UO{sub 2}){sub 4}(Cr(V)O{sub 5})(Cr(VI)O{sub 4}){sub 4}](H{sub 2}O){sub 17} (1), (Mg(H{sub 2}O){sub 6}){sub 5}[(UO{sub 2}){sub 8}(Cr(V)O{sub 5}){sub 2}(Cr(VI)O{sub 4}){sub 8}] (2) and (NH{sub 4}){sub 5}[(UO{sub 2}){sub 4}(Cr(V)O{sub 5})(Cr(VI)O{sub 4}){sub 2}]H{sub 2}O{sub 11} (3) have been synthesized and characterized. Each contains an identical sheet of cation-centered polyhedra. Central to the connectivity of the sheet are four uranyl pentagonal bipyramids that share some of their equatorial vertices, giving a four-membered ring. The Cr(V) cation located near the center of this ring is coordinated by O atoms in a square pyramidal arrangement. The Cr(VI) is tetrahedrally coordinated by O atoms, and these tetrahedra link the four-membered rings of bipyramids. The mixed-valence nature of the sheet was verified by XANES, an EPR spectrum, and bond-valence analysis. Low-valence cations and H{sub 2}O groups reside between the sheets of uranyl and chromate polyhedra, where they provide linkages between adjacent sheets. - Graphical abstract: Three uranyl chromate compounds contain both pentavalent and hexavalent chromium. The unusual topology of the uranyl chromate sheet contains unusual pentavalent chromium in a square pyramidal coordination environment. Highlights: Black-Right-Pointing-Pointer The first uranyl compounds with mixed Cr valences are reported. Black-Right-Pointing-Pointer A sheet of uranyl polyhedra stabilizes pentavalent chromium. Black-Right-Pointing-Pointer Uranyl and chromate polyhedra form a topologically novel sheet.

  14. Multi-scale modelling of uranyl chloride solutions

    SciTech Connect

    Nguyen, Thanh-Nghi; Duvail, Magali Villard, Arnaud; Dufrêche, Jean-François; Molina, John Jairo; Guilbaud, Philippe

    2015-01-14

    Classical molecular dynamics simulations with explicit polarization have been successfully used to determine the structural and thermodynamic properties of binary aqueous solutions of uranyl chloride (UO{sub 2}Cl{sub 2}). Concentrated aqueous solutions of uranyl chloride have been studied to determine the hydration properties and the ion-ion interactions. The bond distances and the coordination number of the hydrated uranyl are in good agreement with available experimental data. Two stable positions of chloride in the second hydration shell of uranyl have been identified. The UO{sub 2}{sup 2+}-Cl{sup −} association constants have also been calculated using a multi-scale approach. First, the ion-ion potential averaged over the solvent configurations at infinite dilution (McMillan-Mayer potential) was calculated to establish the dissociation/association processes of UO{sub 2}{sup 2+}-Cl{sup −} ion pairs in aqueous solution. Then, the association constant was calculated from this potential. The value we obtained for the association constant is in good agreement with the experimental result (K{sub UO{sub 2Cl{sup +}}} = 1.48 l mol{sup −1}), but the resulting activity coefficient appears to be too low at molar concentration.

  15. Modeling and Simulation of Complex Network Attributes on Coordinating Large Multiagent System

    PubMed Central

    Li, Xiang; Liu, Ming

    2014-01-01

    With the expansion of distributed multiagent systems, traditional coordination strategy becomes a severe bottleneck when the system scales up to hundreds of agents. The key challenge is that in typical large multiagent systems, sparsely distributed agents can only communicate directly with very few others and the network is typically modeled as an adaptive complex network. In this paper, we present simulation testbed CoordSim built to model the coordination of network centric multiagent systems. Based on the token-based strategy, the coordination can be built as a communication decision problem that agents make decisions to target communications and pass them over to the capable agents who will potentially benefit the team most. We have theoretically analyzed that the characters of complex network make a significant difference with both random and intelligent coordination strategies, which may contribute to future multiagent algorithm design. PMID:24955399

  16. Spin-labelled cyclometallated palladium complexes. EPR study of dynamic processes in coordination sphere

    NASA Astrophysics Data System (ADS)

    Kozhanov, K. A.; Bubnov, M. P.; Abakumov, G. A.; Cherkasov, V. K.

    2012-12-01

    New four-, five- and six-coordinated cyclometallated o-semiquinonato palladium complexes were obtained and characterized in solution by EPR. Interaction of square-planar azaphenyl palladium semiquinonate with mono and bidentate phosphane donors leads to formation of five- and six-coordinated adducts. Typical values of HFC constants on apical and basal phosphorouses are observed for such compounds. In one case the reversible addition of tri-phenyl-phosphane was observed. The coordination mode of pincer ligand (bi- or tridentate) in o-semiquinonato pincer complexes depends on the nature of linker between coordinating group and pincer aryl ring. In the case of sbnd CH2sbnd linker five coordinated complexes are formed. The "swing" and "fan" oscillations are observed for these compounds. Complexes with sbnd Osbnd linker are the first examples of compounds with bidentate bonded phosphorous-based pincer ligand. Most of complexes are unstable and decompose during some hours. Only the application of o-semiquinones as spin labels and using the EPR technique made possible to observe and interpret their structure.

  17. Surprising Coordination Geometry Differences in Ce(IV)- and Pu(IV)-Maltol Complexes

    SciTech Connect

    Lawrence Berkeley National Laboratory; Raymond, Kenneth; Szigethy, Geza; Xu, Jide; Gorden, Anne E.V.; Teat, Simon J.; Shuh, David K.; Raymond, Kenneth N.

    2008-02-12

    As part of a study to characterize the detailed coordination behavior of Pu(IV), single crystal X-ray diffraction structures have been determined for Pu(IV) and Ce(IV) complexes with the naturally-occurring ligand maltol (3-hydroxy-2-methyl-pyran-4-one) and its derivative bromomaltol (5-bromo-3-hydroxy-2-methyl-pyran-4-one). Although Ce(IV) is generally accepted as a structural analog for Pu(IV), and the maltol complexes of these two metals are isostructural, the corresponding bromomaltol complexes are strikingly different with respect to ligand orientation about the metal ion: All complexes exhibit trigonal dodecahedral coordination geometry but the Ce(IV)-bromomaltol complex displays an uncommon ligand arrangement not mirrored in the Pu(IV) complex, although the two metal species are generally accepted to be structural analogs.

  18. Scribble1/AP2 complex coordinates NMDA receptor endocytic recycling.

    PubMed

    Piguel, Nicolas H; Fievre, Sabine; Blanc, Jean-Michel; Carta, Mario; Moreau, Maïté M; Moutin, Enora; Pinheiro, Vera L; Medina, Chantal; Ezan, Jerome; Lasvaux, Léa; Loll, François; Durand, Christelle M; Chang, Kai; Petralia, Ronald S; Wenthold, Robert J; Stephenson, F Anne; Vuillard, Laurent; Darbon, Hervé; Perroy, Julie; Mulle, Christophe; Montcouquiol, Mireille; Racca, Claudia; Sans, Nathalie

    2014-10-23

    The appropriate trafficking of glutamate receptors to synapses is crucial for basic synaptic function and synaptic plasticity. It is now accepted that NMDA receptors (NMDARs) internalize and are recycled at the plasma membrane but also exchange between synaptic and extrasynaptic pools; these NMDAR properties are also key to governing synaptic plasticity. Scribble1 is a large PDZ protein required for synaptogenesis and synaptic plasticity. Herein, we show that the level of Scribble1 is regulated in an activity-dependent manner and that Scribble1 controls the number of NMDARs at the plasma membrane. Notably, Scribble1 prevents GluN2A subunits from undergoing lysosomal trafficking and degradation by increasing their recycling to the plasma membrane following NMDAR activation. Finally, we show that a specific YxxR motif on Scribble1 controls these mechanisms through a direct interaction with AP2. Altogether, our findings define a molecular mechanism to control the levels of synaptic NMDARs via Scribble1 complex signaling. PMID:25310985

  19. New water soluble heterometallic complex showing unpredicted coordination modes of EDTA

    NASA Astrophysics Data System (ADS)

    Mudsainiyan, R. K.; Jassal, A. K.; Chawla, S. K.

    2015-10-01

    A mesoporous 3D polymeric complex (I) having formula {[Zr(IV)O-μ3-(EDTA)Fe(III)OH]·H2O}n has been crystallized and characterized by various techniques. Single-crystal X-ray diffraction analysis revealed that complex (I) crystallized in chiral monoclinic space group Cc (space group no. 9) with unexpected coordination modes of EDTA and mixture of two transition metal ions. In this complex, the coordination number of Zr(IV) ion is seven where four carboxylate oxygen atoms, two nitrogen atoms, one oxide atom are coordinating with Zr(IV). Fe(III) is four coordinated and its coordination environment is composed of three different carboxylic oxygen atoms from three different EDTA and one oxygen atom of -OH group. The structure consists of 4-c and 16-c (2-nodal) net with new topology and point symbol for net is (336·454·530)·(36). TGA study and XRPD pattern showed that the coordination polymer is quite stable even after losing water molecule and -OH ion. Quenching behavior in fluorescence of ligand is observed by complexation with transition metal ions is due to n-π* transition. The SEM micrograph shows the morphology of complex (I) exhibits spherical shape with size ranging from 50 to 280 nm. The minimum N2 (SBET=8.7693 m2/g) and a maximum amount of H2 (high surface area=1044.86 m2/g (STP)) could be adsorbed at 77 K. From DLS study, zeta potential is calculated i.e. -7.94 shows the negative charges on the surface of complex. Hirshfeld surface analysis and fingerprint plots revealed influence of weak or non bonding interactions in crystal packing of complex.

  20. Effects of aqueous uranyl speciation on the kinetics of microbial uranium reduction

    NASA Astrophysics Data System (ADS)

    Belli, Keaton M.; DiChristina, Thomas J.; Van Cappellen, Philippe; Taillefert, Martial

    2015-05-01

    The ability to predict the success of the microbial reduction of soluble U(VI) to highly insoluble U(IV) as an in situ bioremediation strategy is complicated by the wide range of geochemical conditions at contaminated sites and the strong influence of aqueous uranyl speciation on the bioavailability and toxicity of U(VI) to metal-reducing bacteria. To determine the effects of aqueous uranyl speciation on uranium bioreduction kinetics, incubations and viability assays with Shewanella putrefaciens strain 200 were conducted over a range of pH and dissolved inorganic carbon (DIC), Ca2+, and Mg2+ concentrations. A speciation-dependent kinetic model was developed to reproduce the observed time series of total dissolved uranium concentration over the range of geochemical conditions tested. The kinetic model yielded the highest rate constant for the reduction of uranyl non-carbonate species (i.e., the 'free' hydrated uranyl ion, uranyl hydroxides, and other minor uranyl complexes), indicating that they represent the most readily reducible fraction of U(VI) despite being the least abundant uranyl species in solution. The presence of DIC, Ca2+, and Mg2+ suppressed the formation of more bioavailable uranyl non-carbonate species and resulted in slower bioreduction rates. At high concentrations of bioavailable U(VI), however, uranium toxicity to S. putrefaciens inhibited bioreduction, and viability assays confirmed that the concentration of non-carbonate uranyl species best predicts the degree of toxicity. The effect of uranium toxicity was accounted for by incorporating the free ion activity model of metal toxicity into the bioreduction rate law. Overall, these results demonstrate that, in the absence of competing terminal electron acceptors, uranium bioreduction kinetics can be predicted over a wide range of geochemical conditions based on the bioavailability and toxicity imparted on U(VI) by solution composition. These findings also imply that the concentration of uranyl non

  1. Adsorption of uranyl species on hydroxylated titanium carbide nanosheet: A first-principles study.

    PubMed

    Zhang, Yu-Juan; Lan, Jian-Hui; Wang, Lin; Wu, Qun-Yan; Wang, Cong-Zhi; Bo, Tao; Chai, Zhi-Fang; Shi, Wei-Qun

    2016-05-01

    In this work, hydroxylated titanium carbide Ti3C2(OH)2, a representative of the two-dimensional transition metal carbides, has been predicted to be an effective adsorbent for uranyl ions in aqueous environments for the first time using density functional theory simulations. The calculations revealed that the uranyl ion can strongly bind with Ti3C2(OH)2 nanosheet in aqueous solution regardless of the presence of anionic ligands such as OH(-), Cl(-) and NO3(-). The bidentate coordination of uranyl to the surface is energetically more favorable than other adsorption configurations, and the uranyl ion prefers to bind with the deprotonated O adsorption site rather than the protonated one on the hydroxylated surface. During the adsorption process, the chemical adsorption as well as the formation of hydrogen bonds is the dominant factor. PMID:26859616

  2. Slow magnetic relaxation in mononuclear seven-coordinate cobalt(II) complexes with easy plane anisotropy.

    PubMed

    Chen, Lei; Chen, Shu-Yang; Sun, Yi-Chen; Guo, Yu-Mei; Yu, Lu; Chen, Xue-Tai; Wang, Zhenxing; Ouyang, Z W; Song, You; Xue, Zi-Ling

    2015-07-01

    Two mononuclear seven-coordinate cobalt(II) complexes [Co(L)3(NO3)2] (L = 4-tert-butylpyridine, 1; L = isoquinoline, 2) were prepared and structurally analyzed by single-crystal X-ray crystallography. The coordination spheres of 1 and 2 exhibit distorted pentagonal bipyramid geometry. Analysis of their direct-current magnetic data reveals the existence of easy plane anisotropy (D > 0) with a small transverse anisotropy (E), which was further confirmed by high-field electron paramagnetic resonance (HFEPR) spectroscopy. Field-induced slow magnetic relaxations were observed under the applied dc field in complexes 1 and 2 by alternating-current magnetic susceptibility measurements. Importantly, these complexes are new instances of mononuclear high-coordinate cobalt(II)-based single-molecule magnets. PMID:26027953

  3. Increasing phonological complexity reveals heightened instability in inter-articulatory coordination in adults who stutter

    PubMed Central

    Smith, Anne; Sadagopan, Neeraja; Walsh, Bridget; Weber-Fox, Christine

    2010-01-01

    The potential role of phonological complexity in destabilizing the speech motor systems of adults who stutter was explored by assessing the performance of 17 adults who stutter and 17 matched control participants on a nonword repetition task. The nonwords varied in length and phonological complexity. Behavioral results revealed no differences between the stuttering and normally fluent groups on accuracy of nonword repetition. In contrast, dramatic differences between groups were observed in the kinematic data. Indices of the consistency of inter-articulator coordination revealed that adults who stutter were much less consistent in their coordinative patterns over repeated productions. With increasing length and complexity of the nonwords, between-group differences in coordinative consistency were more pronounced. Coordination consistency measures revealed that adults who stutter (but not normally fluent adults) showed within-session practice effects; their coordinative consistency improved in five later compared to five earlier productions. Adults who stutter produced the nonwords at a slower rate, but both groups showed increased rates of production on the later trials, indicating a practice effect for duration for both groups. We conclude that, though the adults who stutter performed behaviorally with the same accuracy as normally fluent adults, the nonword repetition task reveals remarkable differences in the speech motor dynamics underlying fluent speech production in adults who stutter compared to their normally fluent peers. These results support a multifactorial, dynamic model of stuttering in which linguistic complexity and utterance length are factors that contribute to the probability of breakdown of the speech motor system. PMID:20412979

  4. Control of oxo-group functionalization and reduction of the uranyl ion.

    PubMed

    Arnold, Polly L; Pécharman, Anne-Frédérique; Lord, Rianne M; Jones, Guy M; Hollis, Emmalina; Nichol, Gary S; Maron, Laurent; Fang, Jian; Davin, Thomas; Love, Jason B

    2015-04-01

    Uranyl complexes of a large, compartmental N8-macrocycle adopt a rigid, "Pacman" geometry that stabilizes the U(V) oxidation state and promotes chemistry at a single uranyl oxo-group. We present here new and straightforward routes to singly reduced and oxo-silylated uranyl Pacman complexes and propose mechanisms that account for the product formation, and the byproduct distributions that are formed using alternative reagents. Uranyl(VI) Pacman complexes in which one oxo-group is functionalized by a single metal cation are activated toward single-electron reduction. As such, the addition of a second equivalent of a Lewis acidic metal complex such as MgN″2 (N″ = N(SiMe3)2) forms a uranyl(V) complex in which both oxo-groups are Mg functionalized as a result of Mg-N bond homolysis. In contrast, reactions with the less Lewis acidic complex [Zn(N″)Cl] favor the formation of weaker U-O-Zn dative interactions, leading to reductive silylation of the uranyl oxo-group in preference to metalation. Spectroscopic, crystallographic, and computational analysis of these reactions and of oxo-metalated products isolated by other routes have allowed us to propose mechanisms that account for pathways to metalation or silylation of the exo-oxo-group. PMID:25799215

  5. Mechanics of metal-catecholate complexes: the roles of coordination state and metal types.

    PubMed

    Xu, Zhiping

    2013-01-01

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

  6. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts.

    PubMed

    Kim, Sang Bok; Pike, Robert D; Sweigart, Dwight A

    2013-11-19

    Quinonoid metal complexes have potential applications in surface chemistry, coordination polymers, and catalysts. Although quinonoid manganese tricarbonyl complexes have been used as secondary building units (SBUs) in the formation of novel metal-organometallic coordination networks and polymers, the potentially wider applications of these versatile linkers have not yet been recognized. In this Account, we focus on these diverse new applications of quinonoid metal complexes, and report on the variety of quinonoid metal complexes that we have synthesized. Through the use of [(η(6)-hydroquinone)Mn(CO)3](+), we are able to modify the surface of Fe3O4 and FePt nanoparticles (NPs). This process occurs either by the replacement of oleylamine with neutral [(η(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(η(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(η(5)-semiquinone)Mn(CO)3] at the NP surface. We have demonstrated chemistry at the intersection of surface-modified NPs and coordination polymers through the growth of organometallic coordination polymers onto the surface modified Fe3O4 NPs. The resulting magnetic NP/organometallic coordination polymer hybrid material exhibited both the unique superparamagnetic behavior associated with Fe3O4 NPs and the paramagnetism attributable to the metal nodes, depending upon the magnetic range examined. By the use of functionalized [(η(5)-semiquinone)Mn(CO)3] complexes, we attained the formation of an organometallic monolayer on the surface of highly ordered pyrolitic graphite (HOPG). The resulting organometallic monolayer was not simply a random array of manganese atoms on the surface, but rather consisted of an alternating "up and down" spatial arrangement of Mn atoms extending from the HOPG surface due to hydrogen bonding of the quinonoid complexes. We also showed that the topology of metal atoms on the surface could be controlled through the use of quinonoid metal complexes. A quinonoid

  7. Coordination of Care for Complex Pediatric Patients: Perspectives from Providers and Parents

    PubMed Central

    Horsky, Jan; Morgan, Stephen J.; Ramelson, Harley Z.

    2014-01-01

    Coordinators help patients requiring complex chronic care manage frequent ambulatory visits and services received at home or from community-based agencies. EHRs directly support only a few of the required tasks as they do not allow access to all parties involved in care. Our goal was to examine how technology was used to coordinate efforts and to describe common barriers and facilitators. Insights may inform the design of tools that would effectively support identified goals. We conducted five hours of interviews with sixteen parents and six clinicians and characterized emergent themes from transcripts. Situational awareness, care and visit planning, document aggregation, abstraction and interpretation were tasks essential to coordination yet generally poorly supported by EHRs. Providers communicated primarily by email, telephone and by exchanging paper and scanned documents. A preliminary model of coordination that could be used in the planning and testing stages of a User Centered Design process is described. PMID:25954374

  8. Electrochemically fabricated polypyrrole-cobalt-oxygen coordination complex as high-performance lithium-storage materials.

    PubMed

    Guo, Bingkun; Kong, Qingyu; Zhu, Ying; Mao, Ya; Wang, Zhaoxiang; Wan, Meixiang; Chen, Liquan

    2011-12-23

    Current lithium-ion battery (LIB) technologies are all based on inorganic electrode materials, though organic materials have been used as electrodes for years. Disadvantages such as limited thermal stability and low specific capacity hinder their applications. On the other hand, the transition metal oxides that provide high lithium-storage capacity by way of electrochemical conversion reaction suffer from poor cycling stability. Here we report a novel high-performance, organic, lithium-storage material, a polypyrrole-cobalt-oxygen (PPy-Co-O) coordination complex, with high lithium-storage capacity and excellent cycling stability. Extended X-ray absorption fine structure and Raman spectroscopy and other physical and electrochemical characterizations demonstrate that this coordination complex can be electrochemically fabricated by cycling PPy-coated Co(3)O(4) between 0.0 V and 3.0 V versus Li(+)/Li. Density functional theory (DFT) calculations indicate that each cobalt atom coordinates with two nitrogen atoms within the PPy-Co coordination layer and the layers are connected with oxygen atoms between them. Coordination weakens the C-H bonds on PPy and makes the complex a novel lithium-storage material with high capacity and high cycling stability. PMID:22127820

  9. Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes

    NASA Astrophysics Data System (ADS)

    Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-Dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

    2015-12-01

    Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest--and more attractive--systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [CoII(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination--without nanoparticle aggregation and without complex dissociation--of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude.

  10. A Mobile Care Coordination System for the Management of Complex Chronic Disease.

    PubMed

    Haynes, Sarah; Kim, Katherine K

    2016-01-01

    There is global concern about healthcare cost, quality, and access as the prevalence of complex and chronic diseases, such as heart disease, continues to grow. Care for patients with complex chronic disease involves diverse practitioners and multiple transitions between medical centers, physician practices, clinics, community resources, and patient homes. There are few systems that provide the flexibility to manage these varied and complex interactions. Participatory and user-centered design methodology was applied to the first stage of building a mobile platform for care coordination for complex, chronic heart disease. Key informant interviews with patients, caregivers, clinicians, and care coordinators were conducted. Thematic analysis led to identification of priority user functions including shared care plan, medication management, symptom management, nutrition, physical activity, appointments, personal monitoring devices, and integration of data and workflow. Meaningful stakeholder engagement contributes to a person-centered system that enhances health and efficiency. PMID:27332252

  11. A three-coordinate iron-silylene complex stabilized by ligand-ligand dispersion forces.

    PubMed

    Hänninen, Mikko M; Pal, Kuntal; Day, Benjamin M; Pugh, Thomas; Layfield, Richard A

    2016-07-28

    The structural and bonding properties of a three-coordinate N-heterocyclic silyene (NHSi) complex of the iron(ii) amide [Fe{N(SiMe3)2}2] are reported. Computational studies reveal that dispersion forces between the amido SiMe3 substituents and the isopropyl substituents on the NHSi ligand significantly enhance the stability of the complex, along with Fe-to-Si π-backbonding. PMID:27362948

  12. XAFS study of copper(II) complexes with square planar and square pyramidal coordination geometries

    NASA Astrophysics Data System (ADS)

    Gaur, A.; Klysubun, W.; Nitin Nair, N.; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

    2016-08-01

    X-ray absorption fine structure of six Cu(II) complexes, Cu2(Clna)4 2H2O (1), Cu2(ac)4 2H2O (2), Cu2(phac)4 (pyz) (3), Cu2(bpy)2(na)2 H2O (ClO4) (4), Cu2(teen)4(OH)2(ClO4)2 (5) and Cu2(tmen)4(OH)2(ClO4)2 (6) (where ac, phac, pyz, bpy, na, teen, tmen = acetate, phenyl acetate, pyrazole, bipyridine, nicotinic acid, tetraethyethylenediamine, tetramethylethylenediamine, respectively), which were supposed to have square pyramidal and square planar coordination geometries have been investigated. The differences observed in the X-ray absorption near edge structure (XANES) features of the standard compounds having four, five and six coordination geometry points towards presence of square planar and square pyramidal geometry around Cu centre in the studied complexes. The presence of intense pre-edge feature in the spectra of four complexes, 1-4, indicates square pyramidal coordination. Another important XANES feature, present in complexes 5 and 6, is prominent shoulder in the rising part of edge whose intensity decreases in the presence of axial ligands and thus indicates four coordination in these complexes. Ab initio calculations were carried out for square planar and square pyramidal Cu centres to observe the variation of 4p density of states in the presence and absence of axial ligands. To determine the number and distance of scattering atoms around Cu centre in the complexes, EXAFS analysis has been done using the paths obtained from Cu(II) oxide model and an axial Cu-O path from model of a square pyramidal complex. The results obtained from EXAFS analysis have been reported which confirmed the inference drawn from XANES features. Thus, it has been shown that these paths from model of a standard compound can be used to determine the structural parameters for complexes having unknown structure.

  13. Characterization of Coordination Complexes by Desorption Electrospray Mass Spectrometry with a Capillary Target

    SciTech Connect

    Gary S. Groenewold; Anthony D. Appelhans; Michael E. McIlwain; Garold L. Gresham

    2011-03-01

    Metal coordination complexes were formed directly from liquid surfaces using desorption electrospray ionization (DESI) mass spectrometry. The approach is attractive because it separates complexities of ESI spray droplet formation from delivery of the analyte solution, and thereby gets around difficulty resulting from alteration of the spray process by changes in solution chemistry. Cs+, Ba2+, and La3+ coordination complexes were formed using 18-crown-6 (18c6) and triethylphosphate (TEP) as ligands (L), that had the general formula [Mn+(NO3-)n-1(L)m]+. Formation of singly charged cation complexes was preferred, with charge reduction at the metal site accomplished by attachment of nitrate. Using TEP as a model phosphoryl ligand, alkali metals coordinate with up to three ligands, with Cs+ preferring fewer than Na+. Ba2+ and La3+ are formed as ion pair complexes [Ba(NO3)]+ and [La(NO3)2]+, and both will coordinate with up to four TEP ligands. Using 18c6, Cs+ forms a bis-ligand complex. In contrast, [Ba(NO3)]+ prefers a single 18c6 ligand, while La forms mainly [La(NO3)2(18c6)]+, for which DFT calculations suggested a structure in which the nitrate ligands occupy pseudo-axial positions on opposing sides of the crown. Lower abundances of bis-18c6 complexes were also formed together with doubly charged [La(NO3)(18c6)n]2+ complexes (n = 2 – 4). The results suggest an alternative strategy for probing metal speciation in solution that is less perturbed by the droplet formation and ionization mechanisms operating in conventional electrospray ionization mass spectrometry.

  14. Two-coordinate, quasi-two-coordinate, and distorted three coordinate, T-shaped chromium(II) amido complexes: unusual effects of coordination geometry on the lowering of ground state magnetic moments.

    PubMed

    Boynton, Jessica N; Merrill, W Alexander; Reiff, William M; Fettinger, James C; Power, Philip P

    2012-03-01

    The synthesis and characterization of the mononuclear chromium(II) terphenyl substituted primary amido-complexes Cr{N(H)Ar(Pr(i)(6))}(2) (Ar(Pr(i)(6)) = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-(i)Pr(3))(2) (1), Cr{N(H)Ar(Pr(i)(4))}(2) (Ar(Pr(i)(4)) = C(6)H(3)-2,6-(C(6)H(3)-2,6-(i)Pr(2))(2) (2), Cr{N(H)Ar(Me(6))}(2) (Ar(Me(6)) = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-Me(3))(2) (4), and the Lewis base adduct Cr{N(H)Ar(Me(6))}(2)(THF) (3) are described. Reaction of the terphenyl primary amido lithium derivatives Li{N(H)Ar(Pr(i)(6))} and Li{N(H)Ar(Pr(i)(4))} with CrCl(2)(THF)(2) in a 2:1 ratio afforded complexes 1 and 2, which are extremely rare examples of two coordinate chromium and the first stable chromium amides to have linear coordinated high-spin Cr(2+). The reaction of the less crowded terphenyl primary amido lithium salt Li{N(H)Ar(Me(6))} with CrCl(2)(THF)(2) gave the tetrahydrofuran (THF) complex 3, which has a distorted T-shaped metal coordination. Desolvation of 3 at about 70 °C gave 4 which has a formally two-coordinate chromous ion with a very strongly bent core geometry (N-Cr-N= 121.49(13)°) with secondary Cr--C(aryl ring) interactions of 2.338(4) Å to the ligand. Magnetometry studies showed that the two linear chromium species 1 and 2 have ambient temperature magnetic moments of about 4.20 μ(B) and 4.33 μ(B) which are lower than the spin-only value of 4.90 μ(B) typically observed for six coordinate Cr(2+). The bent complex 4 has a similar room temperature magnetic moment of about 4.36 μ(B). These studies suggest that the two-coordinate chromium complexes have significant spin-orbit coupling effects which lead to moments lower than the spin only value of 4.90 μ(B) because λ (the spin orbit coupling parameter) is positive. The three-coordinated complex 3 had a magnetic moment of 3.79 μ(B). PMID:22356657

  15. Synthesis and Base Hydrolysis of a Cobalt(III) Complex Coordinated by a Thioether Ligand

    ERIC Educational Resources Information Center

    Roecker, Lee

    2008-01-01

    A two-week laboratory experiment for students in advanced inorganic chemistry is described. Students prepare and characterize a cobalt(III) complex coordinated by a thioether ligand during the first week of the experiment and then study the kinetics of Co-S bond cleavage in basic solution during the second week. The synthetic portion of the…

  16. Chromogenic detection of Sarin by discolouring decomplexation of a metal coordination complex.

    PubMed

    Ordronneau, Lucie; Carella, Alexandre; Pohanka, Miroslav; Simonato, Jean-Pierre

    2013-10-11

    An innovative chromogenic sensing concept based on decomplexation of a tris-(bipyridine)iron(II) coordination complex has been developed for the detection of organophosphorus nerve agents. It was evaluated both on a simulant and real Sarin in vapour and liquid phases. PMID:23963476

  17. Assessment of CE-ICP/MS hyphenation for the study of uranyl/protein interactions.

    PubMed

    Huynh, Thi-Ngoc Suong; Bourgeois, Damien; Basset, Christian; Vidaud, Claude; Hagège, Agnès

    2015-06-01

    Identification of uranyl transport proteins is key to develop efficient detoxification approaches. Therefore, analytical approaches have to be developed to cope with the complexity of biological media and allow the analysis of metal speciation. CE-ICP/MS was used to combine the less-intrusive character and high separation efficiency of CE with the sensitive detection of ICP/MS. The method was based on the incubation of samples with uranyl prior to the separation. Electrophoretic buffers were compared to select a 10 mM Tris to 15 mM NaCl buffer, which enabled analyses at pH 7.4 and limited dissociation. This method was applied to the analysis of a serum. Two main fractions were observed. By comparison with synthetic mixtures of proteins, the first one was attributed to fetuin and in a lesser extent to HSA, and the second one to uranyl unbound to proteins. The analysis showed that fetuin was likely to be the main target of uranyl. CE-ICP/MS was also used to investigate the behavior of the fetuin-uranyl complex, in the presence of carbonate, an abundant complexing agent of uranyl in blood. This method enabled association constants determination, suggesting the occurrence of both FETUA(UO2(2+)) and FETUA(UO2(2+))(CO3(2-)) complexes, depending on the carbonate concentration. PMID:25630637

  18. Care coordination for patients with complex health profiles in inpatient and outpatient settings.

    PubMed

    Berry, Leonard L; Rock, Beth L; Smith Houskamp, Beth; Brueggeman, Joan; Tucker, Lois

    2013-02-01

    Patients with the most complex health profiles consume a disproportionate percentage of health care expenditures, yet often receive fragmented, suboptimal care. Since 2003, Wisconsin-based Gundersen Health has improved the quality of life and reduced the cost burden of patients with complex health profiles with an integrated care coordination program. Those results are consistent with data from the most successful care coordination demonstration projects funded by the Centers for Medicare and Medicaid Services. Specifically, Gundersen's program has been associated with reduced hospital stays, lower costs for inpatients, less use of inpatient services, and increased patient satisfaction. Gundersen's success is rooted in its team-based approach to coordinated care. Teams, led by a subspecialty-trained nurse, have regular, face-to-face contact with patients and their physicians in both inpatient and outpatient settings; involve patients deeply in care-related decisions; access a system-wide electronic medical record database that tracks patients' care; and take a macrolevel view of care-related factors and costs. Gundersen's model offers specific take-home lessons for institutions interested in coordinated care as they design programs aimed at improving quality and lowering costs. This institutional case study provides a window into well-executed care coordination at a large health care system in an era when major changes in health care provision and reimbursement mechanisms are on the horizon. PMID:23290738

  19. The Role of Care Coordinator for Children with Complex Care Needs: A Systematic Review

    PubMed Central

    Hillis, Rowan; Larkin, Philip J; Cawley, Des; Connolly, Michael

    2016-01-01

    Introduction: This systematic review seeks to identify the intended components of the role of care coordinator for children with complex care needs and the factors that determine its composition in practice. Theory and methods: The initial search identified 1,157 articles, of which 37 met the inclusion criteria. They were quality assessed using the SIGN hierarchy of evidence structure. Results: Core components of the role include: coordination of care needs, planning and assessment, specialist support, emotional support, administration and logistics and continuing professional development. Influencing factors on the role include the external environment (political and socio-economic), the internal environment (organisational structure and funding protocols), the skills, qualifications and experience of the coordinator, the family circumstances and the nature of the interaction between the care coordinator and the family. Discussion: The lack of consistent terminology creates challenges and there is a need for greater consensus on this issue. Organisations and healthcare professionals need to recognise the extent to which contextual factors influence the role of a care coordinator in practice and plan accordingly. Despite evidence that suggests that the role is pivotal in ensuring that care needs are sustained, there remains great variability in the understanding of the role of a care coordinator for this population. Conclusions: As the provision of care increasingly moves closer to home there is a need for greater understanding of the nature and composition of the interaction between care coordinators and families to determine the extent to which appropriate services are being provided. Further work in this area should take into consideration any potential variance in service provision, for example any potential inequity arising due to geographic location. It is also imperative, where appropriate, to seek the views of children with complex care needs and their

  20. Synthesis and theoretical studies on rare three-coordinate lead complexes.

    PubMed

    Chen, Matthew; Fulton, J Robin; Hitchcock, Peter B; Johnstone, Nick C; Lappert, Michael F; Protchenko, Andrey V

    2007-07-14

    A series of beta-diketiminate lead halide complexes has been synthesised LPbCl (2), LPbBr (3) and LPbI (4) (L = {N(2,6-(i)Pr(2)C(6)H(3))C(Me)}2CH]), which includes a rare example of a three-coordinate lead iodide (4). The chloride and bromide complexes, 2 and 3, are relatively stable in both the solid and solution states, only slowly decomposing to elemental lead over the course of a month in solution, the lead iodide 4 appears to be less stable and decomposes after 3 d in the solid state at ambient temperatures. The lead chloride complex 2 was treated with KN(SiMe3)2 to yield an unusual terminal lead amide complex LPbN(SiMe3)2 (5). Unlike three-coordinate beta-diketiminate transition metal-halide complexes, the ligands are present in a pyramidal arrangement around the lead centre, commonly attributed to the presence of a stereochemically active lone pair. We have investigated the influence of this lone pair on the geometry of the metal halide complexes 2-4, as well as the isostructural germanium and tin complexes (6 and 7, respectively) using DFT calculations. The lone pair in the lead complexes is significantly more diffuse than in the tin and germanium analogues and only a small amount of hybridisation between the 6s and 6p orbitals is observed. PMID:17592593

  1. Density functional theory and molecular dynamics study of the uranyl ion (UO₂)²⁺.

    PubMed

    Rodríguez-Jeangros, Nicolás; Seminario, Jorge M

    2014-03-01

    The detection of uranium is very important, especially in water and, more importantly, in the form of uranyl ion (UO₂)²⁺, which is one of its most abundant moieties. Here, we report analyses and simulations of uranyl in water using ab initio modified force fields for water with improved parameters and charges of uranyl. We use a TIP4P model, which allows us to obtain accurate water properties such as the boiling point and the second and third shells of water molecules in the radial distribution function thanks to a fictitious charge that corrects the 3-point models by reproducing the exact dipole moment of the water molecule. We also introduced non-bonded interaction parameters for the water-uranyl intermolecular force field. Special care was taken in testing the effect of a range of uranyl charges on the structure of uranyl-water complexes. Atomic charges of the solvated ion in water were obtained using density functional theory (DFT) calculations taking into account the presence of nitrate ions in the solution, forming a neutral ensemble. DFT-based force fields were calculated in such a way that water properties, such as the boiling point or the pair distribution function stand. Finally, molecular dynamics simulations of a water box containing uranyl cations and nitrate anions are performed at room temperature. The three peaks in the oxygen-oxygen radial distribution function for water were found to be kept in the presence of uranyl thanks to the improvement of interaction parameters and charges. Also, we found three shells of water molecules surrounding the uranyl ion instead of two as was previously thought. PMID:24573498

  2. Computational study of the coordination of methane to first row transition metal dication complexes.

    PubMed

    Roffe, Gavin W; Cox, Hazel

    2013-04-11

    The coordination of methane, the first step in methane activation, to coordinately unsaturated first row transition metal dication complexes has been studied computationally to determine the most stable metal-methane interaction. The geometries and the vibrational frequencies of the encounter complexes [M(pyridine)2(CH4)](2+) have been determined using density functional theory with the ωB97XD hybrid functional and triple-ζ basis sets. The structure is dependent on the metal center; for the early transition metals η(3) coordination is favored, whereas η(2) is more favorable for the later transition metals. The periodic trend in methane binding energies in the [M(pyridine)2(CH4)](2+) complexes follows the trend in electron affinity until the Mn complex but then exhibits decreasing energies from Fe to Zn. This is attributed to increasing Pauli repulsion and ligand-ligand repulsion. For the most stable complex, [Cr(pyridine)2(CH4)](2+), the structures, energies, and spin states of the key intermediates and products in the oxidative addition/reductive elimination pathway have been investigated. It is found that the reaction is thermodynamically favorable and indicates that two-state reactivity may play an important role in lowering the energy of the hydridomethyl intermediate. PMID:23485017

  3. Evolutionary dynamics of the traveler's dilemma and minimum-effort coordination games on complex networks

    NASA Astrophysics Data System (ADS)

    Iyer, Swami; Killingback, Timothy

    2014-10-01

    The traveler's dilemma game and the minimum-effort coordination game are social dilemmas that have received significant attention resulting from the fact that the predictions of classical game theory are inconsistent with the results found when the games are studied experimentally. Moreover, both the traveler's dilemma and the minimum-effort coordination games have potentially important applications in evolutionary biology. Interestingly, standard deterministic evolutionary game theory, as represented by the replicator dynamics in a well-mixed population, is also inadequate to account for the behavior observed in these games. Here we study the evolutionary dynamics of both these games in populations with interaction patterns described by a variety of complex network topologies. We investigate the evolutionary dynamics of these games through agent-based simulations on both model and empirical networks. In particular, we study the effects of network clustering and assortativity on the evolutionary dynamics of both games. In general, we show that the evolutionary behavior of the traveler's dilemma and minimum-effort coordination games on complex networks is in good agreement with that observed experimentally. Thus, formulating the traveler's dilemma and the minimum-effort coordination games on complex networks neatly resolves the paradoxical aspects of these games.

  4. New water soluble heterometallic complex showing unpredicted coordination modes of EDTA

    SciTech Connect

    Mudsainiyan, R.K. Jassal, A.K.; Chawla, S.K.

    2015-10-15

    A mesoporous 3D polymeric complex (I) having formula ([Zr(IV)O-μ{sup 3}-(EDTA)Fe(III)OH]·H{sub 2}O){sub n} has been crystallized and characterized by various techniques. Single-crystal X-ray diffraction analysis revealed that complex (I) crystallized in chiral monoclinic space group Cc (space group no. 9) with unexpected coordination modes of EDTA and mixture of two transition metal ions. In this complex, the coordination number of Zr(IV) ion is seven where four carboxylate oxygen atoms, two nitrogen atoms, one oxide atom are coordinating with Zr(IV). Fe(III) is four coordinated and its coordination environment is composed of three different carboxylic oxygen atoms from three different EDTA and one oxygen atom of –OH group. The structure consists of 4-c and 16-c (2-nodal) net with new topology and point symbol for net is (3{sup 36}·4{sup 54}·5{sup 30})·(3{sup 6}). TGA study and XRPD pattern showed that the coordination polymer is quite stable even after losing water molecule and –OH ion. Quenching behavior in fluorescence of ligand is observed by complexation with transition metal ions is due to n–π⁎ transition. The SEM micrograph shows the morphology of complex (I) exhibits spherical shape with size ranging from 50 to 280 nm. The minimum N{sub 2} (S{sub BET}=8.7693 m{sup 2}/g) and a maximum amount of H{sub 2} (high surface area=1044.86 m{sup 2}/g (STP)) could be adsorbed at 77 K. From DLS study, zeta potential is calculated i.e. −7.94 shows the negative charges on the surface of complex. Hirshfeld surface analysis and fingerprint plots revealed influence of weak or non bonding interactions in crystal packing of complex. - Graphical abstract: The complex (I) crystallized with unexpected coordination modes of EDTA having 4-c, 16-c net with new topology and point symbol is (3{sup 36}·4{sup 54}·5{sup 30})·(3{sup 6}). TGA study and XRPD pattern proved its stability with high preference of H{sub 2} uptake by complex. - Highlights: • 3D complex

  5. EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

    DOEpatents

    Furman, N.H.; Mundy, R.J.

    1957-12-10

    An improvement in the process is described for extracting aqueous uranyl nitrate solutions with an organic solvent such as ether. It has been found that the organic phase will extract a larger quantity of uranyl nitrate if the aqueous phase contains in addition to the uranyl nitrate, a quantity of some other soluble nitrate to act as a salting out agent. Mentioned as suitable are the nitrates of lithium, calcium, zinc, bivalent copper, and trivalent iron.

  6. Hybrid uranyl-vanadium nano-wheels.

    PubMed

    Senchyk, G A; Wylie, E M; Prizio, S; Szymanowski, J E S; Sigmon, G E; Burns, P C

    2015-06-25

    Hybrid uranyl-vanadium oxide clusters intermediate between transition metal polyoxometalates and uranyl peroxide cage clusters were obtained by dissolving uranyl nitrate in the ionic liquid 3-ethyl-1-methylimidazolium ethyl sulfate mixed with an aqueous solution containing vanadium. Where sulfate was present, wheel-shaped {U20V20} crystallized and contains ten sulfate tetrahedra, and in the absence of added sulfate, {U2V16}, a derivative of {V18}, was obtained. PMID:26008125

  7. Homoleptic Transition Metal Complexes of the 7-Azaindolide Ligand Featuring κ1-N1 Coordination

    PubMed Central

    Fillman, Kathlyn L.; Arman, Hadi D.; Tonzetich, Zachary J.

    2015-01-01

    Homoleptic complexes of the anion of 7-azaindole (AzaIn) have been synthesized and characterized for a series of 3d transition metals. For Mn(II), Fe(II), and Co(II), complexes of formula Na2[M(AzaIn)4]·2L (L = THF, 2-MeTHF, toluene, or benzene) have been isolated by treatment of the corresponding metal chloride salts with 7-azaindole in the presence of sodium hexamethyldisilazide. The complexes adopt tetrahedral geometries with exclusive coordination to the transition metal ion through the pyrrolic N1 nitrogen atoms of the AzaIn ligands. Solid-state structures of the complexes demonstrate that the sodium cations remain tightly associated to the coordination entities through interaction with both the pyrrolic and pyridine nitrogen atoms of the azaindolide ligands. For Fe(II), replacement of the sodium cations by other alkali metal ions (Li or K) generates new complexes that demonstrate similar coordination geometries to the sodium salts. As a means of comparison, the Fe(II) complex of 4-azaindolide was also investigated. Na2[Fe(4-AzaIn)4]·2L adopts a similar solution structure to the 7-azaindolide complexes as judged by NMR spectroscopy and cyclic voltammetry. DFT calculations have been performed to investigate the bonding in the 7-azaindolide complexes. Results demonstrate that 7-azaindolide-κ1-N1 is a nearly pure sigma donor ligand that features a high degree of ionic character in its bonding to mid 3d transition metal ions. PMID:26378471

  8. Supramolecular inclusion-based molecular integral rigidity: a feasible strategy for controlling the structural connectivity of uranyl polyrotaxane networks.

    PubMed

    Mei, Lei; Wang, Lin; Yuan, Li-yong; An, Shu-wen; Zhao, Yu-liang; Chai, Zhi-fang; Burns, Peter C; Shi, Wei-qun

    2015-08-01

    The assembly of two-dimensional (2D) large channel uranyl-organic polyrotaxane networks as well as structural regulation of uranyl-bearing units using jointed cucurbit[6]uril-based pseudorotaxanes with integral rigidity based on supramolecular inclusion is presented for the first time. This construction strategy concerning controlling molecular integral rigidity based on supramolecular inclusion may afford an entirely new methodology for coordination chemistry. PMID:26121567

  9. 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

  10. Investigation of the complex reaction coordinate of acid catalyzed amide hydrolysis from molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Zahn, Dirk

    2004-05-01

    The rate-determining step of acid catalyzed peptide hydrolysis is the nucleophilic attack of a water molecule to the carbon atom of the amide group. Therein the addition of the hydroxyl group to the amide carbon atom involves the association of a water molecule transferring one of its protons to an adjacent water molecule. The protonation of the amide nitrogen atom follows as a separate reaction step. Since the nucleophilic attack involves the breaking and formation of several bonds, the underlying reaction coordinate is rather complex. We investigate this reaction step from path sampling Car-Parrinello molecular dynamics simulations. This approach does not require the predefinition of reaction coordinates and is thus particularly suited for investigating reaction mechanisms. From our simulations the most relevant components of the reaction coordinate are elaborated. Though the C⋯O distance of the oxygen atom of the water molecule performing the nucleophilic attack and the corresponding amide carbon atom is a descriptor of the reaction progress, a complete picture of the reaction coordinate must include all three molecules taking part in the reaction. Moreover, the proton transfer is found to depend on favorable solvent configurations. Thus, also the arrangement of non-reacting, i.e. solvent water molecules needs to be considered in the reaction coordinate.

  11. Prebiotic coordination chemistry: The potential role of transition-metal complexes in the chemical evolution

    NASA Technical Reports Server (NTRS)

    Beck, M.

    1979-01-01

    In approaching the extremely involved and complex problem of the origin of life, consideration of the coordination chemistry appeared not only as a possibility but as a necessity. The first model experiments appear to be promising because of prebiotic-type synthesis by means of transition-metal complexes. It is especially significant that in some instances various types of vitally important substances (nucleic bases, amino acids) are formed simultaneously. There is ground to hope that systematic studies in this field will clarify the role of transition-metal complexes in the organizatorial phase of chemical evolution. It is obvious that researchers working in the fields of the chemistry of cyano and carbonyl complexes, and of the catalytic effect of transition-metal complexes are best suited to study these aspects of the attractive and interesting problem of the origin of life.

  12. Affinity of the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) for large metal ions of higher charge. A crystallographic and thermodynamic study of PDA complexes of thorium(IV) and the uranyl(VI) ion.

    PubMed

    Dean, Nolan E; Hancock, Robert D; Cahill, Christopher L; Frisch, Mark

    2008-03-17

    The hydrothermal synthesis and structures of [UO2(PDA)] (1) and [Th(PDA)2(H2O)2].H2O (2) (PDA = 1,10-phenanthroline-2,9-dicarboxylic acid) are reported. 1 is orthorhombic, Pnma, a = 11.1318(7) A, b = 6.6926(4) A, c = 17.3114(12) A, V = 1289.71(14), Z = 4, R = 0.0313; 2 is triclinic, P1, a = 7.6190(15) A, b = 10.423(2) A, c = 17.367(4) A, alpha = 94.93(3) degrees , beta = 97.57(3) degrees , gamma = 109.26(3) degrees , V = 1278.3(4) A (3), Z = 2, R = 0.0654. The local geometry around the U in 1 is a pentagonal bipyramid with the two uranyl oxygens occupying the apical positions. The donor atoms in the plane comprise the four donor atoms from the PDA ligand (average U-N = 2.558 and U-O = 2.351 A) with the fifth site occupied by a bridging carboxylate oxygen from a neighboring UO2/PDA individual. The PDA ligand in 1 is exactly planar, with the U lying in the plane of the ligand. The latter planarity, as well as the near-ideal U-O and U-N bond lengths, and O-U-N and N-U-N bond angles within the chelate rings of 1 suggest that PDA binds to the uranyl cation in a low-strain manner. In 2, there are two PDA ligands bound to the Th (average Th-N = 2.694 and Th-O = 2.430 A) as well as two water molecules (Th-O = 2.473 and 2.532 A) to give the Th a coordination number of 10. The PDA ligands in 2 are bowed, with the Th lying out of the plane of the ligand. Molecular mechanics calculations suggest that the distortion of the PDA ligands in 2 arises because of steric crowding. UV spectroscopic studies of solutions containing 1:1 ratios of PDA and Th(4+) in 0.1 M NaClO4 at 25 degrees C indicate that log K1 for the Th(4+)/PDA complex is 25.7(9). The latter result confirms the previous prediction that complexes of PDA with metal ions of higher charge and an ionic radius of about 1.0 A such as Th(IV) would have remarkably high log K1 values with PDA. The origins of this very high stability are discussed in terms of a synergy between the pyridyl and the carboxylate donor groups of PDA

  13. XAFS study of copper(II) diethylenetriamine complexes having different coordination geometries

    NASA Astrophysics Data System (ADS)

    Gaur, A.; Klysubun, W.; Joshi, S. K.; Soni, Balram; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

    2016-05-01

    XAFS of three Cu(II) diethylenetriamine complexes (in crystalline form) having different coordination geometries have been investigated. First complex has distorted tetragonal pyramidal, second has distorted square planar and third has distorted square pyramidal geometry. The difference in coordination geometries has been inferred from the differences in pre-edge peak, rising part of edge and in shape of white line, which are seen clearly in the derivative XANES spectra. The distortion in geometry has been correlated with the intensity of peaks in derivative spectra. These inferences have been corroborated from EXAFS analysis where the different paths have been used in the theoretical fits in R space to show contributions of different scatterers at different distances.

  14. An unsymmetrical, doubly bridged diiron(II) complex with readily accessible coordination sites

    SciTech Connect

    Satcher, J.H. Jr.; Droege, M.W.

    1996-03-27

    The reactivity of the unsymmetrical diiron(II) complex ({mu}-alkoxo)({mu}-carboxylato)diiron(II) (1) toward the thiocyanate ion is directed to the iron center which has the lesser number of donor atoms contributed by the unsymmetrical bridging ligand rather than by availability of a vacant coordination site. Structural evidence for 1 and the product of reaction with SCN{sup -} is presented.

  15. Uranyl sorption by smectites: spectroscopic assessment of thermodynamic modeling.

    PubMed

    Chisholm-Brause, C J; Berg, J M; Little, K M; Matzner, R A; Morris, D E

    2004-09-15

    Batch sorption experiments and thermodynamic modeling of the interaction of UO2(2+) and its hydrolysis products with two smectitic clay minerals, the reference material SWy-1 [McKinley et al., Clays Clay Miner. 43 (1995) 586] and the soil isolate LK-1 [Turner et al., Geochim. Cosmochim. Acta 30 (1996) 3399], have established a conceptual framework for uranyl/smectite surface complexation based on general reactions between aqueous uranyl species and the reactive sites on the mineral surfaces. In this report, we have formulated and spectroscopically tested a set of hypotheses based on this conceptual framework using samples prepared under similar or identical conditions to evaluate the agreement between surface complexation/speciation as enumerated by spectroscopic characterization and that elaborated by the surface complexation model. Both steady-state and time-resolved optical emission spectral data are presented for uranyl on both smectite minerals as well as on the analogue phases SiO2 and Al(OH)3 spanning the pH range from approximately 4 to 8 and the background electrolyte concentrations from approximately 0.001 to 0.1 M. The spectral data enable the explicit identification of an outer-sphere exchange-site population of the hydrated cation [UO2(OH2)5(2+) ] in SWy-1. Spectral data also clearly establish the existence of inner-sphere surface complexes on the analogue phases and on the amphoteric clay crystallite edge sites [aluminol (>Al-OH) and silanol (>Si-OH)]. Based on the spectral characteristics of these uranyl edge-site populations, it is possible to readily infer for the SiO2, Al(OH)3, and SWy-1 samples the evolution in surface speciation with increasing pH to more hydrolyzed uranyl-surface complexes consistent with the conceptual model. The spectral domain characteristics of the edge-site populations on LK-1 with increasing pH suggest that there is no change in the hydrolysis of the uranyl-surface species. However, emission lifetime data are interpreted

  16. Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates

    DOE PAGESBeta

    Miskowiec, Andrew J.; Kirkegaard, Marie C.; Huq, Ashfia; Mamontov, Eugene; Herwig, Kenneth W.; Trowbridge, Lee D.; Rondinone, Adam Justin; Anderson, Brian B.

    2015-11-17

    We report a novel production method for uranium oxy uoride [(UO2)7F14(H2O)7] 4H2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl uoride, UO2F2, through the gas phase at ambient temperatures fol- lowed by desiccation by equilibration with a dry environment. We follow the structure of [(UO2)7F14(H2O)7] 4H2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous struc- ture), and a water molecule binds as an equatorial ligand to the uranyl ion. Quasielas- tic neutron scattering results compare well with previousmore » measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform re- stricted motion on a length scale commensurate with the O{H bond (r = 0.92 A). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps-1) than their hydrogen-bonded partners (Dr = 28.7 ps-1).« less

  17. Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates.

    PubMed

    Miskowiec, Andrew; Kirkegaard, Marie C; Huq, Ashfia; Mamontov, Eugene; Herwig, Kenneth W; Trowbridge, Lee; Rondinone, Adam; Anderson, Brian

    2015-12-10

    We report a novel production method for uranium oxyfluoride [(UO2)7F14(H2O)7]·4H2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl fluoride, UO2F2, through the gas phase at ambient temperatures followed by desiccation by equilibration with a dry environment. We follow the structure of [(UO2)7F14(H2O)7]·4H2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous structure), and a water molecule binds as an equatorial ligand to the uranyl ion. Quasielastic neutron scattering results compare well with previous measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform restricted motion on a length scale commensurate with the O-H bond (r = 0.92 Å). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps(-1)) than their hydrogen-bonded partners (Dr = 28.7 ps(-1)). PMID:26575434

  18. Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates

    SciTech Connect

    Miskowiec, Andrew J.; Kirkegaard, Marie C.; Huq, Ashfia; Mamontov, Eugene; Herwig, Kenneth W.; Trowbridge, Lee D.; Rondinone, Adam Justin; Anderson, Brian B.

    2015-11-17

    We report a novel production method for uranium oxy uoride [(UO2)7F14(H2O)7] 4H2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl uoride, UO2F2, through the gas phase at ambient temperatures fol- lowed by desiccation by equilibration with a dry environment. We follow the structure of [(UO2)7F14(H2O)7] 4H2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous struc- ture), and a water molecule binds as an equatorial ligand to the uranyl ion. Quasielas- tic neutron scattering results compare well with previous measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform re- stricted motion on a length scale commensurate with the O{H bond (r = 0.92 A). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps-1) than their hydrogen-bonded partners (Dr = 28.7 ps-1).

  19. Dipyridylamide ligand dependent dimensionality in luminescent zinc 2,4-pyridinedicarboxylate coordination complexes

    NASA Astrophysics Data System (ADS)

    Wudkewych, Megan J.; LaDuca, Robert L.

    2016-09-01

    Zinc nitrate, 2,4-pyridinedicarboxylic acid (2,4-pdcH2), and a hydrogen-bonding capable dipyridylamide ligand were combined in aqueous solution and subjected to hydrothermal reaction conditions. Three new crystalline coordination complexes were generated; their dimensionality depends crucially on the dipyridylamide length and geometric disposition of the pyridyl nitrogen donors. The three new phases were structurally characterized via single-crystal X-ray diffraction. {[H23-pina][Zn(2,4-pdc)2(H2O)2]·H2O} (1, 3-pina = 3-pyridylisonicotinamide) is a salt with protonated dipyridylamide cations and coordination complex anions. {[Zn2(2,4-pdc)2(H2O)4(3-pna)]·3H2O}n (2, 3-pna = 3-pyridylnicotinamide) shows a system of two-fold interpenetrated ruffled (6,3) coordination polymer layers. {[Zn(2,4-pdc)(H2O)2(3-pmna)]n (3, 3-pmna = 3-pyridylmethylnicotinamide) manifests a simple 1D chain topology. Luminescence was observed for two of the zinc complexes; this behavior is attributed to π-π* or π-n molecular orbital transitions. Thermal decomposition properties of the new phases are also probed.

  20. SIDEROPHILIN METAL COORDINATION. 1. COMPLEXATION OF THORIUM BY TRANSFERRIN: STRUCTURE-FUNCTION IMPLICATIONS

    SciTech Connect

    Harris, Wesley R.; Carrano, Carl J.; Pecoraro, Vincent L.; Raymond, Kenneth N.

    1980-08-01

    As part of a program to develop actinide-specific sequestering agents, the coordination of actinide ions by human transferrin is being investigated. Therapeutically useful synthetic ligands must be able to compete with this iron-transport protein for the bound actinide ion. As in the Fe(III) complex of the native protein, two Th(IV) ions bind at pH 7. This coordination has been monitored at several pH values by using difference ultraviolet spectroscopy. The corresponding coordination of a phenolic ligand, ethylene-bis-(o-hydroxyphenylglycine) [EHPG], has been used to determine {Delta}{epsilon} for a tyrosyl group coordinated to Th(IV), in contrast to the common practice of assuming the {Delta}{epsilon} for protons and all metal ions is the same. This in turn is used to determine, from the observed {Delta}{epsilon} upon protein coordination, the number of transferrin tyrosine residues that coordinate. Maxima in the Th(IV) + EHPG difference UV spectra occur at 292 and 238 nm, with corresponding {Delta}{epsilon} values per phenolic group of 2330 and 8680 cm{sup -1} M{sup -1}, respectively. At pH 7.2, the Th(IV) transferrin spectrum is closely similar to the TH(IV) EHPG spectrum, with maxima at 292 and 240 nm. The {Delta}{epsilon} at 240 nm reaches a maximum of 24700 cm{sup -1} M{sup -1}, which corresponds to coordination of three tyrosine residues in the dithorium-transferrin complex; the stronger binding site (“A” or C-terminal) coordinates via two tyrosines and the weaker (“B” or N-terminal) via one. There is evidence suggesting that the N-terminal site is slightly smaller than the C-terminal site; while Th(IV) easily fits into the C-terminal site, the large ionic radius of Th(IV) makes this ion of borderline size to fit into the N-terminal site. This may be an important biological difference between Th(IV) and the slightly smaller Pu(IV), which should easily fit into both sites. At pH values below 7, the complexation of Th(IV) by transferrin decreases

  1. The DREAM complex: master coordinator of cell cycle-dependent gene expression.

    PubMed

    Sadasivam, Subhashini; DeCaprio, James A

    2013-08-01

    The dimerization partner, RB-like, E2F and multi-vulval class B (DREAM) complex provides a previously unsuspected unifying role in the cell cycle by directly linking p130, p107, E2F, BMYB and forkhead box protein M1. DREAM mediates gene repression during the G0 phase and coordinates periodic gene expression with peaks during the G1/S and G2/M phases. Perturbations in DREAM complex regulation shift the balance from quiescence towards proliferation and contribute to the increased mitotic gene expression levels that are frequently observed in cancers with a poor prognosis. PMID:23842645

  2. New Iridium Complex Coordinated with Tetrathiafulvalene Substituted Triazole-pyridine Ligand: Synthesis, Photophysical and Electrochemical Properties.

    PubMed

    Niu, Zhi-Gang; Xie, Hui; He, Li-Rong; Li, Kai-Xiu; Xia, Qing; Wu, Dong-Min; Li, Gao-Nan

    2016-01-01

    A new iridium(III) complex based on the triazole-pyridine ligand with tetrathiafulvalene unit, [Ir(ppy)2(L)]PF6 (1), has been synthesized and structurally characterized. The absorption spectra, luminescent spectra and electrochemical behaviors of L and 1 have been investigated. Complex 1 is found to be emissive at room temperature with maxima at 481 and 510 nm. The broad and structured emission bands are suggested a mixing of 3LC (3π-π*) and 3CT (3MLCT) excited states. The influence of iridium ion coordination on the redox properties of the TTF has also been investigated by cyclic voltammetry. PMID:27333555

  3. Coordination Structure Conversion of Hydrazone-Palladium(II) Complexes in the Solid State and in Solution.

    PubMed

    Kitamura, Fumi; Sawaguchi, Kana; Mori, Asami; Takagi, Shoji; Suzuki, Takayoshi; Kobayashi, Atsushi; Kato, Masako; Nakajima, Kiyohiko

    2015-09-01

    We prepared hydrazone-palladium(II) complexes of [PdCl2(HL(n))] and [PdCl(L(n))] (n = 1-3) by the reaction of [PdCl2(cod)] or [PdCl2(PhCN)2] and the hydrazone ligands of HL(n) {N'-(pyridin-2-ylmethylene)picolinohydrazide (HL(1)), N'-[1-(pyridin-2-yl)ethylidene]picolinohydrazide (HL(2)), and N'-[(6-methylpyridin-2-yl)methylene]picolinohydrazide (HL(3))}. The structures of the complexes were determined by X-ray analysis. The hydrazone ligands had κN(py1),κN(imine) and κN(amidate),κN(py2) bidentate coordination modes in [PdCl2(HL(n))] (1, n = 1; 2, n = 2) and in [PdCl2(HL(3))] (3), respectively. In contrast, tridentate coordination modes of κN(py1),κN(imine),κN(py2) and κN(py1),κN(amidate),κN(py2) were observed in [PdCl(L(n))] (4, n = 1; 5, n = 2) and in [PdCl(L(n))] (6, n = 1; 7, n = 2; 8, n = 3). Thermal conversion of complexes 1-3 to complexes 6-8 proceeded in acetonitrile. Complexes 4 and 5 were obtained from complexes 1 and 2, respectively, in a basic acetonitrile solution under dark conditions. Complex 4 reverted immediately to complex 1 in an acidic acetonitrile solution that included hydrochloric acid. However, under room light, in the basic acetonitrile solution that included trimethylamine, complex 4 converted photochemically to complex 6. The thermochromic or vapochromic structure conversion of these complexes also occurred in the solid state. On heating at 180 °C, the color of the crystals of complexes 1, 2, and 3 changed from yellow to orange in the solid state. (1)H NMR and/or UV-vis absorption spectroscopy confirmed that the orange complexes 6-8 were produced. The reddish-orange crystals of complexes 4 and 5 were exposed to hydrogen chloride vapor to yield the yellow products of complexes 1 and 2, respectively. PMID:26305775

  4. Computational Study of Coordinated Ni(II) Complex with High Nitrogen Content Ligands

    PubMed Central

    Tang, Bo; Ye, Jia-Hai; Ju, Xue-Hai

    2011-01-01

    Density functional computations were performed on two tetracoordinated Ni(II) complexes as high nitrogen content energetic materials (1: dinickel bishydrazine ter[(1H-Tetrazol-3-yl)methan-3yl]-1H-tetrazole and 2: dinickel tetraazide ter[(1H-Tetrazol-3-yl)methan-3yl]-1H-tetrazolate). The geometrical structures, relative stabilities and sensitivities, and thermodynamic properties of the complexes were investigated. The energy gaps of frontier molecular orbital (HOMO and LUMO) and vibrational spectroscopies were also examined. There are minor Jahn-Teller distortions in both complexes 1 and 2, with two long Ni–N bond lengths and two short ones. The enthalpies of combustion for both complexes are over 3600 kJ/mol. The N–N bond lengths in the moieties of hydrazine and azide ligands increase in the coordination process compared to those of the isolated molecules. PMID:24052834

  5. Control of Lanthanide Coordination Environment: Synthesis, Structure, and Oxygen-Sensitive Luminescence Properties of an Eight-Coordinate Tb(III) Complex.

    PubMed

    Nakai, Hidetaka; Seo, Juncheol; Kitagawa, Kazuhiro; Goto, Takahiro; Nonaka, Kyoshiro; Matsumoto, Takahiro; Ogo, Seiji

    2016-07-01

    Coordination environment of the Tb(3+) ion in oxygen-sensitive luminescent complexes can be successfully controlled through the size of alkyl substituents on ligands {((RMe)ArOH)4cyclen} (R = tBu or Me; cyclen = 1,4,7,10-tetraazacyclododecane); a newly prepared eight-coordinate complex 1(tBu) shows higher oxygen sensitivity (KSV = 17 600) and lower luminescence quantum yield (Φ = 0.67 under N2) than those of the previously reported seven-coordinate analogues 1(Me) and [{((MeMe)ArO)3tacn}Tb(III)(THF)] (KSV = 12 600 and 8300, Φ = 0.91 and 0.91 under N2, respectively; tacn = 1,4,7-triazacyclononane; THF = tetrahydrofuran). The oxygen-sensitive mechanism is discussed on the basis of the photophysical properties of the corresponding Gd(III) complexes. PMID:27326826

  6. Hybrid uranyl-carboxyphosphonate cage clusters.

    PubMed

    Adelani, Pius O; Ozga, Michael; Wallace, Christine M; Qiu, Jie; Szymanowski, Jennifer E S; Sigmon, Ginger E; Burns, Peter C

    2013-07-01

    Two new hybrid uranyl-carboxyphosphonate cage clusters built from uranyl peroxide units were crystallized from aqueous solution under ambient conditions in approximately two months. The clusters are built from uranyl hexagonal bipyramids and are connected by employing a secondary metal linker, the 2-carboxyphenylphosphonate ligand. The structure of cluster A is composed of a ten-membered uranyl polyhedral belt that is capped on either end of an elongated cage by five-membered rings of uranyl polyhedra. The structure of cluster B consists of 24 uranyl cations that are arranged into 6 four-membered rings of uranyl polyhedra. Four of the corresponding topological squares are fused together to form a sixteen-membered double uranyl pseudobelt that is capped on either end by 2 topological squares. Cluster A crystallizes over a wide pH range of 4.6-6.8, while cluster B was isolated under narrower pH range of 6.9-7.8. Studies of their fate in aqueous solution upon dissolution of crystals by electrospray ionization mass spectrometry (ESI-MS) and small-angle X-ray scattering (SAXS) provide evidence for their persistence in solution. The well-established characteristic fingerprint from the absorption spectra of the uranium(VI) cations disappears and becomes a nearly featureless peak; nonetheless, the two compounds fluoresce at room temperature. PMID:23763595

  7. Optical apparatus and method for sensing uranyl

    DOEpatents

    Baylor, L.C.; Buchanan, B.R.

    1994-01-01

    An optical sensing device for uranyl and other substances, a method for making an optical sensing device and a method for chemically binding uranyl and other indicators to glass, quartz, cellulose and similar substrates. The indicator, such as arsenazo III, is immobilized on the substrate using a chemical binding process. The immobilized arsenazo III causes uranyl from a fluid sample to bind irreversibly to the substrate at its active sites, thus causing absorption of a portion of light transmitted through the substrate. Determination of the amount of light absorbed, using conventional means, yields the concentration of uranyl present in the sample fluid. The binding of uranyl on the substrate can be reversed by subsequent exposure of the substrate to a solution of 2,6-pyridinedicarboxylic acid. The chemical binding process is suitable for similarly binding other indicators, such as bromocresol green.

  8. Assembling a bi-coordinated Cr complex for ferromagnetic nanorings: insight from first-principles calculations.

    PubMed

    Zhu, Guizhi; Liu, Junyi; Sun, Qiang; Jena, Puru

    2016-07-21

    Motivated by the recent synthesis of bi-coordinated transition metal-organic complexes [Samuel, et al., Chem. Sci., 2015, 6, 3148], we have studied the structure and magnetic properties of a series of bi-coordinated transition metal based nanorings by folding quasi-1D chains. Among the cyclic alkyl(amino)carbine (CAAC) based quasi-1D chains (TM-CAAC, TM = Cr, Mn, Fe, Co, Ni), only Cr-CAAC is found to be ferromagnetic. First-principles calculations combined with Heisenberg-Dirac-van Vleck models were performed to understand the onset of robust ferromagnetism in Cr-based systems. With increasing size, the infrared intensity increases and the exchange energy oscillates. In particular, when the number, n, of TM-CAAC units is even and larger than 3, the magnetic coupling in nanorings is stronger than that in quasi-1D chains. The band gap changes very slowly with size. More importantly, compared with the highly coordinated Cr single molecular magnets, the low coordination of Cr ions enhances magnetic moment and stabilizes ferromagnetic coupling. PMID:27315141

  9. A spectroscopic study of uranyl-cytochrome b5/cytochrome c interactions

    NASA Astrophysics Data System (ADS)

    Sun, Mei-Hui; Liu, Shuang-Quan; Du, Ke-Jie; Nie, Chang-Ming; Lin, Ying-Wu

    2014-01-01

    Uranium is harmful to human health due to its radiation damage and the ability of uranyl ion (UO22+) to interact with various proteins and disturb their biological functions. Cytochrome b5 (cyt b5) is a highly negatively charged heme protein and plays a key role in mediating cytochrome c (cyt c) signaling in apoptosis by forming a dynamic cyt b5-cyt c complex. In previous molecular modeling study in combination with UV-Vis studies, we found that UO22+ is capable of binding to cyt b5 at surface residues, Glu37 and Glu43. In this study, we further investigated the structural consequences of cyt b5 and cyt c, as well as cyt b5-cyt c complex, upon uranyl binding, by fluorescence spectroscopic and circular dichroism techniques. Moreover, we proposed a uranyl binding site for cyt c at surface residues, Glu66 and Glu69, by performing a molecular modeling study. It was shown that uranyl binds to cyt b5 (KD = 10 μM), cyt c (KD = 87 μM), and cyt b5-cyt c complex (KD = 30 μM) with a different affinity, which slightly alters the protein conformation and disturbs the interaction of cyt b5-cyt c complex. Additionally, we investigated the functional consequences of uranyl binding to the protein surface, which decreases the inherent peroxidase activity of cyt c. The information of uranyl-cyt b5/cyt c interactions gained in this study likely provides a clue for the mechanism of uranyl toxicity.

  10. Structural studies of six and four coordinate zinc(II), nickel(II) and dioxovanadium(V) complexes with thiosemicarbazones

    NASA Astrophysics Data System (ADS)

    Sreekanth, A.; Sivakumar, S.; Prathapachandra Kurup, M. R.

    2003-07-01

    Three Zn(II) complexes of di-2-pyridyl ketone thiosemicarbazone, an octahedral Ni(II) complex of 2-acetylpyridine hexamethyleneiminyl-3-thiosemicarbazone, and a V(V) complex of 2-acetylpyridine morpholyl-3-thiosemicarbazone were prepared and characterized. Crystal structure of Ni(II) and V(V) complexes are reported. The ligand in the nickel complex is found to coordinate in the thione form with a pseudo octahedral geometry and the vanadium(V) complex has trigonal bipyramidal geometry.

  11. Investigating the pharmacodynamic and magnetic properties of pyrophosphate-bridged coordination complexes

    NASA Astrophysics Data System (ADS)

    Ikotun, Oluwatayo (Tayo) F.

    The multidentate nature of pyrophosphate makes it an attractive ligand for complexation of metal cations. The participation of pyrophosphate in a variety of biological pathways and its metal catalyzed hydrolysis has driven our investigation into its coordination chemistry. We have successfully synthesized a library of binuclear pyrophosphate bridge coordination complexes. The problem of pyrophosphate hydrolysis to phosphate in the presence of divalent metal ions was overcome by incorporating capping ligands such as 1,10-phenanthroline and 2,2'-bipyridine prior to the addition of the pyrophosphate. The magnetic properties of these complexes was investigated and magneto-structural analysis was conducted. The biological abundance of pyrophosphate and the success of metal based drugs such as cisplatin, prompted our investigation of the cytotoxic properties of M(II) pyrophosphate dimeric complexes (where M(II) is CoII, CuII, and NiII) in adriamycin resistant human ovarian cancer cells. Thess compounds were found to exhibit toxicity in the nanomolar to picomolar range. We conducted in vitro stability studies and the mechanism of cytoxicity was elucidated by performing DNA mobility and binding assays, enzyme inhibition assays, and in vitro oxidative stress studies.

  12. Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes.

    PubMed

    Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

    2015-01-01

    Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest--and more attractive--systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [Co(II)(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination--without nanoparticle aggregation and without complex dissociation--of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude. PMID:26634987

  13. Influence of symmetry on the luminescence and radiative lifetime of nine-coordinate europium complexes.

    PubMed

    Shavaleev, Nail M; Eliseeva, Svetlana V; Scopelliti, Rosario; Bünzli, Jean-Claude G

    2015-09-21

    Homoleptic mononuclear nine-coordinate lanthanum(III) and europium(III) tris-complexes [Ln(N(∧)N(∧)O)3]·nH2O with two tridentate N-benzylbenzimidazole pyridine-2-carboxylates exhibit a rare C3-symmetry of the lanthanide coordination polyhedron in the solid state, as confirmed by luminescence spectroscopy and by X-ray crystallography (the three N(∧)N(∧)O ligands are arranged "up-up-up" around the lanthanide ion). The symmetry, however, is changed to the more common C1 upon dissolution of the complexes in dichloromethane, as revealed by luminescence spectroscopy (the three ligands are likely to be arranged "up-up-down"). The new europium complexes emit efficient ligand-sensitized metal-centered luminescence with excited-state lifetimes of 1.56-2.18 ms and quantum yields of 25-41% in the solid and in solution. The change of the symmetry from (a higher) C3 to (a lower) C1 alters the luminescence spectrum, shortens the radiative lifetime, and increases the luminescence efficiency of the europium complexes. PMID:26340341

  14. Structural Variations in the Uranyl/4,4'-Biphenyldicarboxylate System. Rare Examples of 2D → 3D Polycatenated Uranyl-Organic Networks.

    PubMed

    Thuéry, Pierre; Harrowfield, Jack

    2015-08-17

    4,4'-Biphenyldicarboxylic acid (H2L) was reacted with uranyl ions under solvo-hydrothermal conditions with variations in the experimental procedure (organic cosolvent, presence of additional 3d-block metal cations, and N-donor species), thus giving six complexes of the fully deprotonated acid that were characterized by their crystal structure and, in most cases, their emission spectrum. The three complexes [UO2(L)(DMA)] (1), [UO2(L)(NMP)] (2), and [UO2(L)(NMP)] (3) include the cosolvent as a coligand, and they crystallize as two-dimensional (2D) assemblies, with different combinations of the chelating and bridging-bidentate carboxylate coordination modes, resulting in two different topologies. Complex 4, [Ni(bipy)3][(UO2)2(L)2(C2O4)]·H2O, includes oxalate coligands generated in situ and contains an anionic planar two-dimensional (2D) assembly with a {6(3)} honeycomb topology. The same hexagonal geometry is found in the homoleptic complexes [Ni(bipy)3][(UO2)2(L)3]·6H2O (5) and [Ni(phen)3][(UO2)2(L)3]·4H2O (6), but the large size of the hexagonal rings in these cases (∼27 Å in the longest dimension) allows 2D → three-dimensional (3D) inclined polycatenation to occur, with the two families of networks either orthogonal in tetragonal complex 5 or at an angle of 73.4° in orthorhombic complex 6. The parallel networks are arranged in closely spaced groups of two, with possible π···π stacking interactions, and as many as four rods from four parallel nets pass through each ring of the inclined family of nets, an unusually high degree of catenation. These are the second cases only of 2D → 3D inclined polycatenation in uranyl-organic species. Emission spectra measured in the solid state show the usual vibronic fine structure, with variations in intensity and positions of maxima that are not simply connected with the number of equatorial donors and the presence of additional metal cations. PMID:26241368

  15. Kinetic and Thermodynamic Stabilization of Metal Complexes by Introverted Coordination in a Calix[6]azacryptand.

    PubMed

    Inthasot, Alex; Brunetti, Emilio; Lejeune, Manuel; Menard, Nicolas; Prangé, Thierry; Fusaro, Luca; Bruylants, Gilles; Reinaud, Olivia; Luhmer, Michel; Jabin, Ivan; Colasson, Benoit

    2016-03-24

    The Huisgen thermal reaction between an organic azide and an acetylene was employed for the selective monofunctionalization of a X6 -azacryptand ligand bearing a tren coordinating unit [X6 stands for calix[6]arene and tren for tris(2-aminoethyl)amine]. Supramolecular assistance, originating from the formation of a host-guest inclusion complex between the reactants, greatly accelerates the reaction while self-inhibition affords a remarkable selectivity. The new ligand possesses a single amino-leg appended at the large rim of the calixarene core and the corresponding Zn(2+) complex was characterized both in solution and in the solid state. The coordination of Zn(2+) not only involves the tren cap but also the introverted amino-leg, which locks the metal ion in the cavity. Compared with the parent ligand deprived of the amino-leg, the affinity of the new monofunctionalized X6 tren ligand 6 for Zn(2+) is found to have a 10-fold increase in DMSO, which is a very competitive solvent, and with an enhancement of at least three orders of magnitude in CDCl3 /CD3 OD (1:1, v/v). In strong contrast with the fast binding kinetics, decoordination of Zn(2+) as well as transmetallation appeared to be very slow processes. The monofunctionalized X6 tren ligand 6 fully protects the metal ion from the external medium thanks to the combination of a cavity and a closed coordination sphere, leading to greater thermodynamic and kinetic stabilities. PMID:26916610

  16. QM and QM/MM Studies of Uranyl Fluorides in the Gas and Aqueous Phases and in the Hydrophobic Cavities of Tetrabrachion

    SciTech Connect

    Odoh, Samuel O.; Walker, Sean M.; Meier, Markus; Stetefeld, Jörg; Schreckenbach, Georg

    2011-04-04

    The structural properties and electronic structures of pentacoordinated uranyl complexes belonging to the [UO₂Fn(H₂O)5-n]2-n series have been studied in the gas and aqueous phases using density functionals with relativistic pseudopotentials and all-electron basis sets in the gas-phase calculations in combination with COSMO in the aqueous phase. In addition, the conformational orientation and structural and electronic properties of [UO₂F₅]³¯ in the hydrophobic cavities of the right-handed coiled-coil (RHCC) protein of tetrabrachion have been determined using the hybrid QM/MM method. Although there is good agreement between the available experimental geometrical parameters and the values obtained in the aqueous phase using pseudopotentials or all-electron basis sets, variation of the uranyl U=O bond with the number of fluoride ligands is only truly captured after the inclusion of five water molecules in the second coordination sphere around the molecules. The docking procedure used in this work shows that there are only two possible orientations of the uranyl group of [UO₂F₅]³¯ embedded in the hydrophobic cavities of the RHCC protein. The two orientations are exclusively along the axes perpendicular to the protein axial channel with no possible orientation of the uranyl group along the axial channel because of both steric effects and interaction with the alkyl chain of the isoleucine residues pointing into the axial channel. In addition, the embedded complex is always positioned nearer to the isoleucine residues at the N-terminal ends of the hydrophobic cavities. Energy analysis, however, reveals that both conformations can only be observed in cavity 2, the largest hydrophobic cavity. The structural and electronic properties of the ligand embedded in this cavity are very similar to those of the gas-phase structure. A comparable study of [Pt(CN)₆]²¯ and the anticancer drug cisplatin, [PtCl₂(NH₃)₂], in cavity 2, revealed

  17. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    SciTech Connect

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  18. Actinide immobilization in the subsurface environment by in-situ treatment with a hydrolytically unstable organophosphorus complexant: Uranyl uptake by calcium phytate

    SciTech Connect

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

    1997-12-31

    In addition to naturally occurring uranium and thorium, actinide ions exist in the subsurface environment as a result of accidental releases and intentional disposal practices associated with nuclear weapons production. These species present a significant challenge to cost-effective remediation of contaminated environments. An attractive approach to decreasing the probability of actinide migration in the subsurface is to transform the ions into a less mobile form by remote treatment. We have under development a process which relies on a polyfunctional organophosphorus complexant to sequester the mobile metal ions by complexation/cation exchange in the near term, and to subsequently decompose, transforming the actinides into insoluble phosphate mineral forms in the long term. Studies to date include identification of a suitable organophosphorus reagent, profiling of its decomposition kinetics, verification of the formation of phosphate mineral phases upon decomposition of the reagent, and extensive comparison of the actinide uptake ability of the calcium salt of the reagent as compared with hydroxyapatite. In this report, we briefly describe the process with focus on the cation exchange behavior of the calcium salt of the organophosphorus sequestrant.

  19. Three-coordinate iron(IV) bisimido complexes with aminocarbene ligation: synthesis, structure, and reactivity.

    PubMed

    Wang, Lei; Hu, Lianrui; Zhang, Hezhong; Chen, Hui; Deng, Liang

    2015-11-11

    High-valent iron imido species are implicated as reactive intermediates in many iron-catalyzed transformations. However, isolable complexes of this type are rare, and their reactivity is poorly understood. Herein, we report the synthesis, characterization, and reactivity studies on novel three-coordinate iron(IV) bisimido complexes with aminocarbene ligation. Using our recently reported synthetic method for [LFe(NDipp)2] (L = IMes, 1; Me2-cAAC, 2), four new iron(IV) imido complexes, [(IPr)Fe(NDipp)2] (3) and [(Me2-cAAC)Fe(NR)2] (R = Mes, 4; Ad, 5; CMe2CH2Ph, 6), were prepared from the reactions of three-coordinate iron(0) compounds with organic azides. Characterization data acquired from (1)H and (13)C NMR spectroscopy, (57)Fe Mössbauer spectroscopy, and X-ray diffraction studies suggest a low-spin singlet ground state for these iron(IV) complexes and the multiple-bond character of their Fe-N bonds. A reactivity study taking the reactions of 1 as representative revealed an intramolecular alkane dehydrogenation of 1 to produce the iron(II) complex [(IMes)Fe(NHDipp)(NHC6H3-2-Pr(i)-6-CMe═CH2)] (7), a Si-H bond activation reaction of 1 with PhSiH3 to produce the iron(II) complex [(IMes)Fe(NHDipp)(NDippSiPhH2)] (8), and a [2+2]-addition reaction of 1 with PhNCNPh and p-Pr(i)C6H4NCO to form the corresponding open-shell formal iron(IV) monoimido complexes [(IMes)Fe(NDipp)(N(Dipp)C(NPh)(═NPh))] (9) and [(IMes)Fe(NDipp)(N(Dipp)C(O)N(p-Pr(i)C6H4))] (10), as well as [NDipp]-group-transfer reactions with CO and Bu(t)NC. Density functional theory calculations suggested that the alkane chain dehydrogenation reaction starts with a hydrogen atom abstraction mechanism, whereas the Si-H activation reaction proceeds in a [2π+2σ]-addition manner. Both reactions have the pathways at the triplet potential energy surfaces being energetically preferred, and have formal iron(IV) hydride and iron(IV) silyl species as intermediates, respectively. The low-coordinate nature and low d

  20. Surprising coordination for low-valent actinides resembling uranyl(vi) in thorium(iv) organic hybrid layered and framework structures based on a graphene-like (6,3) sheet topology.

    PubMed

    Li, Yuxiang; Weng, Zhehui; Wang, Yanlong; Chen, Lanhua; Sheng, Daopeng; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2016-01-21

    Three thorium(iv)-based metal-organic hybrid compounds with 2D layered and 3D framework structures exhibiting graphene-like (6,3) sheet topologies were prepared with linkers with threefold symmetry. These compounds contain rare and relatively anisotropic coordination environments for low-valent actinides that are similar to those often observed for high-valent actinide ions. PMID:26672441

  1. A Codeposition Route to CuI-Pyridine Coordination Complexes for OLEDs

    PubMed Central

    Liu, Zhiwei; Qayyum, Munzarin F.; Wu, Chao; Whited, Matthew T.; Djurovich, Peter I.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.; Thompson, Mark E.

    2011-01-01

    We demonstrate a new approach to utilize copper(I) iodide coordination complexes as emissive layers in organic light-emitting diodes (OLEDs), by in situ codeposition of copper(I) iodide and 3,5-bis(carbazol-9-yl)pyridine (mCPy). With a simple three-layer device structure, pure green electroluminescence at 530 nm from a copper(I) complex was observed. Maximum luminance and external quantum efficiency (EQE) of 9700 cd/m2 and 4.4% have been achieved, respectively. The luminescent species has been identified as [CuI(mCPy)2]2 based on photophysical studies of model complexes and X-ray absorption spectroscopy (XAS). PMID:21366248

  2. Advances in actinide solid-state and coordination chemistry

    SciTech Connect

    Burns, Peter C; Ikeda, Y.; Czerwinski, K.

    2011-01-31

    Actinide solid-state and coordination chemistry has advanced through unexpected results that have further revealed the complex nature of the 5f elements. Nanoscale control of actinide materials is emerging, as shown by the creation of a considerable range of cluster and tubular topologies. Departures from established structural trends for actinyl ions are provided by cation-cation interactions in which an O atom of one actinyl ion is an equatorial ligand of a bipyramid of another actinyl ion. The solid-state structural complexity of actinide materials has been further demonstrated by open framework materials with interesting properties. The U(VI) tetraoxide core has been added to this cation's repertoire of coordination possibilities. The emergence of pentavalent uranium solid-state and coordination chemistry has resulted from the prudent selection of ligands. Finally, analogues of the uranyl ion have challenged our understanding of this normally unreactive functional group.

  3. Low-Coordinate First Row Early Transition Metal Complexes Stabilized by Modified Terphenyl Ligands

    NASA Astrophysics Data System (ADS)

    Boynton, Jessica Nicole

    The research in this dissertation is focused on the synthesis, structural, and magnetic characterization of two-coordinate open shell (d1-d4) transition metal complexes. Background information on this field of endeavor is provided in Chapter 1. In Chapter 2 I describe the synthesis and characterization of the mononuclear chromium (II) terphenyl substituted primary amido complexes and a Lewis base adduct. These studies suggest that the two-coordinate chromium complexes have significant spin-orbit coupling effects which lead to moments lower than the spin only value of 4.90 muB owing to the fact that lambda (the spin orbit coupling parameter) is positive. The three-coordinated complex 2.3 had a magnetic moment of 3.77 muB. The synthesis and characterization of the first stable two-coordinate vanadium complexes are described in Chapter 3. The values suggest a significant spin orbital angular momentum contribution that leads to a magnetic moment that is lower than their spin only value of 3.87 muB. DFT calculations showed that the major absorptions in their UV-Vis spectra were due to ligand to metal charge transfer transitions. The titanium synthesis and characterization of the bisamido complex along with its three-coordinate titanium(III) precursor are described in Chapter 4. Compound 4.1 was obtained via the stoichiometric reaction of LiN(H)AriPr 6 with the Ti(III) complex TiCl3 *2NMe 3 in trimethylamine. The precursor 4.1 has trigonal pyramidal coordination at the titanium atom, with bonding to two amido nitrogens and a chlorine as well as a secondary interaction to a flanking aryl ring of a terphenyl substituent. Compound 4.2 displays a very distorted four-coordinate metal environment in which the titanium atom is bound to two amido nitrogens and to two carbons from a terphenyl aryl ring. This structure is in sharp contrast to the two-coordinate linear structure that was observed in its first row metal (V-Ni) analogs. The synthesis and characterization of

  4. Complexation of Lanthanides with Glutaroimide-dioxime: Binding Strength and Coordination Modes.

    PubMed

    Ansari, Seraj A; Yang, Yanqiu; Zhang, Zhicheng; Gagnon, Kevin J; Teat, Simon J; Luo, Shunzhong; Rao, Linfeng

    2016-02-01

    The complexation of lanthanides (Nd(3+) and Eu(3+)) with glutaroimide-dioxime (H2L), a cyclic imide dioxime ligand that has been found to form stable complexes with actinides (UO2(2+) and NpO2(+)) and transition metal ions (Fe(3+), Cu(2+), etc.), was studied by potentiometry, absorption spectrophotometry, luminescence spectroscopy, and microcalorimetry. Lanthanides form three successive complexes, M(HL)(2+), M(HL)L, and M(HL)2(+) (where M stands for Nd(3+)/Eu(3+) and HL(-) stands for the singly deprotonated ligand). The enthalpies of complexation, determined by microcalorimetry, show that the formation of these complexes is exothermic. The stability constants of Ln(3+)/H2L complexes are several orders of magnitude lower than that of the corresponding Fe(3+)/H2L complexes but are comparable with that of UO2(2+)/H2L complexes. A structure of Eu(3+)/H2L complex, identified by single-crystal X-ray diffractometry, shows that the ligand coordinates to Eu(3+) in a tridentate mode, via the two oxygen atoms of the oxime group and the nitrogen atom of the imide group. The relocation of protons of the oxime groups (-CH═N-OH) from the oxygen to the nitrogen atom, and the deprotonation of the imide group (-CH-NH-CH-) result in a conjugated system with delocalized electron density on the ligand (-O-N-C-N-C-N-O-) that forms strong complexes with the lanthanide ions. PMID:26765525

  5. An europium(III) diglycolamide complex: insights into the coordination chemistry of lanthanides in solvent extraction.

    PubMed

    Antonio, Mark R; McAlister, Daniel R; Horwitz, E Philip

    2015-01-14

    The synthesis, stoichiometry, and structural characterization of a homoleptic, cationic europium(III) complex with three neutral tetraalkyldiglycolamide ligands are reported. The tri(bismuth tetrachloride)tris(N,N,N',N'-tetra-n-octyldiglycolamide)Eu salt, [Eu(TODGA)3][(BiCl4)3] obtained from methanol was examined by Eu L3-edge X-ray absorption spectroscopy (XAS) to reveal an inner-sphere coordination of Eu(3+) that arises from 9 O atoms and two next-nearest coordination spheres that arise from 6 carbon atoms each. A structural model is proposed in which each TODGA ligand with its O=Ca-Cb-O-Cb-Ca=O backbone acts as a tridentate O donor, where the two carbonyl O atoms and the one ether O atom bond to Eu(3+). Given the structural rigidity of the tridentate coordination motif in [Eu(TODGA)3](3+) with six 5-membered chelate rings, the six Eu-Ca and six Eu-Cb interactions are readily resolved in the EXAFS (extended X-ray absorption fine structure) spectrum. The three charge balancing [BiCl4](-) anions are beyond the cationic [Eu(TODGA)3](3+) cluster in an outer sphere environment that is too distant to be detected by XAS. Despite their sizeable length and propensity for entanglement, the four n-octyl groups of each TODGA (for a total of twelve) do not perturb the Eu(3+) coordination environment over that seen from previously reported single-crystal structures of tripositive lanthanide (Ln(3+)) complexes with tetraalkyldiglycolamide ligands (of the same 1:3 metal-to-ligand ratio stoichiometry) but having shorter i-propyl and i-butyl groups. The present results set the foundation for understanding advanced solvent extraction processes for the separation of the minor, tripositive actinides (Am, Cm) from the Ln(3+) ions in terms of the local structure of Eu(3+) in a solid state coordination complex with TODGA. PMID:25310364

  6. Cation–cation interactions and cation exchange in a series of isostructural framework uranyl tungstates

    SciTech Connect

    Balboni, Enrica; Burns, Peter C.

    2014-05-01

    The isotypical compounds (UO{sub 2}){sub 3}(WO{sub 6})(H{sub 2}O){sub 5} (1), Ag(UO{sub 2}){sub 3}(WO{sub 6})(OH)(H{sub 2}O){sub 3} (2), K(UO{sub 2}){sub 3}(WO{sub 6})OH(H{sub 2}O){sub 4} (3), Rb(UO{sub 2}){sub 3}(WO{sub 6})(OH)(H{sub 2}O){sub 3.5} (4), and Cs(UO{sub 2}){sub 3}(WO{sub 6})OH(H{sub 2}O){sub 3} (5) were synthesized, characterized, and their structures determined. Each crystallizes in space group Cc. (1): a=12.979 (3), b=10.238 (2), c=11.302 (2), β=102.044 (2); (2): a=13.148 (2), b=9.520 (1), c=11.083 (2), β=101.568 (2); (3): a=13.111 (8), b=9.930 (6), c=11.242 (7), β=101.024 (7); (4): a=12.940 (2), b=10.231 (2), c=11.259(2), β=102.205 (2); (5): a=12.983 (3), b=10.191 (3), c=11.263 (4), β=101.661 (4). Compounds 1–5 are a framework of uranyl and tungsten polyhedra containing cation–cation interactions. The framework has three symmetrically distinct U(VI) cations, one tungsten, sixteen to eighteen oxygen atoms, and in 2–5, one monovalent cation. Each atom occupies a general position. Each U(VI) cation is present as a typical (UO{sub 2}){sup 2+} uranyl ion in an overall pentagonal bipyramidal coordination environment. Each pentagonal bipyramid shares two equatorial edges with two other pentagonal bipyramids, forming a trimer. Trimers are connected into chains by edge-sharing with WO{sub 6} octahedra. Chains are linked through cation–cation interactions between two symmetrically independent uranyl ions. This yields a remarkably complex system of intersecting channels that extend along [0 0 1] and [−1 1 0]. The cation exchange properties of 2 and 3 were characterized at room temperature and at 140 °C. - Graphical abstract: Chains of uranium and tungsten polyhedra are connected into a three dimensional framework by cation–cation interactions occurring between two symmetrically independent uranyl pentagonal bipyramids. Monovalent cations present in channels within the structure can be exchanged by room temperature or mild hydrothermal

  7. Desymmetrization of an Octahedral Coordination Complex Inside a Self-Assembled Exoskeleton.

    PubMed

    Johnstone, Mark D; Schwarze, Eike K; Ahrens, Jennifer; Schwarzer, Dirk; Holstein, Julian J; Dittrich, Birger; Pfeffer, Frederick M; Clever, Guido H

    2016-07-25

    The synthesis of a centrally functionalized, ribbon-shaped [6]polynorbornane ligand L that self-assembles with Pd(II) cations into a {Pd2 L4 } coordination cage is reported. The shape-persistent {Pd2 L4 } cage contains two axial cationic centers and an array of four equatorial H-bond donors pointing directly towards the center of the cavity. This precisely defined supramolecular environment is complementary to the geometry of classic octahedral complexes [M(XY)6 ] with six diatomic ligands. Very strong binding of [Pt(CN)6 ](2-) to the cage was observed, with the structure of the host-guest complex {[Pt(CN)6 ]@Pd2 L4 } supported by NMR spectroscopy, MS, and X-ray data. The self-assembled shell imprints its geometry on the encapsulated guest, and desymmetrization of the octahedral platinum species by the influence of the D4h -symmetric second coordination sphere was evidenced by IR spectroscopy. [Fe(CN)6 ](3-) and square-planar [Pt(CN)4 ](2-) were strongly bound. Smaller octahedral anions such as [SiF6 ](2-) , neutral carbonyl complexes ([M(CO)6 ]; M=Cr, Mo, W) and the linear [Ag(CN)2 ](-) anion were only weakly bound, showing that both size and charge match are key factors for high-affinity binding. PMID:27245358

  8. An interesting coordination complex formed between the azo dye Sudan Red G and cobalt ion

    NASA Astrophysics Data System (ADS)

    Garcia, Humberto C.; Ferreira, Gilson Rodrigues; de Oliveira, Luiz Fernando C.

    2014-03-01

    In this study, the synthesis, spectroscopic analysis (Raman and infrared) and crystal structure of compound denominated [Co(SRG)2]·CH3CH2OH have been investigated, were SRG is 1-(2-methoxyphenyl-azo)-2-naphthol or simply Sudan Red G and CH3CH2OH is one molecule of ethanol. The repeating unit is formed by the presence of an adduct complex constituted by two SRG ligands coordinated to the cobalt ion in a slightly distorted octahedral geometry. The other building block consists of a molecule of ethanol, which was used as the reaction solvent. The spectroscopic analysis provided important information related to coordination and formation of molecular complex through its mains bands. In the Raman spectrum the presence of marker bands as in at 1224 cm-1 ascribed to the binder SRG [δ(NH) + ν(COC) + δ(CH) + ν(CC)] were displaced in the complex formed to 1232 cm-1 due to the loss of the proton from the azo group and the formation of a bond between the oxygen of the ether group with the metal ion. In the infrared spectrum the bands at 653/489 cm-1 and 622/528 cm-1 were attributed to [ν(CoO) + νCC)] and [νCoN + νCC] characteristic of the metal-ligand bond.

  9. Talking about the institutional complexity of the integrated rehabilitation system—the importance of coordination

    PubMed Central

    Miettinen, Sari; Ashorn, Ulla; Lehto, Juhani

    2013-01-01

    Rehabilitation in Finland is a good example of functions divided among several welfare sectors, such as health services and social services. The rehabilitation system in Finland is a complex one and there have been many efforts to create a coordinated entity. The purpose of this study is to open up a complex welfare system at the upper policy level and to understand the meaning of coordination at the level of service delivery. We shed light in particular on the national rehabilitation policy in Finland and how the policy has tried to overcome the negative effects of institutional complexity. In this study we used qualitative content analysis and frame analysis. As a result we identified four different welfare state frames with distinct features of policy problems, policy alternatives and institutional failure. The rehabilitation policy in Finland seems to be divided into different components which may cause problems at the level of service delivery and thus in the integration of services. Bringing these components together could at policy level enable a shared view of the rights of different population groups, effective management of integration at the level of service delivery and also an opportunity for change throughout the rehabilitation system. PMID:23687479

  10. Weak coordination of neutral S- and O-donor proximal ligands to a ferrous porphyrin nitrosyl. Characterization of 6-coordinate complexes at low T.

    PubMed

    Martirosyan, G G; Kurtikyan, T S; Azizyan, A S; Iretskii, A V; Ford, P C

    2013-04-01

    The interaction of the S- and O-donor ligands tetrahydrothiophen (THT) and tetrahydrofuran (THF) with the ferrous nitrosyl complex Fe(TTP)(NO) (TTP(2-) is meso-tetra-p-tolyl-porphyrinatodianion) was studied at various temperatures both in solid state and solution using electronic and infrared absorption spectroscopy. Upon addition of these ligands to a cryostat containing sublimed layers of Fe(TTP)(NO), no complex formation was detected at room temperature. However, upon lowering the temperature, spectral changes were observed that are consistent with ligand binding in axial position trans to the NO (the proximal site) and formation of the six-coordinate adducts. Analogous behavior was observed in solution. In both media, the six-coordinate adducts are stable only at low temperature and dissociate to the 5-coordinate nitrosyl complexes upon warming. The NO stretching frequencies of the six-coordinate thioether and ether complexes were recorded and binding constants for the weak bonding of proximal THF and THT ligands were determined from the spectral changes. These parameters are compared with those obtained for the N-donor ligand pyrrolidine. PMID:23376554

  11. The DREAM complex: Master coordinator of cell cycle dependent gene expression

    PubMed Central

    Sadasivam, Subhashini; DeCaprio, James A.

    2014-01-01

    Preface The dimerization partner (DP), retinoblastoma (RB)-like, E2F and MuvB (DREAM) complex provides a previously unsuspected unifying role in the cell cycle by directly linking p130, p107, E2F, BMYB and FOXM1. DREAM mediates gene repression during G0 and coordinates periodic gene expression with peaks during G1/S and G2/M. Perturbations in DREAM regulation shift the balance from quiescence towards proliferation and contribute to increased mitotic gene expression levels frequently observed in cancers with poor prognosis. PMID:23842645

  12. Complex Coordinate Methods for Hydrodynamic Instabilities and Sturm-Liouville Eigenproblems with an Interior Singularity

    NASA Astrophysics Data System (ADS)

    Boyd, John P.

    1985-02-01

    Calculations of inviscid, linearized waves in fluids are very difficult when a mean wind or current U( y) is included because the differential equation is singular wherever U( y)= c, the phase speed. These "critical latitude," "critical level," or "critical point" singularities are particularly severe for Chebyshev methods since these global expansion algorithms are very sensitive to the analytic properties of the solution. A simple remedy is described: by making a change of coordinates y= f( x) where y is the original variable and x is the new coordinate with f( x) a complex function, one can solve the problem on an arc in the complex plane that makes a wide detour around the singularity. Specific guidelines for choosing f( x) for different problems are given in the text. Results are impressive: for an eigenvalue problem with a pole in the middle of the original real interval (a "Sturm-Liouville problem of the fourth kind"), just six basis functions suffice to calculate the real and imaginary parts of the lowest eigenvalue to within 1.4%. For strong instability, i.e., modes whose phase speeds have large imaginary parts, the complex mapping is unnecessary because the critical latitudes are complex and distant from the real axis. Even so, the mapping is useful for instability problems because it can be used to make calculations for very slowly growing modes to follow the changes in c right up to the "neutral curve" where the imaginary part of c=0. Although especially valuable for spectral algorithms, the same trick can be applied with finite difference methods also. The main disadvantage of the algorithm is that the eigenfunction must be calculated in a second, separate step, but this is usually a minor flaw in comparison to the complex mapping's virtues for coping with singular eigenvalue problems.

  13. Car-Parrinello molecular dynamics study of the uranyl behaviour at the gibbsite/water interface

    NASA Astrophysics Data System (ADS)

    Lectez, Sébastien; Roques, Jérôme; Salanne, Mathieu; Simoni, Eric

    2012-10-01

    The uranyl cation UO22+ adsorption on the basal face of gibbsite is studied via Car-Parrinello molecular dynamics. In a first step, we study the water sorption on a gibbsite surface. Three different sorption modes are observed and their hydrogen bond patterns are, respectively, characterized. Then we investigate the sorption properties of an uranyl cation, in the presence of water. In order to take into account the protonation state of the (001) gibbsite face, both a neutral (001) face and a locally deprotonated (001) face are modeled. In the first case, three adsorbed uranyl complexes (1 outer sphere and 2 inner spheres) with similar stabilities are identified. In the second case, when the gibbsite face is locally deprotonated, two adsorbed complexes (1 inner sphere and 1 outer one) are characterized. The inner sphere complex appears to be the most strongly linked to the gibbsite face.

  14. Exploring chemical reactivity of complex systems with path-based coordinates: role of the distance metric.

    PubMed

    Zinovjev, Kirill; Tuñón, Iñaki

    2014-09-01

    Path-based reaction coordinates constitute a valuable tool for free-energy calculations in complex processes. When a reference path is defined by means of collective variables, a nonconstant distance metric that incorporates the nonorthonormality of these variables should be taken into account. In this work, we show that, accounting for the correct metric tensor, these kind of variables can provide iso-hypersurfaces that coincide with the iso-committor surfaces and that activation free energies equal the value that would be obtained if the committor function itself were used as reaction coordinate. The advantages of the incorporation of the variable metric tensor are illustrated with the analysis of the enzymatic reaction catalyzed by isochorismate-pyruvate lyase. Hybrid QM/MM techniques are used to obtain the free energy profile and to analyze reactive trajectories initiated at the transition state. For this example, the committor histogram is peaked at 0.5 only when a variable metric tensor is incorporated in the definition of the path-based coordinate. PMID:24986052

  15. Exploring Coordination Modes: Late Transition Metal Complexes with a Methylene-bridged Macrocyclic Tetra-NHC Ligand.

    PubMed

    Altmann, Philipp J; Weiss, Daniel T; Jandl, Christian; Kühn, Fritz E

    2016-05-20

    A tetranuclear silver(I) N-heterocyclic carbene (NHC) complex bearing a macrocyclic, exclusively methylene-bridged, tetracarbene ligand was synthesized and employed as transmetalation agent for the synthesis of nickel(II), palladium(II), platinum(II), and gold(I) derivatives. The transition metal complexes exhibit different coordination geometries, the coinage metals being bound in a linear fashion forming molecular box-type complexes, whereas the group 10 metals adapt an almost ideal square planar coordination geometry within the ligand's cavity, resulting in saddle-shaped complexes. Both the Ag(I) and the Au(I) complexes show ligand-induced metal-metal contacts, causing photoluminescence in the blue region for the gold complex. Distinct metal-dependent differences of the coordination behavior between the group 10 transition metals were elucidated by low-temperature NMR spectroscopy and DFT calculations. PMID:27017146

  16. Antitumor properties of five-coordinate gold(III) complexes bearing substituted polypyridyl ligands.

    PubMed

    Sanghvi, Chinar D; Olsen, Pauline M; Elix, Catherine; Peng, Shifang Bruce; Wang, Dongsheng; Chen, Zhuo Georgia; Shin, Dong M; Hardcastle, Kenneth I; MacBeth, Cora E; Eichler, Jack F

    2013-11-01

    In an on-going effort to discover metallotherapeutic alternatives to the chemotherapy drug cisplatin, neutral distorted square pyramidal gold(III) coordination complexes possessing 2,9-disubstituted-1,10-phenanthroline ligands {[((R)phen)AuCl3]; R = n-butyl, sec-butyl} have been previously synthesized and characterized. A structurally analogous gold(III) complex bearing a 6,6'-di-methylbipyridine ligand ([((methyl)bipy)AuCl3]) has been synthesized and fully characterized to probe the effect of differing aromatic character of the ligand on solution stability and tumor cell cytotoxicity. The two compounds [((sec-butyl)phen)AuCl3] and [((methyl)bipy)AuCl3]) were subsequently assessed for their stability against the biological reductant glutathione, and it was found that the [((sec-butyl)phen)AuCl3] complex exhibits slightly enhanced stability compared to the [((methyl)bipy)AuCl3] complex and significantly higher stability than previously reported square planar gold(III) complex ions. Furthermore, these complexes were tested for cytotoxic effects against existing lung and head and neck cancer cell lines in vitro. The [((sec-butyl)phen)AuCl3] complex was found to be more cytotoxic than cisplatin against five different tumor cell lines, whereas [((methyl)bipy)AuCl3] had more limited in vitro antitumor activity. Given that [((sec-butyl)phen)AuCl3] had significantly higher antitumor activity, it was tested against an in vivo tumor model. It was found that this complex did not significantly reduce the growth of xenograft tumors in mice and initial model binding studies with bovine serum albumin indicate that interactions with serum albumin proteins may be the cause for the limited in vivo activity of this potential metallotherapeutic. PMID:23948576

  17. Different Coordination Modes of a Tripod Phosphine in Gold(I) and Silver(I) Complexes

    PubMed Central

    Sevillano, P.; Habtemariam, A.; Parsons, S.; Sadler, P. J.

    1999-01-01

    The following gold(I) and silver(I) complexes of the tritertiary phosphine 1,1,1- tris(diphenylphosphinomethyl)ethane, tripod , have been synthesised: Au3(tripod)X3 [X = Cl(1), Br(2), I(3)]; [Au3(tripod)2Cl2]Cl (4); Au(tripod)X [X = Br(5), I(6)]; Ag3(tripod) (NO3)4 (7), Ag(tripod)NO3 (8). They were characterized by X-ray diffraction (complexes 2, 3 and 4), 31P NMR spectroscopy, electrospray and FAB mass spectrometry and infrared spectroscopy. Complexes 2 and 3 show a linear coordination geometry for Au(I), with relatively short Au-P bond distances. Complex 3 has a Au•••Au intramolecular distance of 3.326 A ° , while complex 2 had a short Au•••Au intermolecular interaction of 3.048 A ° . Complexes 4-6 were found by 31P NMR spectroscopy studies to contain a mixture of species in solution, one of which crystallised as [Au3(tripod|)2Cl2]Cl which was shown by X-ray diffraction to contain both tetrahedral and linear Au(I), the first example of a Au(I) complex containing such a mixture of geometries. The reaction of [Au3 (tripod)Cl3] (1) with tripod led successfully to the formation of [Au3(tripod|)2Cl2]+ and [Au3(tripod)2Cl3]+ and [Au3(tripod|)3Cl]2+. The silver(I) complexes, 7 and 8 appear to contain linear and tetrahedral Ag(I), respectively. PMID:18475895

  18. Adsorption studies of divalent, dinuclear coordination complexes as molecular spacers on SWCNTs.

    PubMed

    Alston, Jeffrey R; Banks, David J; McNeill, Chauncey X; Mitchell, James B; Popov, Leonid D; Shcherbakov, Igor N; Poler, J C

    2015-11-28

    In order to enhance the electrical energy storage capabilities of nanostructured carbon materials, inter-particle spacer strategies are needed to maintain ion-accessible surface area between the nanoparticles. This paper presents a comparison between different classes of divalent, dinuclear coordination complexes which both show strong adsorption to SWCNTs and have molecular spacer properties that maintain electrochemical activity. We find that a novel, dinuclear zinc hydrazone complex binds as an ion-pair at very high loading while not inducing significant aggregation as compared to our previously studies of dinuclear ruthenium complexes. These conclusions are supported by conductivity and dispersion stability data. Moreover, since zinc is an earth abundant metal, these complexes can be used as components in sustainable energy storage materials. Binding kinetics and binding equilibrium data are presented. Modeling of the adsorption isotherm is best fit with the BET model. Kinetics data support an independent binding model. Preliminary capacitance and membrane resistance data are consistent with the complexes acting as molecular spacers between the SWCNTs in a condensed thin film. PMID:26457656

  19. Cation-cation interactions and cation exchange in a series of isostructural framework uranyl tungstates

    NASA Astrophysics Data System (ADS)

    Balboni, Enrica; Burns, Peter C.

    2014-05-01

    The isotypical compounds (UO2)3(WO6)(H2O)5 (1), Ag(UO2)3(WO6)(OH)(H2O)3 (2), K(UO2)3(WO6)OH(H2O)4 (3), Rb(UO2)3(WO6)(OH)(H2O)3.5 (4), and Cs(UO2)3(WO6)OH(H2O)3 (5) were synthesized, characterized, and their structures determined. Each crystallizes in space group Cc. (1): a=12.979 (3), b=10.238 (2), c=11.302 (2), β=102.044 (2); (2): a=13.148 (2), b=9.520 (1), c=11.083 (2), β=101.568 (2); (3): a=13.111 (8), b=9.930 (6), c=11.242 (7), β=101.024 (7); (4): a=12.940 (2), b=10.231 (2), c=11.259(2), β=102.205 (2); (5): a=12.983 (3), b=10.191 (3), c=11.263 (4), β=101.661 (4). Compounds 1-5 are a framework of uranyl and tungsten polyhedra containing cation-cation interactions. The framework has three symmetrically distinct U(VI) cations, one tungsten, sixteen to eighteen oxygen atoms, and in 2-5, one monovalent cation. Each atom occupies a general position. Each U(VI) cation is present as a typical (UO2)2+ uranyl ion in an overall pentagonal bipyramidal coordination environment. Each pentagonal bipyramid shares two equatorial edges with two other pentagonal bipyramids, forming a trimer. Trimers are connected into chains by edge-sharing with WO6 octahedra. Chains are linked through cation-cation interactions between two symmetrically independent uranyl ions. This yields a remarkably complex system of intersecting channels that extend along [0 0 1] and [-1 1 0]. The cation exchange properties of 2 and 3 were characterized at room temperature and at 140 °C.

  20. New water oxidation chemistry of a seven-coordinate ruthenium complex with a tetradentate polypyridyl ligand.

    PubMed

    Muckerman, James T; Kowalczyk, Marta; Badiei, Yosra M; Polyansky, Dmitry E; Concepcion, Javier J; Zong, Ruifa; Thummel, Randolph P; Fujita, Etsuko

    2014-07-01

    The mononuclear ruthenium(II) complex [Ru](2+) (Ru = Ru(dpp)(pic)2, where dpp is the tetradentate 2,9-dipyrid-2'-yl-1,10-phenanthroline ligand and pic is 4-picoline) reported by Thummel's group (Inorg. Chem. 2008, 47, 1835-1848) that contains no water molecule in its primary coordination shell is evaluated as a catalyst for water oxidation in artificial photosynthesis. A detailed theoretical characterization of the energetics, thermochemistry, and spectroscopic properties of intermediates allowed us to interpret new electrochemical and spectroscopic experimental data, and propose a mechanism for the water oxidation process that involves an unprecedented sequence of seven-coordinate ruthenium complexes as intermediates. This analysis provides insights into a mechanism that generates four electrons and four protons in the solution and a gas-phase oxygen molecule at different pH values. On the basis of the calculations and corroborated substantially by experiments, the catalytic cycle goes through [(2)Ru(III)](3+) and [(2)Ru(V)(O)](3+) to [(1)Ru(IV)(OOH)](3+) then [(2)Ru(III)(···(3)O2)](3+) at pH 0, and through [(3)Ru(IV)(O)](2+), [(2)Ru(V)(O)](3+), and [(1)Ru(IV)(OO)](2+) at pH 9 before reaching the same [(2)Ru(III)(···(3)O2)](3+) species, from which the liberation of the weakly bound O2 might require an additional oxidation to form [(3)Ru(IV)(O)](2+) to initiate further cycles involving all seven-coordinate species. PMID:24911180

  1. Coordination functionalization of graphene oxide with tetraazamacrocyclic complexes of nickel(II): Generation of paramagnetic centers

    NASA Astrophysics Data System (ADS)

    Basiuk, Vladimir A.; Alzate-Carvajal, Natalia; Henao-Holguín, Laura V.; Rybak-Akimova, Elena V.; Basiuk, Elena V.

    2016-05-01

    We describe a novel approach to functionalization of graphene oxide (GO) which allows for a facile generation of paramagnetic centers from two diamagnetic components. Coordination attachment of [Ni(cyclam)]2+ or [Ni(tet b)]2+ tetraazamacrocyclic cations to carboxylic groups of GO takes place under basic conditions in aqueous-based reaction medium. The procedure is very straightforward and does not require high temperatures or other harsh conditions. Changing the coordination geometry of Ni(II) from square-planar tetracoordinated to pseudooctahedral hexacoordinated brings about the conversion from low-spin to high-spin state of the metal centers. Even though the content of tetraazamacrocyclic complexes in functionalized GO samples was found to be relatively low (nickel content of ca. 1 wt%, as determined by thermogravimetric analysis, elemental analysis and energy dispersive X-ray spectroscopy), room temperature magnetic susceptibility measurements easily detected the appearance of paramagnetic properties in GO + [Ni(cyclam)] and GO + [Ni(tet b)] nanohybrids, with effective magnetic moments of 1.95 BM and 2.2 BM for, respectively. According to density functional theory calculations, the main spin density is localized at the macrocyclic complexes, without considerable extension to graphene sheet, which suggests insignificant ferromagnetic coupling in the nanohybrids, in agreement with the results of magnetic susceptibility measurements. The coordination attachment of Ni(II) tetraazamacrocycles to GO results in considerable changes in Fourier-transform infrared and X-ray photoelectron spectra, as well as in GO morphology, as observed by scanning and transmission electron microscopy, atomic force and scanning tunneling microscopy.

  2. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    NASA Astrophysics Data System (ADS)

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

    2015-04-01

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [{Mn(acacen)}2Ru(NO)(CN)5]n and two complexes composed of different cyanorhenates, [Ni(cyclam)]2[ReO(OH)(CN)4](ClO4)2(H2O)1.25 and [Cu(cyclam)]2[Re(CN)7](H2O)12, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]3[Re(CN)7]2 (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]3[Re(CN)7]2 complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN)n]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu4N)2[Ru(NO)(CN)5], soluble in organic media.

  3. Core-Shell Coating Silicon Anode Interfaces with Coordination Complex for Stable Lithium-Ion Batteries.

    PubMed

    Zhou, Jinqiu; Qian, Tao; Wang, Mengfan; Xu, Na; Zhang, Qi; Li, Qun; Yan, Chenglin

    2016-03-01

    In situ core-shell coating was used to improve the electrochemical performance of Si-based anodes with polypyrrole-Fe coordination complex. The vast functional groups in the organometallic coordination complex easily formed hydrogen bonds when in situ modifying commercial Si nanoparticles. The incorporation of polypyrrole-Fe resulted in the conformal conductive coating surrounding each Si nanoparticle, not only providing good electrical connection to the particles but also promoting the formation of a stable solid-electrolyte-interface layer on the Si electrode surface, enhancing the cycling properties. As an anode material for Li-ion batteries, modified silicon powders exhibited high reversible capacity (3567 mAh/g at 0.3 A/g), good rate property (549.12 mAh/g at 12 A/g), and excellent cycling performance (reversible capacity of 1500 mAh/g after 800 cycles at 1.2 A/g). The constructed novel concept of core-shell coating Si particles presented a promising route for facile and large-scale production of Si-based anodes for extremely durable Li-ion batteries, which provided a wide range of applications in the field of energy storage of the renewable energy derived from the solar energy, hydropower, tidal energy, and geothermal heat. PMID:26863089

  4. Coordination chemistry of a low-coordinate non-metal element: the case of electrophilic terminal phosphinidene complexes.

    PubMed

    Villalba Franco, José Manuel; Schnakenburg, Gregor; Espinosa Ferao, Arturo; Streubel, Rainer

    2016-09-21

    3-Imino-azaphosphiridine complex 1 reacts with carbon monoxide to give 1,3-azaphosphetidinone complex 2, whereas with isocyanides 3a,b substitution occurred to yield complexes 4a,b. Oxidation of 1 using elemental sulfur afforded the first 1,3,2-thiazaphosphetidine-4-imine complex 5. DFT calculations provide insight into a manifold of pathways based on a common intermediate, a carbodiimide-to-phosphinidene complex, leading to P-N and P-C bond insertion products as well as ligand substitution products. PMID:27527532

  5. Adsorption of Uranyl ions on Amine-functionalization of MIL-101(Cr) Nanoparticles by a Facile Coordination-based Post-synthetic strategy and X-ray Absorption Spectroscopy Studies

    PubMed Central

    Zhang, Jian-Yong; Zhang, Na; Zhang, Linjuan; Fang, Yongzheng; Deng, Wei; Yu, Ming; Wang, Ziqiang; Li, Lina; Liu, Xiyan; Li, Jingye

    2015-01-01

    By a facile coordination-based post-synthetic strategy, the high surface area MIL-101(Cr) nanoparticles was functionallized by grafting amine group of ethylenediamine (ED) on coordinatively unsaturated Cr(III) centers, yielding a series of ED-MIL-101(Cr)-based adsorbents and their application for adsorption of U(VI) from aqueous solution were also studied. The obtained ED-functionallized samples with different ED contents were characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), FTIR, elemental analysis (EA) and N2 adsorption and desorption isothermal. Compared with the pristine MIL-101(Cr) sorbents, the ED-functionallized MIL-101(Cr) exhibits significantly higher adsorption capacity for U(VI) ions from water with maximum adsorption capacities as high as 200 mg/g (corresponding to 100% extraction rate) at pH of 4.5 with ED/Cr ratio of 0.68 and the sorbed U(VI) ions can easily be desorbed at lower pH (pH ≤ 2.0). The adsorption mode of U(VI) ions and effects of grafted ED on the MIL-101(Cr) frameworks were also been studied by X-ray absorption spectroscopy (XAS). We believe that this work establishes a simple and energy efficient route to a novel type of functional materials for U(VI) ions extraction from solution via the post-synthetic modification (PSM) strategy. PMID:26354407

  6. Adsorption of Uranyl ions on Amine-functionalization of MIL-101(Cr) Nanoparticles by a Facile Coordination-based Post-synthetic strategy and X-ray Absorption Spectroscopy Studies

    NASA Astrophysics Data System (ADS)

    Zhang, Jian-Yong; Zhang, Na; Zhang, Linjuan; Fang, Yongzheng; Deng, Wei; Yu, Ming; Wang, Ziqiang; Li, Lina; Liu, Xiyan; Li, Jingye

    2015-09-01

    By a facile coordination-based post-synthetic strategy, the high surface area MIL-101(Cr) nanoparticles was functionallized by grafting amine group of ethylenediamine (ED) on coordinatively unsaturated Cr(III) centers, yielding a series of ED-MIL-101(Cr)-based adsorbents and their application for adsorption of U(VI) from aqueous solution were also studied. The obtained ED-functionallized samples with different ED contents were characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), FTIR, elemental analysis (EA) and N2 adsorption and desorption isothermal. Compared with the pristine MIL-101(Cr) sorbents, the ED-functionallized MIL-101(Cr) exhibits significantly higher adsorption capacity for U(VI) ions from water with maximum adsorption capacities as high as 200 mg/g (corresponding to 100% extraction rate) at pH of 4.5 with ED/Cr ratio of 0.68 and the sorbed U(VI) ions can easily be desorbed at lower pH (pH ≤ 2.0). The adsorption mode of U(VI) ions and effects of grafted ED on the MIL-101(Cr) frameworks were also been studied by X-ray absorption spectroscopy (XAS). We believe that this work establishes a simple and energy efficient route to a novel type of functional materials for U(VI) ions extraction from solution via the post-synthetic modification (PSM) strategy.

  7. Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes

    PubMed Central

    Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

    2015-01-01

    Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest—and more attractive—systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [CoII(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination—without nanoparticle aggregation and without complex dissociation—of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude. PMID:26634987

  8. Combination of optically measured coordinates and displacements for quantitative investigation of complex objects

    NASA Astrophysics Data System (ADS)

    Andrae, Peter; Beeck, Manfred-Andreas; Jueptner, Werner P. O.; Nadeborn, Werner; Osten, Wolfgang

    1996-09-01

    Holographic interferometry makes it possible to measure high precision displacement data in the range of the wavelength of the used laser light. However, the determination of 3D- displacement vectors of objects with complex surfaces requires the measurement of 3D-object coordinates not only to consider local sensitivities but to distinguish between in-plane deformation, i.e. strains, and out-of-plane components, i.e. shears, too. To this purpose both the surface displacement and coordinates have to be combined and it is advantageous to make the data available for CAE- systems. The object surface has to be approximated analytically from the measured point cloud to generate a surface mesh. The displacement vectors can be assigned to the nodes of this surface mesh for visualization of the deformation of the object under test. They also can be compared to the results of FEM-calculations or can be used as boundary conditions for further numerical investigations. Here the 3D-object coordinates are measured in a separate topometric set-up using a modified fringe projection technique to acquire absolute phase values and a sophisticated geometrical model to map these phase data onto coordinates precisely. The determination of 3D-displacement vectors requires the measurement of several interference phase distributions for at least three independent sensitivity directions depending on the observation and illumination directions as well as the 3D-position of each measuring point. These geometric quantities have to be transformed into a reference coordinate system of the interferometric set-up in order to calculate the geometric matrix. The necessary transformation can be realized by means of a detection of object features in both data sets and a subsequent determination of the external camera orientation. This paper presents a consistent solution for the measurement and combination of shape and displacement data including their transformation into simulation systems. The

  9. Assembly of Heterometallic Rigid-Rod Complexes and Coordination Oligomers from Gold(I) Metalloligands.

    PubMed

    Cámara, Verónica; Barquero, Natalia; Bautista, Delia; Gil-Rubio, Juan; Vicente, José

    2015-07-01

    The reactions of TpylC6H4C≡CAuL (Tpyl = 2,2':6',2″-terpyridin-4'-yl; L = PPh3, CNXy; Xy = 2,6-dimethylphenyl) with MX2·nH2O (M = Fe, X = ClO4; M = Co, X = BF4; M = Zn, X = TfO, ClO4) in a 2:1 molar ratio give complexes [M(TpylC6H4C≡CAuL)2]X2. Similarly, the reactions of PPN[(TpylC6H4C≡C)2Au] (PPN = (Ph3P)2N) with an equimolar amount of MX2·nH2O give coordination oligomers [M{(TpylC6H4C≡C)2Au}]nXn (M = Fe, Zn, X = ClO4; M = Co, X = BF4). The complexes and oligomers have been isolated and characterized. The crystal structures of [Fe(TpylC6H4C≡CAuCNXy)2](ClO4)2 and [Co(TpylC6H4C≡CAuPPh3)2](BF4)2 have been determined by X-ray diffraction. The hydrodynamic sizes of complexes [M(TpylC6H4C≡CAuPPh3)2]X2 and coordination oligomers [M{(TpylC6H4C≡C)2Au}]nXn have been studied by NMR diffusion spectroscopy and dynamic light scattering measurements. PMID:26087239

  10. A theoretical study of an unusual Y-shaped three-coordinate Pt complex: Pt(0) σ-disilane complex or Pt(II) disilyl complex?

    PubMed

    Takagi, Nozomi; Sakaki, Shigeyoshi

    2012-07-18

    The unusual Y-shaped structure of the recently reported three-coordinate Pt complex Pt[NHC(Dip)(2)](SiMe(2)Ph)(2) (NHC = N-heterocyclic carbene; Dip = 2,6-diisopropylphenyl) was considered a snapshot of the reductive elimination of disilane. A density functional theory study indicates that this structure arises from the strong trans influence of the extremely σ-donating carbene and silyl ligands. Though this complex can be understood to be a Pt(II) disilyl complex bearing a distorted geometry due to the Jahn-Teller effect, its (195)Pt NMR chemical shift is considerably different from those of Pt(II) complexes but close to those of typical Pt(0) complexes. Its Si···Si bonding interaction is ~50% of the usual energy of a Si-Si single bond. The interaction between the Pt center and the (SiMe(2)Ph)(2) moiety can be understood in terms of donation and back-donation interactions of the Si-Si σ-bonding and σ*-antibonding molecular orbitals with the Pt center. Thus, we conclude that this is likely a Pt(0) σ-disilane complex and thus a snapshot after a considerable amount of the charge transfer from disilane to the Pt center has occurred. Phenyl anion (Ph(-)) and [R-Ar](-) [R-Ar = 2,6-(2,6-iPr(2)C(6)H(3))(2)C(6)H(3)] as well as the divalent carbon(0) ligand C(NHC)(2) also provide similar unusual Y-shaped structures. Three-coordinate digermyl, diboryl, and silyl-boryl complexes of Pt and a disilyl complex of Pd are theoretically predicted to have similar unusual Y-shaped structures when a strongly donating ligand coordinates to the metal center. In a trigonal-bipyramidal Ir disilyl complex [Ir{NHC(Dip)(2)}(PH(3))(2)(SiMe(3))(2)](+), the equatorial plane has a similar unusual Y-shaped structure. These results suggest that various snapshots can be shown for the reductive eliminations of the Ge-Ge, B-B, and B-Si σ-bonds. PMID:22680620

  11. Thermal expansion and structural complexity of Ba silicates with tetrahedrally coordinated Si atoms

    NASA Astrophysics Data System (ADS)

    Gorelova, Liudmila A.; Bubnova, Rimma S.; Krivovichev, Sergey V.; Krzhizhanovskaya, Maria G.; Filatov, Stanislav K.

    2016-03-01

    Thermal expansion of Ba silicates with tetrahedrally coordinated Si atoms in the temperature range of 25-1100 °C had been studied by high-temperature X-ray powder diffraction. The volume thermal expansion coefficients (TECs) are in the range 41-50×10-6 °C-1 with an average value of <αV > = 45 ×10-6 °C-1. In the structures with chain and layered silicate anions, thermal expansion is anisotropic: the direction of maximal TEC is parallel to the extension of the zweier chains of silicate tetrahedra, which are strained owing to the interactions with Ba2+. The strain is released during thermal expansion due to the increasing effective size of Ba2+ induced by thermal vibrations. Information-theoretic analysis of the structural and topological complexities of Ba silicates indicates that their structural complexity is a function of the topological complexity of their silicate anions. The latter displays a non-linear behaviour with increasing SiO2 content (=the increasing degree of polymerization and increasing dimensionality): it starts from simple topologies, reaches a maximum at topologies of intermediate complexity, and ends up at simple topologies again. The specificity of the interactions of Ba2+ with the silicate anions results in higher complexity of high-temperature α-BaSi2O5 compared to that of low-temperature β-BaSi2O5. This uncommon behaviour may be explained by the vibrational advantages provided by flatter and more complex silicate layers in the α-phase, which overcome negative differences in configurational entropies of the two modifications apparent in the differences of their structural Shannon information.

  12. Coordination between manganese and nitrogen within the ligands in the manganese complexes facilitates the reconstitution of the water-oxidizing complex in manganese-depleted photosystem II preparations.

    PubMed

    Li, Shuqin; Chen, Guiying; Han, Guangye; Ling, Lin; Huang, Deguang; Khorobrykh, A A; Zharmukhamedov, S K; Liu, Qiutian; Klimov, V V; Kuang, Tingyun

    2006-09-01

    The water-oxidizing complex (WOC) within photosystem II (PSII) can be reconstituted with synthetic manganese complexes by a process called photoactivation; however, the key factors affecting the efficiency of synthetic manganese complexes in reconstitution of electron transport and oxygen evolution activity in manganese-depleted PSII remain unclear. In the present study, four complexes with different manganese coordination environments were used to reconstitute the WOC, and an interesting relationship was found between the coordination environment of the manganese atom in the complexes and their efficiency in restoring electron transport and oxygen evolution. If Mn(II) is coordinated to nitrogen atoms within the ligand, it can restore significant rates of electron transport and oxygen evolution; however, if the manganese atom is coordinated only to oxygen atoms instead of nitrogen atoms, it has no capability to restore electron transport and oxygen evolution. So, our results demonstrate that the capability of manganese complexes to reconstitute the WOC is mainly determined by the coordination between nitrogen atoms from ligands and the manganese atom. It is suggested from our results that the ligation between the nitrogen atom and the manganese atom within the manganese complex facilitates the photoligation of the manganese atom to histidyl residues on the apo-protein in manganese-depleted PSII during photoactivation. PMID:16791637

  13. Metal carbonyl complexes of phosphaamidines. Coordinative integrity detected in C-amino(λ(3),σ(2))-phosphaalkene isomers coordinated through n(P) HOMO-1 donor orbitals.

    PubMed

    Masuda, Jason D; Boeré, René T

    2016-02-01

    Metal(0) complexes L(Cr,Mo,W)(CO)5 have been prepared from 1,3-bis(2,6-diisopropylphenyl)-2-(4-methylphenyl)-3-aza-1(λ(3),σ(2))-phosphapropene and 1,3-bis(2,6-diisopropylphenyl)-2-(4-methoxyphenyl)-3-aza-1(λ(3),σ(2))-phosphapropene using standard methods. Full characterization of four products and crystal structures of these complexes as well as the methoxyphenyl-phosphapropene are reported. The ligands coordinate κP, common for simple phosphaalkenes, despite the strongly-perturbing amino substitution at the double bond C atoms. Analyses of the NMR and vibrational spectroscopic data reveal that the complexes have very similar character to similarly-coordinated phosphaalkenes, with strong σ-donor character. The presence of some net π-interactions (acceptor or donor) is indicated by structures in which the ligands coordinate fully eclipsed with the M-CO groups. The synthetic and structural results have been augmented by B3PW91/LANL2DZ calculations that reproduce the structures of the Cr complexes accurately. The calculated vibrational spectra are used to confirm the assignment of the ν(C ≡ O) vibrational data. Detailed orbital interaction diagrams based on DFT calculations are reported for the title complexes as well as for the Cr(CO)5 complex of Mes-P=CPh2. The electronic absorption spectra of the title complexes have intense low-energy absorptions ranging from 24,500 to 25,300 cm(-1), which can be interpreted qualitatively using the DFT results. PMID:26485276

  14. Coordination Complexes of Decamethylytterbocene with4,4'-Disubstituted Bipyridines: An Experimental Study of Spin Coupling inLanthanide Complexes

    SciTech Connect

    Walter, Marc D.; Berg, David J.; Andersen, Richard A.

    2005-12-08

    The paramagnetic 1:1 coordination complexes of (C5Me5)2Ybwith a series of 4,4'-disubstituted bipyridines, bipy-X, where X is Me,tert-Bu, OMe, Ph, CO2Me, and CO2Et have been prepared. All of thecomplexes are paramagnetic and the values of the magnetic susceptibilityas a function of temperature show that these values are less thanexpected for the cation, [(C5Me5)2Yb(III)(bipy-X)]+, which have beenisolated as the cation-anion ion-pairs[(C5Me5)2Yb(III)(bipy-X)]+[(C5Me5)2YbI2]f fnfn where X is CO2Et, OMe andMe. The 1H NMR chemical shifts (293 K) for the methine resonances locatedat the 6,6' site in the bipy-X ring show a linear relationship with thevalues of chiT (300 K) for the neutral complexes which illustrates thatthe molecular behavior does not depend upon the phase with one exception,viz., (C5Me5)2Yb(bipy-Me). Single crystals of the 4,4'-dimethylbipyridinecomplex undergo an irreversible, abrupt first order phase change at 228 Kthat shatters the single crystals. The magnetic susceptibility,represented in a delta vs. T plot, on this complex, in polycrystallineform undergoes reversible abrupt changes in the temperature regime 205 -212 K, which is suggested to be due to the way the individual molec ularunits pack in the unit cell. A qualitative model is proposed thataccounts for the sub-normal magnetic moments in theseytterbocene-bipyridine complexes.

  15. Effect of axial coordination on the electronic structure and biological activity of dirhodium(II,II) complexes.

    PubMed

    Aguirre, J Dafhne; Lutterman, Daniel A; Angeles-Boza, Alfredo M; Dunbar, Kim R; Turro, Claudia

    2007-09-01

    The reactivities toward biomolecules of a series of three dirhodium(II,II) complexes that possess an increasing number of accessible axial coordination sites are compared. In cis-[Rh2(OAc)2(np)2]2+ (1; np=1,8-naphthyridine) both axial sites are available for coordination, whereas for cis-[Rh2(OAc)2(np)(pynp)]2+ (2; pynp=2-(2-pyridyl)1,8-naphthyridine) and cis-[Rh2(OAc)2(pynp)2]2+ (3) the bridging pynp ligand blocks one and two of the axial coordination sites in the complexes, respectively. The electronic absorption spectra of the complexes are consistent with strong metal-to-ligand charge transfer transitions at low energy and ligand-centered peaks localized on the np and/or pynp ligands in the UV and near-UV regions. Time-dependent density functional theory calculations were used to aid in the assignments. The three complexes exhibit metal-centered oxidations and reductions, localized on the aromatic ligands. The ability of the complexes to stabilize duplex DNA and to inhibit transcription in vitro is greatly affected by the availability of an open axial coordination site. The present work shows that open axial coordination sites on the dirhodium complexes are necessary for biological activity. PMID:17685607

  16. Spin Isomers and Ligand Isomerization in a Three-Coordinate Cobalt(I) Carbonyl Complex.

    PubMed

    Al-Afyouni, Malik H; Suturina, Elizaveta; Pathak, Shubhrodeep; Atanasov, Mihail; Bill, Eckhard; DeRosha, Daniel E; Brennessel, William W; Neese, Frank; Holland, Patrick L

    2015-08-26

    Hemilabile ligands, which have one donor that can reversibly bind to a metal, are widely used in transition-metal catalysts to create open coordination sites. This change in coordination at the metal can also cause spin-state changes. Here, we explore a cobalt(I) system that is poised on the brink of hemilability and of a spin-state change and can rapidly interconvert between different spin states with different structures ("spin isomers"). The new cobalt(I) monocarbonyl complex L(tBu)Co(CO) (2) is a singlet ((1)2) in the solid state, with an unprecedented diketiminate binding mode where one of the C═C double bonds of an aromatic ring completes a pseudo-square-planar coordination. Dissolving the compound gives a substantial population of the triplet ((3)2), which has exceptionally large uniaxial zero-field splitting due to strong spin-orbit coupling with a low-lying excited state. The interconversion of the two spin isomers is rapid, even at low temperature, and temperature-dependent NMR and electronic absorption spectroscopy studies show the energy differences quantitatively. Spectroscopically validated computations corroborate the presence of a low minimum-energy crossing point (MECP) between the two potential energy surfaces and elucidate the detailed pathway through which the β-diketiminate ligand "slips" between bidentate and arene-bound forms: rather than dissociation, the cobalt slides along the aromatic system in a pathway that balances strain energy and cobalt-ligand bonding. These results show that multiple spin states are easily accessible in this hemilabile system and map the thermodynamics and mechanism of the transition. PMID:26267848

  17. Cyclic Alkyl(amino) Carbene Stabilized Complexes with Low Coordinate Metals of Enduring Nature.

    PubMed

    Roy, Sudipta; Mondal, Kartik Chandra; Roesky, Herbert W

    2016-03-15

    N-Heterocyclic carbenes (NHCs) are known to stabilize some metal atoms in different oxidation states mostly by their strong σ-donation. After the successful syntheses of cyclic alkyl(amino) carbenes (cAACs), they have been proven to be much more effective in stabilizing electron rich species. In cAAC, one of the σ-withdrawing and π-donating nitrogen atoms of NHC is replaced by a σ-donating quaternary carbon atom leading to a lower lying LUMO. This makes the acceptance of π-back-donation from the element bound to the carbene carbon atom of cAAC energetically more advantageous. Further evidence suggests that the carbene carbon of cAAC can use the lone pair of electrons present on the adjacent nitrogen in a more controlled way depending on the accumulation of electron density on the bound metal. It has been found that cAAC can be utilized as excellent ligand for the stabilization of a complex with three coordinate metal center [(cAAC)2M(I)-Cl; M = Fe, Co, Cr]. Complex (cAAC)2M(II)Cl2 [M = Fe, Co, Cr] was prepared by reacting anhydrous M(II)Cl2 with two equiv of cAAC followed by treatment with one equiv of KC8 (reducing agent) to obtain (cAAC)2M(I)-Cl. The corresponding cation (cAAC)2M(+) was isolated when (cAAC)2M(I)-Cl was reacted with sodium-tetraarylborate (lithium) in toluene or fluorobenzene. The CV of cation (cAAC)2M(+) [M = Co, Fe] suggests that it can reversibly undergo one electron reduction. The cations of Co and Fe were reduced with Na(Hg) or KC8, respectively. (cAAC)2Co(I)Cl can be directly reduced to (cAAC)2Co(0) when reacted with one equiv of KC8. Analogous (cAAC·)2Zn(II) and (cAAC)2Mn complexes are prepared by reduction of (cAAC)MCl2 [M = Zn, Mn] with two equiv of KC8 in the presence of one equiv of cAAC. The square planar (cAAC)2NiCl2 complex was directly reduced by two equiv of LiN(iPr2) (KC8) to (cAAC)2Ni(0). The (cAAC)2Pd(0) and (cAAC)2Pt(0) complexes are prepared by substituting all four triphenylphosphines of (Ph3P)4M(0) [M = Pd, Pt] by two

  18. INCORPORATION OF PENTAVALENT NEPTUNIUM INTO URANYL PHASES THAT MAY FORM AS ALTERATION PRODUCTS OF SPENT NUCLEAR FUEL

    SciTech Connect

    NA

    2005-06-21

    Laboratory-scale simulations and studies of natural analogues have shown that alteration of spent nuclear fuel in a moist, oxidizing environment results in the formation of a variety of uranyl phases. Neptunium-237 has a half-life of 2.14 million years, and the pentavalent oxidation state is soluble in groundwater. Release of Np-237 from spent nuclear fuel in a geological repository may significantly impact the long-term performance of such a repository. Incorporation of Np, in the pentavalent oxidation state, into uranyl phases by substitution for hexavalent U is likely because of the similarity of the coordination environments of these two cations, but a charge-balance mechanism is required for substitution. A preliminary study has shown incorporation of pentavalent Np into powders of the uranyl silicate uranophane, and Na-compreignacite, a uranyl oxyhydrate [1]. Using synthesis experiments under mild hydrothermal conditions, we are examining the incorporation of pentavalent Np into selected uranyl oxyhydrates and silicates as a function of temperature and the pH of the mother solution. Analyses of powders of these uranyl phases has demonstrated both temperature and pH dependences for incorporation. Experiments are underway directed at the synthesis of single crystals of uranyl phases in the presence of 500-750 ppm pentavalent Np. The intent is to develop a basic understanding of the crystallographic and crystal chemical factors that impact incorporation of pentavalent Np into uranyl phases. Following synthesis, crystals are analyzed for Np using laser ablation ICP-MS. Preliminary results for Na-substituted metaschoepite indicate significant Np has been incorporated into the crystals. Additional phases under study include compreignacite, becquerelite, soddyite, zippeite, and (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}(H{sub 2}O){sub 4}.

  19. Adsorption of uranyl on hydroxylated α-SiO₂(001): a first-principle study.

    PubMed

    Wang, Hui; Chai, Zhifang; Wang, Dongqi

    2015-01-28

    The adsorption of [UO2(H2O)5](2+) on a hydroxylated α-SiO2(001) surface was studied by periodic density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulation. The effects of pH, CO2, aqua solution and anionic ligands (OH(-), NO3(-) and Cl(-)) on the adsorption geometry and stability were investigated. The results show that the adsorption of uranyl on a hydroxylated α-SiO2(001) surface leads to the formation of inner-sphere complexes, in which the bidentate complex at the double deprotonated site is most favored. The binding strengths of bidentate and monodentate complexes at the same site are similar, and they become weaker as the number of protons increases at the adsorption site, indicating an enhancement of the adsorption strength at higher pH values within a certain range. Strong chemical interaction plays an important role in all inner-sphere complexes. The hydrogen bonds are formed between uranyl and the hydroxylated surface in all inner- and outer-sphere complexes. The presence of CO2 weakens the adsorption of uranyl on the surface by forming uranyl carbonate (CO3(2-), HCO3(-)) complexes. The effect of the anion ligands depends on their charged state and their concentration in solutions. The explicit treatment of water environment in the models has a slight effect on the adsorption configuration. These results are consistent with the experimental observations. PMID:25437449

  20. Syntheses and Characterization of Ruthenium(II) Tetrakis(pyridine)complexes: An Advanced Coordination Chemistry Experiment or Mini-Project

    ERIC Educational Resources Information Center

    Coe, Benjamin J.

    2004-01-01

    An experiment for third-year undergraduate a student is designed which provides synthetic experience and qualitative interpretation of the spectroscopic properties of the ruthenium complexes. It involves the syntheses and characterization of several coordination complexes of ruthenium, the element found directly beneath iron in the middle of the…

  1. Coordination Complexes as Catalysts: The Oxidation of Anthracene by Hydrogen Peroxide in the Presence of VO(acac)[subscript 2

    ERIC Educational Resources Information Center

    Charleton, Kimberly D. M.; Prokopchuk, Ernest M.

    2011-01-01

    A laboratory experiment aimed at students who are studying coordination chemistry of transition-metal complexes is described. A simple vanadyl acetylacetonate complex can be used as a catalyst in the hydrogen peroxide oxidation of anthracene to produce anthraquinone. The reaction can be performed under a variety of reaction conditions, ideally by…

  2. Catalytic alcohol oxidation by an unsymmetrical 5-coordinate copper complex: electronic structure and mechanism.

    PubMed

    Zueva, Ekaterina; Walton, Paul H; McGrady, John E

    2006-01-01

    Density functional theory reveals the detailed mechanism of alcohol oxidation by a model copper complex, Cu(II)L, L = cis-1-(3',5'-dimethoxy-benzylideneamino)-3,5-[2-hydroxy-(3',5'-di-tert-butyl)benzylideneimino]cyclohexane. Despite the obvious structural and functional parallels between the title compound and the enzyme galactose oxidase, the details of the catalytic pathway are fundamentally different. In the enzyme, coordination of the substrate produces an active form containing a Cu(II) centre and a tyrosyl radical, the latter being responsible for the abstraction of hydrogen from the substrate. In the model system, in marked contrast, the active form contains a Cu(II) centre, but the ligand radical character is localised on the substrate (alcoholate) oxygen, rather than the phenolate ligand. The result is a significantly higher barrier to hydrogen-atom abstraction compared to the enzyme itself. The origin of these significant differences is traced to the rigid nature of the pentadentate ligand, which resists changes in coordination number during the catalytic cycle. PMID:16357972

  3. Insights into copper coordination in the EcoRI-DNA complex by ESR spectroscopy

    NASA Astrophysics Data System (ADS)

    Ji, Ming; Tan, Likun; Jen-Jacobson, Linda; Saxena, Sunil

    2014-12-01

    The EcoRI restriction endonuclease requires one divalent metal ion in each of two symmetrical and identical catalytic sites to catalyse double-strand DNA cleavage. Recently, we showed that Cu2+ binds outside the catalytic sites to a pair of new sites at H114 in each sub-unit, and inhibits Mg2+-catalysed DNA cleavage. In order to provide more detailed structural information on this new metal ion binding site, we performed W-band (∼94 GHz) and X-band (∼9.5 GHz) electron spin resonance spectroscopic measurements on the EcoRI-DNA-(Cu2+)2 complex. Cu2+ binding results in two distinct components with different gzz and Azz values. X-band electron spin echo envelope modulation results indicate that both components arise from a Cu2+ coordinated to histidine. This observation is further confirmed by the hyperfine sub-level correlation results. W-band electron nuclear double resonance spectra provide evidence for equatorial coordination of water molecules to the Cu2+ ions.

  4. [Complexity of social and healthcare coordination in addictions and the role of the nurse].

    PubMed

    Molina Fernández, Antonio Jesús; González Riera, Javier; Montero Bancalero, Francisco José; Gómez-Salgado, Juan

    2016-01-01

    The present article discusses the psychosocial impact of basic and advanced concepts, such as social support and prevention, as well as to establish a link between theoretical models related to the social sphere on one side, and the health aspects on the other. This work is based on the context of the influence on health shared by community psychology and social psychology. Starting from the historical background of current approaches, a review is presented of those first actions focused on the care plan and they are framed in a reaction model to the drug problem, which progressed to the current healthcare network model, through the creation of Spanish National Action Plan on Drugs. The complexity of the problem is then broken down into the following key elements: Multifactorial Model of Drugs and Addictions, importance of prevention, and social support. Subsequently, a description is presented on the different levels of the healthcare network, with their different resources. This is also illustrated using a coordination protocol. Finally, it features the nursing approach to drugs, with its contributions, particularly as regards the coordination of resources, and aspects that must be developed for improvement in this area. PMID:26654277

  5. Divergent Coordination Chemistry: Parallel Synthesis of [2×2] Iron(II) Grid-Complex Tauto-Conformers.

    PubMed

    Schäfer, Bernhard; Greisch, Jean-François; Faus, Isabelle; Bodenstein, Tilmann; Šalitroš, Ivan; Fuhr, Olaf; Fink, Karin; Schünemann, Volker; Kappes, Manfred M; Ruben, Mario

    2016-08-26

    The coordination of iron(II) ions by a homoditopic ligand L with two tridentate chelates leads to the tautomerism-driven emergence of complexity, with isomeric tetramers and trimers as the coordination products. The structures of the two dominant [Fe(II) 4 L4 ](8+) complexes were determined by X-ray diffraction, and the distinctness of the products was confirmed by ion-mobility mass spectrometry. Moreover, these two isomers display contrasting magnetic properties (Fe(II) spin crossover vs. a blocked Fe(II) high-spin state). These results demonstrate how the coordination of a metal ion to a ligand that can undergo tautomerization can increase, at a higher hierarchical level, complexity, here expressed by the formation of isomeric molecular assemblies with distinct physical properties. Such results are of importance for improving our understanding of the emergence of complexity in chemistry and biology. PMID:27411212

  6. Neutral, seven-coordinate dioxime complexes of technetium(III): Synthesis and characterization

    SciTech Connect

    Linder, K.E.; Malley, M.F.; Gougoutas, J.Z.; Unger, S.E.; Nunn, A.D. )

    1990-06-27

    The tin-capped complexes {sup 99}Tc(oxime){sub 3}({mu}-OH)SnCl{sub 3} (oxime = dimethylglyoxime (DMG) or cyclohexanedione dioxime (CDO)) can be prepared by the reduction of NH{sub 4}TcO{sub 4} with 2 equiv of SnCl{sub 2} in the presence of dioxime and HCl. These tin-capped complexes can be readily converted into a new class of uncapped Tc-dioxime compounds, TcCl(oxime){sub 3}, by treatment with HCl. This reaction is reversible. Both the tin-capped and uncapped tris(dioxime) complexes can be converted to the previously reported boron-capped Tc-dioxime complexes TcCl(oxime){sub 3}BR (R = alkyl, OH) by reaction with boronic acids or with boric acid at low pH. All of these complexes (Tc(oxime){sub 3}({mu}-OH)SnCl{sub 3}, TcCl(oxime){sub 3}, and TcCl(oxime){sub 3}BR) appear to be neutral, seven-coordinate compounds of technetium(III). They have been characterized by elemental analysis, {sup 1}H NMR and UV/visible spectroscopy, conductivity, and fast atom bombardment mass spectrometry. The synthesis, characterization, and reactivity of these compounds is discussed. The x-ray crystal structure analysis of TcCl(DMG){sub 3} and an abbreviated structure report on TcCl(DMG){sub 3}MeB are described. Crystal data for TcCl(DMG){sub 3} are reported. 23 refs., 6 figs., 5 tabs.

  7. Enhanced environmental detection of uranyl compounds based on luminescence characterization

    NASA Astrophysics Data System (ADS)

    Nelson, Jean Dennis

    Uranium (U) contamination can be introduced to the environment as a result of mining and manufacturing activities related to nuclear power, detonation of U-containing munitions (DoD), or nuclear weapons production/processing (DOE facilities). In oxidizing environments such as surface soils, U predominantly exists as U(VI), which is highly water soluble and very mobile in soils. U(VI) compounds typically contain the UO22+ group (uranyl compounds). The uniquely structured and long-lived green luminescence (fluorescence) of the uranyl ion (under UV radiation) has been studied and remained a strong topic of interest for two centuries. The presented research is distinct in its objective of improving capabilities for remotely sensing U contamination by understanding what environmental conditions are ideal for detection and need to be taken into consideration. Specific focuses include: (1) the accumulation and fluorescence enhancement of uranyl compounds at soil surfaces using distributed silica gel, and (2) environmental factors capable of influencing the luminescence response, directly or indirectly. In a complex environmental system, matrix effects co-exist from key soil parameters including moisture content (affected by evaporation, temperature and humidity), soil texture, pH, CEC, organic matter and iron content. Chapter 1 is a review of pertinent background information and provides justification for the selected key environmental parameters. Chapter 2 presents empirical investigations related to the fluorescence detection and characterization of uranyl compounds in soil and aqueous samples. An integrative experimental design was employed, testing different soils, generating steady-state fluorescence spectra, and building a comprehensive dataset which was then utilized to simultaneously test three hypotheses: The fluorescence detection of uranyl compounds is dependent upon (1) the key soil parameters, (2) the concentration of U contamination, and (3) time of analysis

  8. A Molecular Artisans Guide to Supramolecular Coordination Complexes and Metal Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Wu, Xialu; Young, David J.; Hor, T. S. Andy

    2015-10-01

    As molecular synthesis advances, we are beginning to learn control of not only the chemical reactivity (and function) of molecules, but also of their interactions with other molecules. It is this basic idea that has led to the current explosion of supramolecular science and engineering. Parallel to this development, chemists have been actively pursuing the design of very large molecules using basic molecular building blocks. Herein, we review the general development of supramolecular chemistry and particularly of two new branches: supramolecular coordination complexes (SCCs) and metal organic frameworks (MOFs). These two fields are discussed in detail with typical examples to illustrate what is now possible and what challenges lie ahead for tomorrow's molecular artisans.

  9. Analytical description for the critical fixations of evolutionary coordination games on finite complex structured populations

    NASA Astrophysics Data System (ADS)

    Zhang, Liye; Zou, Yong; Guan, Shuguang; Liu, Zonghua

    2015-04-01

    Evolutionary game theory is crucial to capturing the characteristic interaction patterns among selfish individuals. In a population of coordination games of two strategies, one of the central problems is to determine the fixation probability that the system reaches a state of networkwide of only one strategy, and the corresponding expectation times. The deterministic replicator equations predict the critical value of initial density of one strategy, which separates the two absorbing states of the system. However, numerical estimations of this separatrix show large deviations from the theory in finite populations. Here we provide a stochastic treatment of this dynamic process on complex networks of finite sizes as Markov processes, showing the evolutionary time explicitly. We describe analytically the effects of network structures on the intermediate fixations as observed in numerical simulations. Our theoretical predictions are validated by various simulations on both random and scale free networks. Therefore, our stochastic framework can be helpful in dealing with other networked game dynamics.

  10. Two-coordinate terminal zinc hydride complexes: synthesis, structure and preliminary reactivity studies.

    PubMed

    Dawkins, Michael J C; Middleton, Ewart; Kefalidis, Christos E; Dange, Deepak; Juckel, Martin M; Maron, Laurent; Jones, Cameron

    2016-08-18

    The first examples of essentially two-coordinate, monomeric zinc hydride complexes, LZnH (L = -N(Ar)(SiR3)) (Ar = C6H2{C(H)Ph2}2R'-2,6,4; R = Me, R' = Pr(i) (L'); R = Pr(i), R' = Me (L*); R = Pr(i), R' = Pr(i) (L(†))) have been prepared and shown by crystallographic studies to have near linear N-Zn-H fragments. The results of computational studies imply that any PhZn interactions in the compounds are weak at best. Preliminary reactivity studies reveal the compounds to be effective for the stoichiometric hydrozincation and catalytic hydrosilylation of carbonyl compounds. PMID:27499232

  11. Synthesis, structure, and spectroscopic characterization of three uranyl phosphates with unique structural units

    NASA Astrophysics Data System (ADS)

    Wylie, Ernest M.; Dawes, Colleen M.; Burns, Peter C.

    2012-12-01

    Single crystals of Zn4(OH)2[(UO2)(PO4)2(OH)2(H2O)] (UZnP), Cs[(UO2)(HPO4)NO3] (UCsP), and In3[(UO2)2(PO4)4OH(H2O)6].2H2O (UInP) were obtained from hydrothermal reactions and have been structurally and chemically characterized. UZnP crystallizes in space group Pbcn, a=8.8817(7), b=6.6109(5), c=19.569(1) Å; UCsP crystallizes in P-1, a=7.015(2), b=7.441(1), c=9.393(2) Å, α=72.974(2), β=74.261(2), γ=79.498(2); and UInP crystallizes in P-1, a=7.9856(5), b=9.159(1), c=9.2398(6) Å α=101.289(1), β=114.642(1), γ=99.203(2). The U6+ cations are present as (UO2)2+ uranyl ions coordinated by five O atoms to give pentagonal bipyramids. The structural unit in UZnP is a finite cluster containing a uranyl pentagonal bipyramid that shares corners with two phosphate tetrahedra. The structural unit in UCsP is composed of uranyl pentagonal bipyramids with one chelating nitrate group that are linked into chains by three bridging hydrogen phosphate tetrahedra. In UInP, the structural unit contains pairs of edge-sharing uranyl pentagonal bipyramids with two chelating phosphate tetrahedra that are linked into chains through two bridging phosphate tetrahedra. Indium octahedra link these uranyl phosphate chains into a 3-dimensional framework. All three compounds exhibit unique structural units that deviate from the typical layered structures observed in uranyl phosphate solid-state chemistry.

  12. Polymer complexes.. XXXX. Supramolecular assembly on coordination models of mixed-valence-ligand poly[1-acrylamido-2-(2-pyridyl)ethane] complexes

    NASA Astrophysics Data System (ADS)

    El-Sonbati, A. Z.; El-Bindary, A. A.; Diab, M. A.

    2003-02-01

    The build-up of polymer metallic supramolecules based on homopolymer (1-acrylamido-2-(2-pyridyl)ethane (AEPH)) and ruthenium, rhodium, palladium as well as platinum complexes has been pursued with great interest. The homopolymer shows three types of coordination behaviour. In the mixed valence paramagnetic trinuclear polymer complexes [( 11)+( 12)] in the paper and in mononuclear polymer complexes ( 1)-( 5) it acts as a neutral bidentate ligand coordinating through the N-pyridine and NH-imino atoms, while in the mixed ligand diamagnetic poly-chelates, which are obtained from the reaction of AEPH with PdX 2 and KPtCl 4 in the presence of N-heterocyclic base consisting of polymer complexes ( 9)+( 10), and in monouclear compounds ( 6)-( 8), it behaves as a monobasic bidentate ligand coordinating through the same donor atoms. In mononuclear compounds ( 13)+( 14) it acts as a monobasic and neutral bidentate ligand coordinating only through the same donor atoms. Monomeric distorted octahedral or trimeric chlorine-bridged, approximately octahedral structures are proposed for these polymer complexes. The poly-chelates are of 1:1, 1:2 and 3:2 (metal-homopolymer) stoichiometry and exhibit six coordination. The values of ligand field parameters were calculated. The homopolymer and their polymer complexes have been characterized physicochemically.

  13. Solution interactions between the uranyl cation [UO2(2+)] and histidine, N-acetyl-histidine, tyrosine, and N-acetyl-tyrosine.

    PubMed

    Xie, Wei; Badawi, Ahmed; Huang, Huan; Van Horn, J David

    2009-01-01

    Complexes of the uranyl cation [UO(2)(2+)] with histidine (His), N-acetyl-histidine (NAH), tyrosine (Tyr), and N-acetyl-tyrosine (NAT) were studied by UV-visible and NMR spectroscopy, and by potentiometric titration. Protonation constants for each ligand are reported, as are cumulative formation constants for uranyl-amino acid complexes. Coupling constant data (J(CH)) for uranyl-histidine complexes indicate that inner-sphere solution interactions between histidine and uranyl cation are solely at the carboxylate site. At 25 degrees C the major uranyl-histidine complex has a cumulative formation constant of logbeta(110)=8.53, and a proposed formula of [UO(2)HisH(2)(OH)(2)](+); the stepwise formation constant, logK(UL), is estimated to be 5.6 ( approximately 8.53-(-6.1)-(-6.1)-15.15). Outer-sphere interactions, H-bonding or electrostatic interactions, are proposed as contributing a significant portion of the stability to the ternary uranyl-hydroxo-amino acid complexes. The temperature dependent protonation constants of histidine and formation constants between uranyl cation and histidine are reported from 10 to 35 degrees C; at 25 degrees C, DeltaG=-43.3 kJ/mol. PMID:18947879

  14. Revision of the biodistribution of uranyl in serum: is fetuin-A the major protein target?

    PubMed

    Basset, Christian; Averseng, Olivier; Ferron, Pierre-Jean; Richaud, Nicolas; Hagège, Agnès; Pible, Olivier; Vidaud, Claude

    2013-05-20

    Uranium is a natural actinide present as uranyl U(VI) species in aqueous environments. Its toxicity is considered to be chemical rather than radiotoxicological. Whatever the route of entry, uranyl reaches the blood, is partly eliminated via the kidneys, and accumulated in the bones. In serum, its speciation mainly involves carbonate and proteins. Direct identification of labile uranyl-protein complexes is extremely difficult because of the complexity of this matrix. Thus, until now the biodistribution of the metal in serum has not been described, and therefore, little is known about the metal transport mechanisms leading to bone accumulation. A rapid screening method based on a surface plasmon resonance (SPR) technique was used to determine the apparent affinities for U(VI) of the major serum proteins. A first biodistribution of uranyl was obtained by ranking the proteins according to the criteria of both their serum concentrations and affinities for this metal. Despite its moderate concentration in serum, fetuin-A (FETUA) was shown to exhibit an apparent affinity within the 30 nM range and to carry more than 80% of the metal. This protein involved in bone mineralization aroused interest in characterizing the U(VI) and FETUA interaction. Using complementary chromatographic and spectroscopic approaches, we demonstrated that the protein can bind 3 U(VI) at different binding sites exhibiting Kd from ∼30 nM to 10 μM. Some structural modifications and functional properties of FETUA upon uranyl complexation were also controlled. To our knowledge, this article presents the first identification of a uranyl carrier involved in bone metabolism along with the characterization of its metal binding sites. PMID:23527557

  15. Cobalamin reduction by dithionite. Evidence for the formation of a six-coordinate cobalamin(II) complex.

    PubMed

    Salnikov, Denis S; Silaghi-Dumitrescu, Radu; Makarov, Sergei V; van Eldik, Rudi; Boss, Gerry R

    2011-10-14

    Evidence for the formation of a unique, six-coordinate cobalamin(II) complex with the anion-radical SO(2)(-) during the reduction of aquacobalamin(III) by sodium dithionite, was obtained from spectrophotometric and EPR measurements. The pK(a) value of the weakly coordinated dimethylbenzimidazole group was found to be 4.8 ± 0.1 at 25 °C. PMID:21879074

  16. ESEEM Analysis of Multi-Histidine Cu(II)-Coordination in Model Complexes, Peptides, and Amyloid-β

    PubMed Central

    2015-01-01

    We validate the use of ESEEM to predict the number of 14N nuclei coupled to a Cu(II) ion by the use of model complexes and two small peptides with well-known Cu(II) coordination. We apply this method to gain new insight into less explored aspects of Cu(II) coordination in amyloid-β (Aβ). Aβ has two coordination modes of Cu(II) at physiological pH. A controversy has existed regarding the number of histidine residues coordinated to the Cu(II) ion in component II, which is dominant at high pH (∼8.7) values. Importantly, with an excess amount of Zn(II) ions, as is the case in brain tissues affected by Alzheimer’s disease, component II becomes the dominant coordination mode, as Zn(II) selectively substitutes component I bound to Cu(II). We confirm that component II only contains single histidine coordination, using ESEEM and set of model complexes. The ESEEM experiments carried out on systematically 15N-labeled peptides reveal that, in component II, His 13 and His 14 are more favored as equatorial ligands compared to His 6. Revealing molecular level details of subcomponents in metal ion coordination is critical in understanding the role of metal ions in Alzheimer’s disease etiology. PMID:25014537

  17. The HITECH Act and electronic health records' limitation in coordinating care for children with complex chronic conditions.

    PubMed

    Cook, Jason E

    2014-01-01

    While the HITECH Act was implemented to promote the use of electronic health records to improve the quality and coordination of healthcare, the limitations established to the setting of the hospital or physician's office affect the care coordination for those who utilize many health-related services outside these settings, including children with complex and chronic conditions. Incentive-based support or nationally supported electronic health record systems for allied and other healthcare professionals are necessary to see the full impact that electronic health records can have on care coordination for individuals who utilize many skilled healthcare services that are not associated with a hospital or physician's office. PMID:24925039

  18. Selective recognition of uranyl ions from bulk of thorium(iv) and lanthanide(iii) ions by tetraalkyl urea: a combined experimental and quantum chemical study.

    PubMed

    Vats, Bal Govind; Das, Debasish; Sadhu, Biswajit; Kannan, S; Pius, I C; Noronha, D M; Sundararajan, Mahesh; Kumar, Mukesh

    2016-06-21

    The selective separation of uranyl ions from an aqueous solution is one of the most important criteria for sustainable nuclear energy production. We report herein a known, but unexplored extractant, tetraalkyl urea, which shows supreme selectivity for uranium in the presence of interfering thorium and other lanthanide ions from a nitric acid medium. The structural characterization of the uranyl complex (UO2X2·2L, where X = NO3(-), Cl(-) and Br(-)) by IR, NMR and single crystal X-ray diffraction provides insight into the strong interaction between the uranyl ion and the ligand. The origin of this supreme selectivity for uranyl ions is further supported by electronic structure calculations. Uranyl binding with the extractant is thermodynamically more favourable when compared to thorium and the selectivity is achieved through a combination of electronic and steric effects. PMID:27241102

  19. Dissecting the cation-cation interaction between two uranyl units.

    PubMed

    Tecmer, Paweł; Hong, Sung W; Boguslawski, Katharina

    2016-07-21

    We present a state-of-the-art computational study of the uranyl(vi) and uranyl(v) cation-cation interactions (dications) in aqueous solution. Reliable electronic structures of two interacting uranyl(vi) and uranyl(v) subunits as well as those of the uranyl(vi) and uranyl(v) clusters are presented for the first time. Our theoretical study elucidates the impact of cation-cation interactions on changes in the molecular structure as well as changes in vibrational and UV-Vis spectra of the bare uranyl(vi) and uranyl(v) moieties for different total spin-states and total charges of the dications. PMID:27335229

  20. Theoretical calculations on the conformation of cyclopentadienyl coordination in Ru nitrosyl and thionitrosyl complexes

    SciTech Connect

    Burns, R.M.; Hubbard, J.L.; McCullough, E.A. Jr.

    1995-12-01

    X-ray structural characterization of a series of CpRu(NE)LL` complexes (Cp = cyclopentadieny), C{sub 5}R{sub 5}; L, L` = ligand; E = O, S) reveals systematic trends in the coordination conformation of the cyclopentadienyl ligand. The thionitrosyl complex (C{sub 5}(CH{sub 3}){sub 5})Ru(NS)Cl{sub 2} exhibits a slipped (eta-3,eta-2 Cp ring, with the central C(skeletal)-CH{sub 3} bond of the more tightly bound eta-3 portion eclipsing the Ru-N-S vector. With NO derivatives, ring {open_quotes}slippage{close_quotes} is not significant, but ring orientation is variable depending upon the L and L` ligand set. NMR spectroscopy measurements show that the barriers to changes in ring conformation become very low in solution. For catalytic purposes, it is of interest to fix the Cp geometry with respect to rotation. Ab initio SCF and DFT calculations have been performed, using the NWChem suite of computer codes, developed at Pacific Northwest Laboratory, to explore three questions: By what mechanism does the choice of ligand affect the Cp orientation? What is the barrier to rotation of the Cp? By what mechanism does salvation affect the barriers to Cp rotation?

  1. Pseudo-symmetry analysis of the d-block molecular orbitals in four-coordinate complexes.

    PubMed

    Falceto, Andrés; Casanova, David; Alemany, Pere; Alvarez, Santiago

    2013-06-01

    A rigorous definition of the concept of pseudo-symmetry, which is as important to chemistry as the concepts of symmetry implemented through group theory, should allow us to apply those group theoretical tools to molecules that are significantly distorted from those ideal symmetries best known and understood by the chemical community. In this paper, we consider four-coordinate transition-metal complexes with geometries along the interconversion path between the square and the tetrahedron and show how their molecular orbitals can be expressed in terms of either the tetrahedral or tetragonal symmetry groups. Furthermore, we analyze how the intensity of a d-d absorption band can be related to the degree of symmetry loss of the d-block molecular orbitals by means of their decomposition in terms of contributions from different pseudo-symmetry representations. As a final example, we also show how the substitution of a single ligand in a square planar complex affects the symmetry of the molecular orbitals and the absorption intensity associated to an electronic transition. PMID:23668721

  2. Reactivity of thiosemicarbazides with redox active metal ions: controlled formation of coordination complexes versus heterocyclic compounds.

    PubMed

    López-Torres, Elena; Dilworth, Jonathan R

    2009-01-01

    The reactions of 1,1-dimethyl-4-phenylthiosemicarbazide (LH) with Cu(II) and Sn(IV) have been investigated. If THF or methanol is used as solvent with Cu(II), oxidative cyclisation and coupling are observed, yielding a 1,2,4-thiadiazole or a 1,3,4-thiadiazolium salt. SnI(4) is also able to induce oxidative coupling of two thiosemicarbazide ligands, yielding 1,2,4-thiadiazolium or 1,2,4-triazolium salts, with I(3)(-) as the counterion, depending on the reaction conditions. By contrast, reaction of LH with SnI(4) in acetone yields a 1,3-thiazolium salt, with I(-) as counterion. Reaction with Cu(II) salts or SnI(4) in basic media leads to the formation of metal complexes containing two deprotonated thiosemicarbazide ligands. In the reaction of CuCl(2) in water in the presence of acid a complex containing two neutral ligands is obtained. Reactions with SnCl(4) are not able to induce ligand cyclisation, although a coordination compound with two neutral ligands was isolated from methanol. PMID:19180593

  3. Vibrational Spectroscopy of Mass-Selected [UO2(ligand)n]2+ Complexes in the Gas Phase: Comparison with Theory

    SciTech Connect

    Gary S. Groenewold; Anita K. Gianotto

    2006-03-01

    The gas-phase infrared spectra of discrete uranyl ([UO2]2+) complexes ligated with acetone and/or acetonitrile were used to evaluate systematic trends of ligation on the position of the OdUdO stretch and to enable rigorous comparison with the results of computational studies. Ionic uranyl complexes isolated in a Fourier transform ion cyclotron resonance mass spectrometer were fragmented via infrared multiphoton dissociation using a free electron laser scanned over the mid-IR wavelengths. The asymmetric OdUdO stretching frequency was measured at 1017 cm-1 for [UO2(CH3COCH3)2]2+ and was systematically red shifted to 1000 and 988 cm-1 by the addition of a third and fourth acetone ligand, respectively, which was consistent with increased donation of electron density to the uranium center in complexes with higher coordination number. The values generated computationally using LDA, B3LYP, and ZORA-PW91 were in good agreement with experimental measurements. In contrast to the uranyl frequency shifts, the carbonyl frequencies of the acetone ligands were progressively blue shifted as the number of ligands increased from two to four and approached that of free acetone. This observation was consistent with the formation of weaker noncovalent bonds between uranium and the carbonyl oxygen as the extent of ligation increases. Similar trends were observed for [UO2(CH3CN)n]2+ complexes, although the uranyl asymmetric stretching frequencies were greater than those measured for acetone complexes having equivalent coordination, which is consistent with the fact that acetonitrile is a weaker nucleophile than is acetone. This conclusion was confirmed by the uranyl stretching frequencies measured for mixed acetone/acetonitrile complexes, which showed that substitution of one acetone for one acetonitrile produced a modest red shift of 3-6 cm-1.

  4. Three new silver uranyl diphosphonates: structures and properties.

    PubMed

    Nelson, Anna-Gay D; Rak, Zsolt; Albrecht-Schmitt, Thomas E; Becker, Udo; Ewing, Rodney C

    2014-03-17

    The hydrothermal reaction of uranium trioxide and methylenediphosphonic acid in the presence of silver nitrate resulted in the formation of three new uranyl coordination polymers: AgUO2[CH2(PO3)(PO3H)] (Ag-1), [Ag2(H2O)1.5]{(UO2)2[CH2(PO3)2]F2}·(H2O)0.5 (Ag-2), and Ag2UO2[CH2(PO3)2] (Ag-3). All consist of uranyl pentagonal bipyramids that form two-dimensional layered structures. Ag-1 and Ag-3 possess the same structural building unit, but the structures are different; Ag-3 is formed through edge-sharing of F atoms to form UO5F2 dimers. The pH and silver cation have significant effects on the structure that is synthesized. Raman spectra of single crystals of Ag-1, Ag-2, and Ag-3 reveal v1 UO2(2+) symmetric stretches of 816 and 829, 822, and 802 cm(-1), respectively. Electronic structure calculations were performed using the projector augmented wave (PAW) method with density functional theory (DFT) to gain insight into the nature of bonding and electronic characteristics of the synthesized compounds. Herein, we report the syntheses, crystal structures, Raman spectroscopy, and luminescent behavior of these three compounds. PMID:24524249

  5. Photochemical reduction of uranyl nitrate

    SciTech Connect

    Duerksen, W.K.

    1993-10-20

    The photochemical reduction of uranyl nitrate solutions to tetravalent uranium was investigated as a means of producing uranium dioxide feed for the saltless direct oxide reduction (SDOR) process. At high uranium concentrations, reoxidation of U{sup +4} occurs rapidly. The kinetics of the nitric oxidation of tetravalent uranium depend on the concentrations of hydrogen ion, nitrate ion, nitrous acid, and tetravalent uranium in the same manner as was reported elsewhere for the nitrate oxidation of PU{sup +3}. Reaction rate data were successfully correlated with a mechanism in which nitrogen dioxide is the reactive intermediate. Addition of a nitrous acid scavenger suppresses the reoxidation reaction. An immersion reactor employing a mercury vapor lamp gave reduction times fast enough for routine production usage. Precipitation techniques for conversion of aqueous U(NO{sub 3}){sub 4} to hydrous UO{sub 2} were evaluated. Prolonged dewatering times tended to make the process time consuming. Use of 3- to 4-M aqueous NaOH gave the best dewatering times observed. Reoxidation of the UO{sub 2} by water of hydration was encountered, which required the drying process to be carried out under a reducing atmosphere.

  6. A Porphyrin Coordination Cage Assembled from Four Silver(I) Triazolyl-Pyridine Complexes.

    PubMed

    Ballester, Pablo; Claudel, Mickaël; Durot, Stéphanie; Kocher, Lucas; Schoepff, Laetitia; Heitz, Valérie

    2015-10-19

    The synthesis of a zinc(II) porphyrin 1 with four appended triazolyl-pyridine chelates is reported. Complexation of the porphyrin peripheral ligands with Ag(I) ions in a 1:2 binding stoichiometry afforded quantitatively the coordination cage [Ag4 (1)2 ](4+) . The assembly and disassembly processes of the cage were investigated in solution using UV/Vis spectroscopy. The mathematical analysis of the data obtained in the UV/Vis titration of 1 with Ag(I) confirmed the assembly in CH2 Cl2 /MeOH (90:10) solution of a species having a 1:2 porphyrin/silver stoichiometry and assigned to it an overall stability constant of 5.0×10(26)  M(-5) . The use of a model system allowed an independent assessment of a microscopic binding constant value (Km ) for the interaction between the triazolyl-pyridine ligand and Ag(I) . The coincidence that existed between the Km values extracted from the model system and the titration of 1 provided an indication of the quality and fit of the data analysis. It also allowed the calculation of the average effective molarity (EM) value for the three intramolecular processes that led to the cage assembly as 2.6 mM. Simulated speciation profiles supported the conclusion that at millimolar concentration and working under strict stoichiometric control of the silver/porphyrin ratio, the cage [Ag4 (1)2 ](4+) was the species exclusively assembled in solution. On the other hand, when the concentration of added Ag(I) was approximately 2.6 mM, 50 % of the coordination cage disassembled into open aggregates. PMID:26338089

  7. Synthesis and structural evaluation of five coordination complexes of benzenepentacarboxylic acid with aza-donor ligands

    NASA Astrophysics Data System (ADS)

    Shimpi, Manishkumar R.; Biswas, Sharmita Nandy; Sarkar, Sohini; Pedireddi, V. R.

    2016-06-01

    Synthesis and structural features of five new coordination assemblies, [Co(bpyH)(H2O)5](BPCH)·(bpyH2)0.5·(H2O) (1a), [{Cu(H2O)3}·{Cu0.5(bpy)0.5(H2O)0.5}2(μ-BPCH)] (1b), [{Cd0.5(BPCH)}2·{Cd0.5(bpy)(H2O)2}2]·6(H2O) (1c), [Cu(BPCH2)(bpyeaH)]·2(H2O) (1d) and [Cd2 (bpyea)0.5(oxalate)0.5(μ-BPC) (H2O)]·(bpyeaH2)·2(H2O) (1e), have been reported. All the assemblies were prepared by co-crystallization of benzenepentacarboxylic acid (BPCH5) either with 4,4‧-bipyridine (bpy) or 1,2-bis(4-pyridyl)ethane (bpyea) in the presence of a transition metal ion (either Co(II), Cu(II) or Cd(II)) as the case may be. All the five compounds were synthesized by hydrothermal method and structures were determined by single crystal X-ray diffraction. All the obtained compounds, 1a-1e, exhibit distinct 3-D polymeric architectures either in the form of stacked layers or host-guest networks in which water molecules play a pivotal role providing additional stabilization by coordinate bonds as well as hydrogen bonds. Other non-covalent interactions such as C-H … π and π … π stacking also participate in the formation of exotic 3-D structures of these complexes.

  8. X-ray Emission Spectroscopy to Study Ligand Valence Orbitals in Mn Coordination Complexes

    SciTech Connect

    Smolentsev, Grigory; Soldatov, Alexander V; Messinger, Johannes; Merz, Kathrin; Weyhermuller, Thomas; Bergmann, Uwe; Pushkar, Yulia; Yano, Junko; Yachandra, Vittal K.; Glatzel, Pieter

    2009-03-02

    We discuss a spectroscopic method to determine the character of chemical bonding and for the identification of metal ligands in coordination and bioinorganic chemistry. It is based on the analysis of satellite lines in X-ray emission spectra that arise from transitions between valence orbitals and the metal ion 1s level (valence-to-core XES). The spectra, in connection with calculations based on density functional theory (DFT), provide information that is complementary to other spectroscopic techniques, in particular X-ray absorption (XANES and EXAFS). The spectral shape is sensitive to protonation of ligands and allows ligands, which differ only slightly in atomic number (e.g., C, N, O...), to be distinguished. A theoretical discussion of the main spectral features is presented in terms of molecular orbitals for a series of Mn model systems: [Mn(H2O)6]2+, [Mn(H2O)5OH]+, [Mn(H2O)5NH2]+, and [Mn(H2O)5NH3]2+. An application of the method, with comparison between theory and experiment, is presented for the solvated Mn2+ ion in water and three Mn coordination complexes, namely [LMn(acac)N3]BPh4, [LMn(B2O3Ph2)(ClO4)], and [LMn(acac)N]BPh4, where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane, acac stands for the 2,4-pentanedionate anion, and B2O3Ph2 represents the 1,3-diphenyl-1,3-dibora-2-oxapropane-1,3-diolato dianion.

  9. Control of the axial coordination of a surface-confined manganese(III) porphyrin complex

    NASA Astrophysics Data System (ADS)

    Beggan, J. P.; Krasnikov, S. A.; Sergeeva, N. N.; Senge, M. O.; Cafolla, A. A.

    2012-06-01

    The organization and thermal lability of chloro(5,10,15,20-tetraphenylporphyrinato)manganese(III) (Cl-MnTPP) molecules on the Ag(111) surface have been investigated under ultra-high vacuum conditions, using scanning tunnelling microscopy, low energy electron diffraction and x-ray photoelectron spectroscopy. The findings reveal the epitaxial nature of the molecule-substrate interface, and moreover, offer a valuable insight into the latent coordination properties of surface-confined metalloporphyrins. The Cl-MnTPP molecules are found to self-assemble on the Ag(111) surface at room temperature, forming an ordered molecular overlayer described by a square unit cell. In accordance with the threefold symmetry of the Ag(111) surface, three rotationally equivalent domains of the molecular overlayer are observed. The primitive lattice vectors of the Cl-MnTPP overlayer show an azimuthal rotation of ±15° relative to those of the Ag(111) surface, while the principal molecular axes of the individual molecules are found to be aligned with the substrate \\langle 0\\bar {1}1\\rangle and \\langle \\bar {2}1 1\\rangle crystallographic directions. The axial chloride (Cl) ligand is found to be orientated away from the Ag(111) surface, whereby the average plane of the porphyrin macrocycle lies parallel to that of the substrate. When adsorbed on the Ag(111) surface, the Cl-MnTPP molecules display a latent thermal lability resulting in the dissociation of the axial Cl ligand at ˜423 K. The thermally induced dissociation of the Cl ligand leaves the porphyrin complex otherwise intact, giving rise to the coordinatively unsaturated Mn(III) derivative. Consistent with the surface conformation of the Cl-MnTPP precursor, the resulting (5,10,15,20-tetraphenylporphyrinato)manganese(III) (MnTPP) molecules display the same lattice structure and registry with the Ag(111) surface.

  10. Challenging conventional f-element separation chemistry--reversing uranyl(VI)/lanthanide(III) solvent extraction selectivity.

    PubMed

    Hawkins, C A; Bustillos, C G; Copping, R; Scott, B L; May, I; Nilsson, M

    2014-08-14

    The water soluble tetradentate Schiff base, N,N'-bis(5-sulfonatosalicylidene)-diaminoethane (H2salen-SO3), will readily coordinate to the uranyl(VI) cation, but not to the same extent to trivalent lanthanide cations. This allows for the reversal of conventional solvent extraction properties and opens the possibility for novel separation processes. PMID:24958394

  11. [DOTA-bis(amide)]lanthanide complexes: NMR evidence for differences in water-molecule exchange rates for coordination isomers.

    PubMed

    Zhang, S; Kovacs, Z; Burgess, S; Aime, S; Terreno, E; Sherry, A D

    2001-01-01

    Two derivatives of 1,4,7,10-tetraazacyclododecane with trans-acetate and trans-amide side-chain ligating groups have been prepared and their complexes with lanthanide cations examined by multinuclear NMR spectroscopy. These lanthanide complexes exist in aqueous solution as a mixture of slowly interconverting coordination isomers with 1H chemical shifts similar to those reported previously for the major (M) and minor (m) forms of the tetraacetate ([Ln(dota)]-) and tetraamide ([Ln(dtma)]3+) complexes. As in the [Ln(dota)]- and [Ln(dtma)]3+ complexes, the m/M ratio proved to be a sensitive function of lanthanide size and temperature. An analysis of 1H hyperfine shifts in spectra of the Yb3+ complexes revealed significant differences between the axial (D1) and non-axial (D2) components of the magnetic susceptibility tensor anisotropy in the m and M coordination isomers and the energetics of ring inversion and m <==> M isomerization as determined by two-dimensional exchange spectroscopy (EXSY). (17)O shift data for the Dy3+ complexes showed that both have one inner-sphere water molecule. A temperature-dependent (17)O NMR study of bulk water linewidths for solutions of the Gd3+ complexes provided direct evidence for differences in water exchange rates for the two coordination isomers. The bound-water lifetimes (tauM298) in the M and m isomers of the Gd3+ complexes ranged from 1.4-2.4 micros and 3-14 ns, respectively. This indicates that 1) the inner-sphere water lifetimes for the complexes with a single positive charge reported here are considerably shorter for both coordination isomers than the corresponding values for the [Gd(dtma)]3+ complex with three positive charges, and 2) the difference in water lifetimes for M and m isomers in these two series is magnified in the [Gd[dota-bis(amide)

  12. Use of metalloligands [CuL] (H2L = salen type di-Schiff bases) in the formation of heterobimetallic copper(II)-uranyl complexes: photophysical investigations, structural variations, and theoretical calculations.

    PubMed

    Ghosh, Soumavo; Biswas, Saptarshi; Bauzá, Antonio; Barceló-Oliver, Miquel; Frontera, Antonio; Ghosh, Ashutosh

    2013-07-01

    Five heterobimetallic copper(II)-uranium(VI) complexes [(CuL(1))UO2(NO3)2] (1), [{CuL(1)(CH3CN)}UO2(NO3)2] (2), [{CuL(1)(CH3COCH3)}UO2(NO3)2] (3), [{CuL(2)(CH3CN)}UO2(NO3)2](4), and [{CuL(2)(CH3COCH3)}UO2(NO3)2][{CuL(2)}UO2(NO3)2] (5) have been synthesized by reacting the Cu(II)-derived metalloligands [CuL(1)] and [CuL(2)] (where, H2L(1) = N,N'-bis(α-methylsalicylidene)-1,3-propanediamine and H2L(2) = N,N'-bis(salicylidene)-1,3-propanediamine) with UO2(NO3)2·6H2O in 1:1 ratio by varying the reaction temperature and solvents. Absorption and fluorescence quenching experiments (steady-state and time-resolved) indicate the formation of 1:1 ground-state charge transfer copper(II)-uranium(VI) complexes in solution. X-ray single-crystal structure reveals that each complex contains diphenoxido bridged Cu(II)-U(VI) dinuclear core with two chelated nitrato coligands. The complexes are solvated (acetonitrile or acetone) in the axial position of the Cu(II) in different manner or desolvated. The supramolecular interactions that depend upon the co-ordinating metalloligands seem to control the solvation. In complexes 2 and 3 a rare NO3(-)···NO3(-) weak interaction plays an important role in forming supramolecular network whereas an uncommon U═O···NO3(-) weak interaction helps to self-assemble heterobinuclear units in complex 5. The significance of the noncovalent interactions in terms of energies and geometries has been analyzed using theoretical calculations. PMID:23786416

  13. Observation of Radiolytic Field Alteration of the Uranyl Cation in Bicarbonate Solution

    SciTech Connect

    Snow, Lanee A.; McNamara, Bruce K.; Sinkov, Sergey I.; Cho, Herman M.; Friese, Judah I.

    2006-12-01

    In previous work we demonstrated that radiolysis of uranyl tris carbonate in near neutral pH to alkaline carbonate solutions, could be followed by 13C NMR. Radiolysis of the complex produced novel uranyl peroxo carbonate solution state species, whose structures depended on the pH and radiolytic dose rate. In this work, we investigate speciation of the uranyl carbonate trimer which is predominant in bicarbonate solution near pH 5.9. We observe radiolytically derived speciation to different mixed peroxy carbonate species than seen in the higher pH solutions. Auto radiolysis of uranium (VI) carbonate solutions between pH 5.9 and 7.2 is shown to alter the uranium speciation over relatively short periods of time and was followed by 13C NMR and visible spectrophotometry, using dissolved 233(UO2)3(CO3)6 6- both as the radiolysis source (D= 14.9 Gy/hr) and as a trap for the newly formed hydrogen peroxide. Direct addition of hydrogen peroxide to solutions of the uranyl-carbonate trimer is shown to reproduce the 13 C NMR signatures of the complexe(s) formed by radiolysis, but additionally a variety of new complexes are revealed. Ratios of H2O2/trimer < 1.5 produced a uranyl peroxo carbonate adduct, that is shown to be common to the radiolytically produced species. Ratios of H2O2/ trimer >1 resulted in formation of stable higher order peroxo carbonate complexes. The 13C NMR signatures and visible spectra of these complexes are described here. Rigorous characterization of the species is an ongoing effort.

  14. Self-assembly of three new coordination complexes: Formation of 2-D square grid, 1-D chain and tape structures

    NASA Astrophysics Data System (ADS)

    Indrani, Murugan; Ramasubramanian, Ramasamy; Fronczek, Frank R.; Vasanthacharya, N. Y.; Kumaresan, Sudalaiandi

    2009-08-01

    Three distinct coordination complexes, viz., [Co(imi) 2(tmb) 2] ( 1) [where imi = imidazole], {[Ni(tmb) 2(H 2O) 3]·2H 2O} n ( 2) and [Cu 2(μ-tmb) 4(CH 3OH) 2] ( 3), have been synthesized hydrothermally by the reactions of metal acetates, 2,4,6-trimethylbenzoic acid (Htmb) and with or without appropriate amine. The Ni analogue of 1 and the Co analogue of 2 have also been synthesized. X-ray single-crystal diffraction suggests that complex 1 represents discrete mononuclear species and complex 2 represents a 1D chain coordination polymer in which the Ni(II) ions are connected by the bridging water molecules. Complex 3 represents a neutral dinuclear complex. In 1, the central metal ions are associated by the carboxylate moiety and imidazole ligands, whereas the central metal atom is coordinated to the carboxylate moiety and the respective solvent molecules in 2 and 3. In 3, the four 2,4,6-trimethylbenzoate moieties act as a bridge connecting two copper (II) ions and the O atoms of methanol coordinate in an anti arrangement to form a square pyramidal geometry, with the methanol molecule at the apical position. In all the three structures the central metal atom sits on a crystallographic inversion centre. In all the cases, the coordination entities are further organized via hydrogen bonding interactions to generate multifarious supramolecular networks. Complexes 1, 2 and 3 have also been characterized by spectroscopic (UV/Vis and IR) and thermal analysis (TGA). In addition, the complexes were found to exhibit antimicrobial activity.The magnetic susceptibility measurements, measured from 8 to 300 K, revealed antiferromagnetic interactions between the Co(II) ions in compound 1 and the Ni(II) ions in 1a, respectively.

  15. Nuclear magnetic resonance study of the kinetics of ligand-exchange reactions in uranyl complexes. Part 5. Exchange reaction of acetylacetonate in bis(acetylacetonato)(dimethyl sulfoxide)dioxouranium(VI)

    SciTech Connect

    Ikeda, Y.; Tomiyasu, H.; Fukutomi, H.

    1984-09-26

    The kinetics of the exchange reaction of acac in UO/sub 2/(acac)/sub 2/Me/sub 2/SO (acac = acetylacetonate, Me/sub 2/SO = dimethyl sulfoxide) has been studied in o-C/sub 6/H/sub 4/Cl/sub 2/ by means of /sup 1/H NMR. The exchange rate depends on the concentration of the enol isomer of acetylacetone in its low region and approaches to the limiting value in its high region. The rate-determining step seems to be ring opening for one of two coordinated acac ions. The kinetic parameters of this step at 25/sup 0/C were found to be: equilibrium constant = 2.04 sec/sup -1/, enthalpy = 66.4 +/- 8.4 kJ mol/sup -1/, and entropy = 17.1 +/- 28.6 J K/sup -1/ mol/sup -1/. It was found that the exchange rate is decreased by addition of free Me/sub 2/SO. This is explained by considering the competition of Me/sub 2/SO with the enol isomer in attacking the four-coordinated intermediate in the equatorial plane or the outer-sphere complex formation between UO/sub 2/(acac)/sub 2/Me/sub 2/SO and free Me/sub 2/SO.

  16. Elucidation of selectivity for uranyl ions with an ICT organosilane-modified fluorescent receptor.

    PubMed

    Karagöz, Fehmi; Güney, Orhan

    2014-05-01

    A fluorescent receptor, isocyanatopropyl trimethoxysilane grafted 9-amino acridine (AcI), was synthesized and characterized by elemental analysis, FTIR and NMR spectroscopy. Photophysical properties and pH-dependent fluorescence behavior of AcI were investigated and its complex stoichiometry with uranyl ion was elucidated. Change in fluorescence emission of AcI with pH of the solution was observed and pKa value was determined by using integrated emission intensity versus pH. It was found that AcI exhibited fluorescence enhancement, which can be attributed to an internal charge transfer (ICT) mechanism, upon titration with uranyl ions in mixture of ethanol-buffer solution while the fluorescence emission of AcI was not affected by addition of other divalent transition metal ions except mercury (II) ions. On the other hand, the both fluorescence and UV-vis titration measurements revealed unique selectivity for uranyl ions over the interfering mercury (II) ions. The spectrofluorometric titration clarified that uranyl interacted with AcI to form AcI 2(UO2(2 +))3 (2:3) complex structure with an apparent association constant of K = 7.41 × 10(6) M(-2/3). The interference effect of some cations on fluorescence enhancement exhibited by complex was also tested. PMID:24407892

  17. Structural observations of heterometallic uranyl copper(II) carboxylates and their solid-state topotactic transformation upon dehydration.

    PubMed

    Olchowka, Jakub; Falaise, Clément; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

    2013-02-01

    The hydrothermal reactions of uranyl nitrate and metallic copper with aromatic polycarboxylic acids gave rise to the formation of five heterometallic UO(2)(2+)-Cu(2+) coordination polymers: (UO(2))Cu(H(2)O)(2)(1,2-bdc)(2) (1; 1,2-bdc = phthalate), (UO(2))Cu(H(2)O)(2)(btec)⋅4 H(2)O (2) and (UO(2))Cu(btec) (2'; btec = pyromellitate), (UO(2))(2)Cu(H(2)O)(4)(mel) (3; mel = mellitate), and (UO(2))(2)O(OH)(2)Cu(H(2)O)(2)(1,3-bdc)⋅H(2)O (4; 1,3-bdc = isophthlalate). Single-crystal X-ray diffraction (XRD) analysis of compound 1 revealed 2D layers of chains of UO(8) and CuO(4)(H(2)O)(2) units that were connected through the phthalate ligands. In compound 2, these sheets were connected to each other through the two additional carboxylate arms of the pyromellitate, thus resulting in a 3D open-framework with 1D channels that trapped water molecules. Upon heating, free and bonded water species (from Cu-OH(2)) were evacuated from the structure. This thermal transition was followed by in situ XRD and IR spectroscopy. Heating induced a solid-state topotactic transformation with the formation of a new set of Cu-O interactions in the crystalline anhydrous structure (2'), in order to keep the square-planar environment around the copper centers. The structure of compound 3 was built up from trinuclear motifs, in which one copper center, CuO(4)(OH(2))(2), was linked to two uranium units, UO(5)(H(2)O)(2). The assembly of this trimer, "U(2)Cu", with the mellitate generated a 3D network. Complex 4 contained a tetranuclear uranyl core of UO(5)(OH)(2) and UO(6)(OH) units that were linked to two copper centers, CuO(OH)(2)(H(2)O)(2), which were then connected to each other through isophthalate ligands and U=O-Cu interactions to create a 3D structure. The common structural feature of these different compounds is a bridging oxo group of U=O-Cu type, which is reflected by apical Cu-O distances in the range 2.350(3)-2.745(5) Å. In the case of a shorter Cu-O distance, a slight lengthening

  18. Coordinatively saturated cationic ruthenium(II) complexes. Preparation, characterization, and reaction with potassium superoxide

    SciTech Connect

    Oshima, N.; Suzuki, H.; Moro-oka, Y.

    1986-09-10

    Coordinatively saturated cationic ruthenium(II) complexes, (eta/sup 5/-C/sub 5/H/sub 5/)(eta/sup 6/-C/sub 6/H/sub 6/)Ru/sup II/)(BF/sub 4/) (1), (eta/sup 5/-C/sub 5/Me/sub 5/)(eta/sup 6/-C/sub 66/)Ru/sup II/)(BF/sub 4/) (2), ((1-5-eta/sup 5/-C/sub 6/H/sub 7/)(eta/sup 6/-C/sub 6/H/sub 6/)Ru/sup II/)(BF/sub 4/) (3), ((1-5-eta/sup 5/-C/sub 7/H/sub 9/)(eta/sup 6/-C/sub 6/H/sub 7/)Ru/sup II/)(BF/sub 4/) (4), ((1-3:5,6-eta/sup 5/-C/sub 8/H/sub 1/exclamation)(eta/sup 6/-C/sub 6/H/sub 6/)Ru/sup II/)(BG/sub 4/)(5), and ((6-EtO-1-5-eta /sup 5/-C/sub 7/H/sub 8/)(eta/sup 6/-C/sub 6/H/sub 6/)Ru/sup II/)(BF/sub 4/) (7), are prepared by the reaction of (eta/sup 6/-C/sub 6/H/sub 6/)RuCl/sub 2/)/sub 2/ with cyclopentadiene, pentamethylcyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,5-cyclooctadiene, and 1,3,5-cycloheptatriene, respectively, in ethanol in the presence of AgBF/sub 4/. Superoxide anion attacks at the terminal position of the dienyl moiety of 3-5 to yield ruthenium(0) complexes 8-10, containing cyclic dienone ligand. 25 references, 4 figures, 4 tables.

  19. Characterization of Ce SUP 3+-tributyl phosphate coordination complexes produced by fused droplet electrospray ionization with a target capillary

    SciTech Connect

    Gary S. Groenewold; Jean-Jacques Gaumet

    2011-12-01

    Coordination complexes containing Ce(III) and tri-n-butyl phosphate (TBP) in the 1+, 2+ and 3+ charge states were generated using desorption electrospray ionization (DESI) mass spectrometry, in which the analyte solutions were supplied via a target capillary orthogonally situated with respect to the electrospray. Comparison with direct electrospray (ESI) showed that the same coordination complexes were produced in each experiment, and could be described by the general formula [Ce(NO3)m=0-2(TBP)n](3-m)+. This result indicates that DESI has utility for measuring metal speciation for metal ligand solutions where the gas-phase complexes generated by ESI have been correlated with solution speciation. Such an application would be useful for analyses where it is desirable to limit the total amount of metal being handled, or that have solvent systems that are not readily amenable to ESI. Both the direct ESI and DESI mass spectra showed similar trends with respect to the TBP:Ce ratio, viz. high values tend to favor formation of a larger fraction of the 1+ species, and the 2+ and 3+ species become relatively more important as the ratio is decreased. Within individual charge state ion envelopes, lower TBP:Ce ratios produce coordination complexes with fewer ligands, a trend also seen using both approaches. These trends again point toward strong similarity between the direct ESI and DESI analyses of the metal-ligand solutions. The DESI experiments were less sensitive for measuring the coordination complexes compared to the direct ESI experiments, by a factor of 10 - 100 depending on whether minimum detectable concentration or absolute ion abundances were considered. Nevertheless, mid-picomolar quantities of coordination complexes were measured using the target capillary, indicating that sensitivity would be sufficient for measuring species in many industrial separations processes.

  20. Distinct Structural Pathways Coordinate the Activation of AMPA Receptor-Auxiliary Subunit Complexes

    PubMed Central

    Dawe, G. Brent; Musgaard, Maria; Aurousseau, Mark R.P.; Nayeem, Naushaba; Green, Tim; Biggin, Philip C.; Bowie, Derek

    2016-01-01

    Summary Neurotransmitter-gated ion channels adopt different gating modes to fine-tune signaling at central synapses. At glutamatergic synapses, high and low activity of AMPA receptors (AMPARs) is observed when pore-forming subunits coassemble with or without auxiliary subunits, respectively. Whether a common structural pathway accounts for these different gating modes is unclear. Here, we identify two structural motifs that determine the time course of AMPAR channel activation. A network of electrostatic interactions at the apex of the AMPAR ligand-binding domain (LBD) is essential for gating by pore-forming subunits, whereas a conserved motif on the lower, D2 lobe of the LBD prolongs channel activity when auxiliary subunits are present. Accordingly, channel activity is almost entirely abolished by elimination of the electrostatic network but restored via auxiliary protein interactions at the D2 lobe. In summary, we propose that activation of native AMPAR complexes is coordinated by distinct structural pathways, favored by the association/dissociation of auxiliary subunits. PMID:26924438

  1. Unique molecular geometries of reduced 4- and 5-coordinate zinc complexes stabilised by diiminopyridine ligand.

    PubMed

    Chu, Terry; Belding, Lee; Poddutoori, Prashanth K; van der Est, Art; Dudding, Travis; Korobkov, Ilia; Nikonov, Georgii I

    2016-09-14

    Stepwise reduction of the diiminopyridine (dimpyr) complex, dimpyrZnCl2, by KC8 leads to molecular zinc compounds dimpyrZnCl (2) and dimpyrZnCl(DMAP) (3, DMAP = 4-dimethylaminopyridine), which were characterized by X-ray diffraction and EPR spectroscopy. Compound 2 shows an unusual nearly square planar geometry of the zinc atom equally ligated by two imine groups. X-ray crystallographic and EPR data suggest significant delocalization of the zinc 4p electron onto the non-innocent dimpyr ligand. The chloride in 2 can also be substituted by a methyl group upon addition of methyl lithium to generate compound 4, dimpyrZnMe. The novel alkylzinc compound displayed approximate square planar geometry around the zinc centre and significant delocalization of electron density onto the dimpyr ligand, as revealed by X-ray crystallographic studies and EPR spectroscopy, akin to 2. Further reduction of 3 leads to compound 5, dimpyrZn(DMAP)2. X-ray diffraction study of 5 revealed an unprecedented see-saw geometry around the four-coordinate zinc center with significant electron density transfer to the dimpyr ligand, supported by DFT calculations. PMID:27488247

  2. Fermi-orbitals for improved electronic structure calculations on coordination complexes

    NASA Astrophysics Data System (ADS)

    Kao, Der-You; Pederson, Mark R.; Lee, James D.

    An improved density-functional formalism proceeds by adopting the Perdew-Zunger expression for a self-interaction-corrected (SIC) density-functional energy but evaluates the total energy based on Fermi Orbitals (FOs). Each localized electron is represented by an FO, determined from the occupied Kohn-Sham orbitals and a semi-classical FO descriptor. The SIC energy is then minimized through the gradients of the energy with respect to these descriptors. In addition to providing a review of the methodology, work here identifies the need for an algorithm which thoroughly searches over initial configurations. The strategy for sampling and prioritizing initial configurations is described. Applications on coordination complexes are presented. The FO descriptors and FOs for semi-classical and quantum-mechanical understanding of bondingis discussed. Cohesive energies are improved andthe eigenvalues are shifted downward relative to the standard DFT results.Spin-dependent vibrational spectra, as a possible means for spectroscopic determination of the transition-metal moment, are also presented. DK acknowledges her fellowship from The George Washington University Institude of Nanotechnology.

  3. Implementation of the external complex scaling method in spheroidal coordinates: Impact ionization of molecular hydrogen

    SciTech Connect

    Serov, Vladislav V.; Joulakian, Boghos B.

    2009-12-15

    We develop an ab initio procedure based on the driven Schroedinger equation formalism and the external complex scaling method for the determination of the multifold differential cross sections of the single and double ionization of molecular hydrogen by single photon and fast electron impact. We take advantage of the separability of the two-center Schrodinger equation in prolate spheroidal coordinates in the numerical calculation of the two-electron two-center wave function of the initial and final states of the target. After having verified our procedure by reproducing existing confirmed triple differential cross sections of the (e,2e) ionization of H{sub 2}, we have extended our calculation to the double ionization of H{sub 2}. Our results on double photoionization agree with existing experimental results. We observe in the mean time a small difference with respect to the absolute results obtained by similar ab initio calculations using spherical bases. For the case of the double ionization by fast electron impact for which very few experimental results exist, our results confirm the existing disagreement between the theoretical results and the unique experimental one in the case of (e,3-1e). This we think makes it clear that for (e,3e) the introduction of the higher terms of the Born series for mean energy electron-impact regime is necessary.

  4. The MAP kinase pathway coordinates crossover designation with disassembly of synaptonemal complex proteins during meiosis

    PubMed Central

    Nadarajan, Saravanapriah; Mohideen, Firaz; Tzur, Yonatan B; Ferrandiz, Nuria; Crawley, Oliver; Montoya, Alex; Faull, Peter; Snijders, Ambrosius P; Cutillas, Pedro R; Jambhekar, Ashwini; Blower, Michael D; Martinez-Perez, Enrique; Harper, J Wade; Colaiacovo, Monica P

    2016-01-01

    Asymmetric disassembly of the synaptonemal complex (SC) is crucial for proper meiotic chromosome segregation. However, the signaling mechanisms that directly regulate this process are poorly understood. Here we show that the mammalian Rho GEF homolog, ECT-2, functions through the conserved RAS/ERK MAP kinase signaling pathway in the C. elegans germline to regulate the disassembly of SC proteins. We find that SYP-2, a SC central region component, is a potential target for MPK-1-mediated phosphorylation and that constitutively phosphorylated SYP-2 impairs the disassembly of SC proteins from chromosomal domains referred to as the long arms of the bivalents. Inactivation of MAP kinase at late pachytene is critical for timely disassembly of the SC proteins from the long arms, and is dependent on the crossover (CO) promoting factors ZHP-3/RNF212/Zip3 and COSA-1/CNTD1. We propose that the conserved MAP kinase pathway coordinates CO designation with the disassembly of SC proteins to ensure accurate chromosome segregation. DOI: http://dx.doi.org/10.7554/eLife.12039.001 PMID:26920220

  5. Distinct Structural Pathways Coordinate the Activation of AMPA Receptor-Auxiliary Subunit Complexes.

    PubMed

    Dawe, G Brent; Musgaard, Maria; Aurousseau, Mark R P; Nayeem, Naushaba; Green, Tim; Biggin, Philip C; Bowie, Derek

    2016-03-16

    Neurotransmitter-gated ion channels adopt different gating modes to fine-tune signaling at central synapses. At glutamatergic synapses, high and low activity of AMPA receptors (AMPARs) is observed when pore-forming subunits coassemble with or without auxiliary subunits, respectively. Whether a common structural pathway accounts for these different gating modes is unclear. Here, we identify two structural motifs that determine the time course of AMPAR channel activation. A network of electrostatic interactions at the apex of the AMPAR ligand-binding domain (LBD) is essential for gating by pore-forming subunits, whereas a conserved motif on the lower, D2 lobe of the LBD prolongs channel activity when auxiliary subunits are present. Accordingly, channel activity is almost entirely abolished by elimination of the electrostatic network but restored via auxiliary protein interactions at the D2 lobe. In summary, we propose that activation of native AMPAR complexes is coordinated by distinct structural pathways, favored by the association/dissociation of auxiliary subunits. PMID:26924438

  6. Hydrothermal syntheses and structures of the uranyl tellurates AgUO 2(HTeO 5) and Pb 2UO 2(TeO 6)

    NASA Astrophysics Data System (ADS)

    Ling, Jie; Ward, Matthew; Burns, Peter C.

    2011-02-01

    Two uranyl tellurates, AgUO 2(HTeO 5) ( 1) and Pb 2UO 2(TeO 6) ( 2), were synthesized under hydrothermal conditions and were structurally, chemically, and spectroscopically characterized. 1 crystallizes in space group Pbca, a=7.085(2) Å, b=11.986(3) Å, c=13.913(4) Å, V=1181.5(5) Å 3, Z=8; 2 is in P2(1)/ c, a=5.742(1) Å, b=7.789(2) Å, c=7.928(2) Å, V=90.703(2) Å 3, and Z=2. These are the first structures reported for uranyl compounds containing tellurate. The U 6+ cations are present as (UO 2) 2+ uranyl ions that are coordinated by O atoms to give pentagonal and square bipyramids in compounds 1 and 2, respectively. The structural unit in 1 is a sheet consisting of chains of edge-sharing uranyl pentagonal bipyramids that are one bipyramid wide, linked through the dimers of TeO 6 octahedra. In 2, uranyl square bipyramids share each of their equatorial vertices with different TeO 6 octahedra, giving a sheet with the autunite-type topology. Sheets in 1 and 2 are connected through the low-valence cations that are located in the interlayer region. The structures of 1 and 2 are compared to those of uranyl compounds containing octahedrally coordinated cations.

  7. Electronic Transitions as a Probe of Tetrahedral versus Octahedral Coordination in Nickel(II) Complexes: An Undergraduate Inorganic Chemistry Experiment.

    ERIC Educational Resources Information Center

    Filgueiras, Carlos A. L.; Carazza, Fernando

    1980-01-01

    Discusses procedures, theoretical considerations, and results of an experiment involving the preparation of a tetrahedral nickel(II) complex and its transformation into an octahedral species. Suggests that fundamental aspects of coordination chemistry can be demonstrated by simple experiments performed in introductory level courses. (Author/JN)

  8. Coordination Complexes of a Neutral 1,2,4-Benzotriazinyl Radical Ligand: Synthesis, Molecular and Electronic Structures, and Magnetic Properties.

    PubMed

    Morgan, Ian S; Mansikkamäki, Akseli; Zissimou, Georgia A; Koutentis, Panayiotis A; Rouzières, Mathieu; Clérac, Rodolphe; Tuononen, Heikki M

    2015-10-26

    A series of d-block metal complexes of the recently reported coordinating neutral radical ligand 1-phenyl-3-(pyrid-2-yl)-1,4-dihydro-1,2,4-benzotriazin-4-yl (1) was synthesized. The investigated systems contain the benzotriazinyl radical 1 coordinated to a divalent metal cation, Mn(II) , Fe(II) , Co(II) , or Ni(II) , with 1,1,1,5,5,5-hexafluoroacetylacetonato (hfac) as the auxiliary ligand of choice. The synthesized complexes were fully characterized by single-crystal X-ray diffraction, magnetic susceptibility measurements, and electronic structure calculations. The complexes [Mn(1)(hfac)2 ] and [Fe(1)(hfac)2 ] displayed antiferromagnetic coupling between the unpaired electrons of the ligand and the metal cation, whereas the interaction was found to be ferromagnetic in the analogous Ni(II) complex [Ni(1)(hfac)2 ]. The magnetic properties of the complex [Co(1)(hfac)2 ] were difficult to interpret owing to significant spin-orbit coupling inherent to octahedral high-spin Co(II) metal ion. As a whole, the reported data clearly demonstrated the favorable coordinating properties of the radical 1, which, together with its stability and structural tunability, make it an excellent new building block for establishing more complex metal-radical architectures with interesting magnetic properties. PMID:26493885

  9. Structural diversity in mercury(II) coordination complexes with asymmetrical hydrazone-based ligands derived from pyridine

    NASA Astrophysics Data System (ADS)

    Masoumi, Asad; Servati Gargari, Masoumeh; Mahmoudi, Ghodrat; Miroslaw, Barbara; Therrien, Bruno; Abedi, Marjan; Hazendonk, Paul

    2015-05-01

    Three novel Hg(II) complexes 1-3 of asymmetrical hydrazone-pyridine based ligands, L1-L3, with distinct coordination structures have been prepared and characterized by a single crystal X-ray diffraction, elemental and thermal analysis, and IR spectroscopy. The complexes form either discrete units with one (1) or two (2) organic ligands, or one-dimensional polymers (3). Hence the ligands can be regarded as chelating (1), mono-dentate (2) or bridging (3) agents. The mercury center is essentially neutralized in each complex by two iodide anions. The coordination in complexes 2 and 3 adopts deformed tetrahedral shapes. In contrast the Hg(II) cation in complex 1 binds three coplanar ligating atoms (O,N,N) and, as with pincer ligands, its coordination polyhedron is supplemented with two I- anions in apical positions. The structural diversity in these complexes is strongly influenced by the position of N atom in pyridine derived moieties. The crystal structure is stabilized by N/O-H⋯N/O/I hydrogen bonds and π⋯π interactions.

  10. Structural Studies of Copper(I) Complexes of Amyloid-Beta Peptide Fragments: Formation of Two-Coordinate Bis(Histidine) Complexes

    SciTech Connect

    Himes, R.A.; Park, G.Young.; Siluvai, G.Sutha.; Blackburn, N.J.; Karlin, K.D.

    2009-05-18

    The beta bind: Copper(I) binds to amyloid {beta}-peptide fragments (see structure) as a stable bis(histidine), two-coordinate, near-linear complex, even in the presence of potential additional ligands. As has been proposed or assumed in other studies, the copper(I)-peptide complexes react with dioxygen to form the reactive oxygen species H{sub 2}O{sub 2}, without the need for a third histidine ligand to promote the chemistry.

  11. Neodymium uranyl peroxide synthesis by ion exchange on ammonium uranyl peroxide nanoclusters.

    PubMed

    Blanchard, F; Ellart, M; Rivenet, M; Vigier, N; Hablot, I; Morel, B; Grandjean, S; Abraham, F

    2016-03-11

    This study demonstrates the ability of ammonium uranyl peroxide nanoclusters U32R-NH4 to undergo exchange in between NH4(+) and trivalent (Nd(3+)) or tetravalent (Th(4+)) cations in the solid state. It paves the way for new promising routes for the synthesis of mixed uranyl peroxides. The exchange ability may also be considered for solution decontamination and synthesis of new mixed actinide-oxide precursors. Both of these applications could be used in the nuclear industry. PMID:26879486

  12. Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(ii).

    PubMed

    Dau, Phuong D; Shuh, David K; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J; Gibson, John K

    2016-08-01

    The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf(II) is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf(II)(CH3SO2)3(-), prepared in the gas phase by reductive elimination of CH3SO2 from Cf(III)(CH3SO2)4(-). Comparison with synthesis of the corresponding Sm and Cm complexes reveals reduction of Cf(III) and Sm(III), and no evidence for reduction of Cm(III). This reflects the comparative 3+/2+ reduction potentials: Cf(3+) (-1.60 V) ≈ Sm(3+) (-1.55 V) ≫ Cm(3+) (-3.7 V). Association of O2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. The new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf(II) coordination complexes and similar chemistry of Cf and Sm. PMID:27424652

  13. Two coordination modes around the Cu(II) cations in complexes with benzo[b]furancarboxylic acids

    NASA Astrophysics Data System (ADS)

    Drzewiecka, Aleksandra; Koziol, Anna E.; Klepka, Marcin T.; Wolska, Anna; Jimenez-Pulido, Sonia B.; Lis, Tadeusz; Ostrowska, Kinga; Struga, Marta

    2013-02-01

    Three Cu(II) complexes with derivatives of the benzo[b]furancarboxylic acid have been synthesized and characterized by the elemental and thermal analyses, and IR spectroscopy. The geometry of metal-ligand interaction for all compounds has been described using X-ray absorption spectroscopy and for one of them by X-ray crystallography. Two mononuclear Cu(II) complexes, with 7-acetyl-5-bromo-6-hydroxy-3-methylbenzo[b]furan-2-carboxylic and 6-acetyl-5-hydroxy-2-methylbenzo[b]furan-3-carboxylic acids, exhibit a tetra-fold coordination, CuO4. The Cu(II) cation in crystals with 7-acetyl-6-methoxy-3-methyl-benzo[b]furan-2-carboxylic acid is penta-coordinated; the bridging COO- groups and ethanol molecule stabilize the dinuclear center Cu2O10. The powdered form of this complex is based on the Cu2O8 units, indicating the absence of the ethanol molecules.

  14. Vibrational Spectroscopy of Mass Selected [UO2(ligand)n]2+ Complexes in the Gas Phase

    SciTech Connect

    Gary S. Groenewold; Anita Gianotto; Michael Vanstipdonk; Kevin C. Cossel; David T. Moore,; Nick Polfer; Jos Oomens

    2006-03-01

    The gas-phase infrared spectra of discrete uranyl ([UO2]2+) complexes ligated with acetone and/or acetonitrile were used to evaluate systematic trends of ligation on the position of the O=U=O stretch, and to enable rigorous comparison with the results of computational studies. Ionic uranyl complexes isolated in a Fourier transform ion cyclotron resonance mass spectrometer were fragmented via infrared multiphoton dissociation using a free electron laser scanned over the mid-IR wavelengths. The asymmetric O=U=O stretching frequency was measured at 1017 cm-1 for [UO2(CH3COCH3)2]2+, and was systematically red shifted to 1000 and 988 cm-1 by the addition of a third and fourth acetone ligands, respectively, which was consistent with more donation of electron density to the uranium center in complexes with higher coordination number. The experimental measurements were in good agreement with values generated computationally using LDA, B3LYP, and ZORA-PW91 approaches. In contrast to the uranyl frequency shifts, the carbonyl frequencies of the acetone ligands were progressively blue shifted as the number of ligands increased from 2 to 4, and approached that of free acetone. This observation was consistent with the formation of weaker noncovalent bonds between uranium and the carbonyl oxygen as the extent of ligation increases. Similar trends were observed for [UO2(CH3CN)n]2+ complexes although the magnitude of the red shift in the uranyl frequency upon addition more acetonitrile ligands was smaller than for acetone, consistent with the more modest nucleophilic nature of acetonitrile. This conclusion was amplified by the uranyl stretching frequencies measured for mixed acetone/acetonitrile complexes, which showed that substitution of one acetone for one acetonitrile produced a modest red shift of 3 to 6 cm-1.

  15. Trinuclear nickel coordination complexes of phenanthrene-9,10-dione dioxime

    PubMed Central

    Williams, Owen M.; Cowley, Alan H.

    2016-01-01

    A trinuclear nickel complex of phenanthrene-9,10-dione dioxime (H2pqd), namely bis­[μ2-9,10-bis­(oxido­imino)­phenanthrene]­bis­[μ2-10-(oxido­imino)phenanthrene-9-one oxime](phenanthrene-9,10-dione dioxime)trinickel(II) toluene disolvate, [Ni3(C14H8N2O2)2(C14H9N2O2)2(C14H10N2O2)]·2C7H8, has been isolated and its crystal structure determined. This complex features three independent NiII atoms that are arranged in a triangular fashion along with five supporting ligands. There are two square-planar NiII atoms and a third pseudo-octa­hedral NiII atom. While the square-planar NiII atoms are stacked, there are no ligand bridges between them. Each square-planar NiII atom, however, bridges with the pseudo-octa­­hedral NiII atom through Ni—N—O—Ni and Ni—O—Ni bonds. A fluorido­bor­ation reaction of the proton-bridged species gave the analogous complex bis­(μ2-bis­{[10-(oxido­imino)-9,10-di­hydro­phenanthren-9-yl­idene]amino}di­fluorido­borato)(phenanthrene-9,10-dione dioxime)trinickel(II) dichloromethane trisolvate, [Ni3(C28H16BF2N4O2)4(C14H10N2O2)]·3CH2Cl2, which shows the same binding structure, but features a widened Ni—Ni inter­action between the square-planar NiII atoms. The proton-bridged complex completes the macrocyclic coordination around the square-planar NiII atoms by means of an O—H⋯O hydrogen bond. Both compounds feature O—H⋯N hydrogen bonds between the oxime and the N atoms attached to square-planar nickel atom. The nickel units show no direct inter­action with their nearest neighbors in the extended lattice. Two π-stacking inter­actions between adjacent mol­ecules are found: one with a centroid–centroid distance of 3.886 (2) Å and the other with a centroid–centroid distance of 4.256 (3) Å. In the latter case, although not aromatic, the distance to the centroid of the central phenanthrene ring is shorter, with a distance of 3.528 (3) Å. Toluene mol­ecules occupy the solvent channels that are

  16. Trinuclear nickel coordination complexes of phenanthrene-9,10-dione dioxime.

    PubMed

    Williams, Owen M; Cowley, Alan H

    2016-04-01

    A trinuclear nickel complex of phenanthrene-9,10-dione dioxime (H2pqd), namely bis-[μ2-9,10-bis-(oxido-imino)-phenanthrene]-bis-[μ2-10-(oxido-imino)phenanthrene-9-one oxime](phenanthrene-9,10-dione dioxime)trinickel(II) toluene disolvate, [Ni3(C14H8N2O2)2(C14H9N2O2)2(C14H10N2O2)]·2C7H8, has been isolated and its crystal structure determined. This complex features three independent Ni(II) atoms that are arranged in a triangular fashion along with five supporting ligands. There are two square-planar Ni(II) atoms and a third pseudo-octa-hedral Ni(II) atom. While the square-planar Ni(II) atoms are stacked, there are no ligand bridges between them. Each square-planar Ni(II) atom, however, bridges with the pseudo-octa--hedral Ni(II) atom through Ni-N-O-Ni and Ni-O-Ni bonds. A fluorido-bor-ation reaction of the proton-bridged species gave the analogous complex bis-(μ2-bis-{[10-(oxido-imino)-9,10-di-hydro-phenanthren-9-yl-idene]amino}di-fluorido-borato)(phenanthrene-9,10-dione dioxime)trinickel(II) dichloromethane trisolvate, [Ni3(C28H16BF2N4O2)4(C14H10N2O2)]·3CH2Cl2, which shows the same binding structure, but features a widened Ni-Ni inter-action between the square-planar Ni(II) atoms. The proton-bridged complex completes the macrocyclic coordination around the square-planar Ni(II) atoms by means of an O-H⋯O hydrogen bond. Both compounds feature O-H⋯N hydrogen bonds between the oxime and the N atoms attached to square-planar nickel atom. The nickel units show no direct inter-action with their nearest neighbors in the extended lattice. Two π-stacking inter-actions between adjacent mol-ecules are found: one with a centroid-centroid distance of 3.886 (2) Å and the other with a centroid-centroid distance of 4.256 (3) Å. In the latter case, although not aromatic, the distance to the centroid of the central phenanthrene ring is shorter, with a distance of 3.528 (3) Å. Toluene mol-ecules occupy the solvent channels that are oriented along the c axis. In

  17. Evaluation of in vitro antimicrobial and in vivo cytotoxic properties of some novel titanium-based coordination complexes.

    PubMed

    Sheikh, Chanmiya; Hossain, Mohammad Shamim; Easmin, Mosammat Sabina; Islam, Mohammad Saidul; Rashid, Mamunur

    2004-05-01

    The aim of the present study was to determine the antimicrobial and cytotoxic activities of eight novel titanium(III) based coordination complexes [Ti(Pht)(2)(DL-serine)(2), S(1)], [Ti(Pht)(2)(glycine)(2), S(2))], [Ti(Pht)(2)(cystine)(2), S(3)], [Ti(Pht)(2)(DL-leucine)(2), S(4)], [Ti(Suc)(2)(L-leucine)(2), S(5)], [Ti(Suc)(2)(cystine)(2), S(6)], [Ti(Suc)(2)(cystein)(2), S(7)] and [Ti(Suc)(2)(DL-serine)(2), S(8)] against several gram-positive and -negative bacteria, fungi and brine shrimp nauplii. The investigation showed that almost all of the complexes were moderately active against tested bacteria and fungi at high concentration (200 microg/disc) compared with the standard antibiotic, amoxicillin and the antifungal agent, nystatin. In vivo lethality bioassay experiment showed that only S(7) and S(8) among the complexes had better cytotoxic effect than standard gallic acid. The LC(50) values of these two complexes were found to be 1.00 and 1.21 microg/ml, respectively. Thus the results suggest that only two complexes (S(7), S(8)) among the titanium(III) based coordination complexes show the anticancer properties comparable to the standard cytotoxic agent, and further studies of these two complexes may be helpful for their clinical implication. PMID:15133251

  18. XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

    SciTech Connect

    Mayes, Richard T.; Piechowicz, Marek; Lin, Zekai; Veith, Gabriel M.; Dai, Sheng; Lin, Wenbin; Abney, C. W.; Bryantsev, V. S.

    2015-11-12

    In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η2 motifs proposed by small molecule and computational studies. Samples exposed to environmental seawater also display a feature consistent with a μ2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.

  19. XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

    DOE PAGESBeta

    Mayes, Richard T.; Piechowicz, Marek; Lin, Zekai; Veith, Gabriel M.; Dai, Sheng; Lin, Wenbin; Abney, C. W.; Bryantsev, V. S.

    2015-11-12

    In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η2 motifs proposed by small molecule and computationalmore » studies. Samples exposed to environmental seawater also display a feature consistent with a μ2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.« less

  20. Evidence of a stable uranyl site in ancient organic-rich calcite.

    PubMed

    Kelly, Shelly D; Rasbury, E Troy; Chattopadhyay, Soma; Kropf, A Jeremy; Kemner, Kenneth M

    2006-04-01

    The mechanism of uranium (U) incorporation into calcite (calcium carbonate) is of fundamental importance to the fate and transport of U at the surface and in the shallow subsurface and has implications for (a) the accuracy of U-Pb and U-series isotope ratio methods used to determine the ages of ancient deposits and (b) potential remediation strategies based on sequestration of U in the subsurface. Extended X-ray absorption fine structure (EXAFS) spectroscopy is uniquely suited to the study of U-calcite systems. The sensitivity of the EXAFS spectrum to the local atomic Ca coordination about U(VI) in the calcite structure results in an increase in the number and amplitude of Ca signals as the U(VI) becomes more ordered within the crystal structure. Our X-ray microprobe (10-microm) measurements of an ancient 298 million-year-old organic-rich calcite (calcrete) clearly revealed three coordination shells of Ca atoms, defining a well-ordered calcite structure about uranyl to a distance of approximately 6.5 angstroms. These results indicate that uranyl is incorporated at the Ca2+ site in calcite and that the uranyl environment may evolve over long time scales, becoming more calcite-like and more stable for long-term sequestration of uranium. These results therefore validate U-related dating methods and show that calcite can be effective at sequestering U in vadose zone sediments. PMID:16646462

  1. Anion recognition in water with use of a neutral uranyl-salophen receptor.

    PubMed

    Dalla Cort, Antonella; Forte, Gianpiero; Schiaffino, Luca

    2011-09-16

    A new water-soluble uranyl-salophen complex incorporating two glucose units has been synthesized. This neutral derivative shows noteworthy binding affinity for fluoride in water thanks to the Lewis acid-base interaction occurring between the metal and the anion. Such interaction is strong enough to overcome the high hydration enthalpy of fluoride. Moreover this complex effectively binds hydrogen phosphate and exhibits remarkably strong association for nucleotide polyanions ADP(3-) and ATP(4-). PMID:21812437

  2. Complexation of uranium(VI) and samarium(III) with oxydiacetic acid: temperature effect and coordination modes.

    PubMed

    Rao, Linfeng; Garnov, Alexander Yu; Jiang, Jun; Di Bernardo, Plinio; Zanonato, PierLuigi; Bismondo, Arturo

    2003-06-01

    The complexation of uranium(VI) and samarium(III) with oxydiacetate (ODA) in 1.05 mol kg(-1) NaClO(4) is studied at variable temperatures (25-70 degrees C). Three U(VI)/ODA complexes (UO(2)L, UO(2)L(2)(2-), and UO(2)HL(2)(-)) and three Sm(III)/ODA complexes (SmL(j)((3-2)(j)+) with j = 1, 2, 3) are identified in this temperature range. The formation constants and the molar enthalpies of complexation are determined by potentiometry and calorimetry. The complexation of uranium(VI) and samarium(III) with oxydiacetate becomes more endothermic at higher temperatures. However, the complexes become stronger due to increasingly more positive entropy of complexation at higher temperatures that exceeds the increase in the enthalpy of complexation. The values of the heat capacity of complexation (Delta C(p) degrees in J K(-1) mol(-1)) are 95 +/- 6, 297 +/- 14, and 162 +/- 19 for UO(2)L, UO(2)L(2)(2-), and UO(2)HL(2)(-), and 142 +/- 6, 198 +/- 14, and 157 +/- 19 for SmL(+), SmL(2)(-), and SmL(3)(3-), respectively. The thermodynamic parameters, in conjunction with the structural information from spectroscopy, help to identify the coordination modes in the uranium oxydiacetate complexes. The effect of temperature on the thermodynamics of the complexation is discussed in terms of the electrostatic model and the change in the solvent structure. PMID:12767209

  3. First-principles molecular dynamics simulations of uranyl ion interaction at the water/rutile TiO2(110) interface

    NASA Astrophysics Data System (ADS)

    Sebbari, K.; Roques, J.; Simoni, E.; Domain, C.; Perron, H.; Catalette, H.

    2012-08-01

    The effects of temperature and solvation on uranyl ion adsorption at the water/rutile TiO2(110) interface are investigated by Density Functional Theory (DFT) in both static and Born-Oppenheimer molecular dynamics approaches. According to experimental observations, uranyl ion can form two surface complexes in a pH range from 1.5 to 4.5. Based on these observations, the structures of the complexes at 293 K are first calculated in agreement with vacuum static calculations. Then, an increase in temperature (293 to 425 K) induces the reinforcement of uranyl ion adsorption due to the release of water molecules from the solvation shell of uranyl ion. Finally, temperature can modify the nature of the surface species.

  4. Pyrophosphate-mediated magnetic interactions in Cu(II) coordination complexes.

    PubMed

    Marino, Nadia; Ikotun, Oluwatayo F; Julve, Miguel; Lloret, Francesc; Cano, Juan; Doyle, Robert P

    2011-01-01

    The reaction in water of Cu(NO(3))(2)·2.5H(2)O with 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), or 1,10-phenanthroline-5-amine (phenam), and sodium pyrophosphate (Na(4)P(2)O(7)), at various pHs, afforded three new copper(II)-pyrophosphate complexes, namely, {[Cu(bipy)(cis-H(2)P(2)O(7))](2)}·3H(2)O (1a), {[Cu(phen)(H(2)O)](4)(HP(2)O(7))(2)}(ClO(4))(2)·4H(2)O (2), and {[Cu(2)(phenam)(2)(P(2)O(7))](2)·25H(2)O}(n) (3). A solvent free crystalline phase of 1a was also isolated with formula {[Cu(bipy)(trans-H(2)P(2)O(7))](2)} (1b), which can be regarded as a pseudo-polymorph of 1a. Single crystal X-ray analyses revealed these compounds to have uncommon molecular architectures, with 3 being an unprecedented pyrophosphate-containing two-dimensional (2D) polymer. Compounds 1a/1b and 2 are discrete di- and tetra-nuclear complexes, respectively. The cationic {[Cu(phen)(H(2)O)](4)(HP(2)O(7))(2)}(2+) unit in 2 presents a unique quasi-flat structure, held together by solely in-plane pyrophosphate bridging modes (short O(eq)-P-O(eq) and long O(eq)-P-O-P-O(eq) pathways), a coordination arrangement also not previously reported. A different tetranuclear copper(II)-pyrophosphate arrangement is found in 3, with two classically bridged dimers (O(eq)-P-O(eq) pathway) joined together by auxiliary equatorial-axial μ-O pyrophosphate bridges. Here, the bidimensionality is reached through bridging phenam ligands, which provide further inter-"tetramer" metal-metal connections [(N,N')(eq)-(N'')(ax) pathway], leading to the formation of an expanded covalent network based on the [Cu(2)(phenam)(2)(P(2)O(7))](2) moiety. Variable-temperature magnetic susceptibility measurements on polycrystalline samples of 2 and 3 revealed net antiferromagnetic coupling between metal centers with J(2a) = -7.9(2) cm(-1), J(2b) = -46.9(3) cm(-1), J(2c) = 0 cm(-1) in 2 (H = -J(2a)[S(Cu(1))·S(Cu(2)) + S(Cu(1a))·S(Cu(2a))] - J(2b)[S(Cu(1))·S(Cu(2a)) + S(Cu(1a))·S(Cu(2))] - J(2c)S(Cu(2))·S(Cu(2a))), and

  5. Uranyl acetate causes DNA single strand breaks in vitro in the presence of ascorbate (vitamin C).

    PubMed

    Yazzie, Monica; Gamble, Shania L; Civitello, Edgar R; Stearns, Diane M

    2003-04-01

    Uranium is a radioactive heavy metal with isotopes that decay on the geological time scale. People are exposed to uranium through uranium mining, processing, the resulting mine tailings, and the use of depleted uranium in the military. Acute exposures to uranium are chemically toxic to the kidney; however, little is known about chronic exposures, for example, if there is a direct chemical genotoxicity of uranium. The hypothesis that is being tested in the current work is that hexavalent uranium, as uranyl ion, may have a chemical genotoxicity similar to that of hexavalent chromium. In the current study, reactions of uranyl acetate (UA) and ascorbate (vitamin C) were observed to produce plasmid relaxation in pBluescript DNA. DNA strand breaks increased with increasing concentrations of a 1:1 reaction of UA and ascorbate but were not affected by increasing the ratio of ascorbate. Plasmid relaxation was inhibited by coincubation of reactions with catalase but not by coincubation with the radical scavengers mannitol, sodium azide, or 5,5-dimethyl-1-pyrroline-N-oxide. Reactions of UA and ascorbate monitored by (1)H NMR spectroscopy showed formation of a uranyl ascorbate complex, with no evidence of a dehydroascorbate product. A previous study inferred that hydroxyl radical formation was responsible for oxidative DNA damage in the presence of reactions of uranyl ion, hydrogen peroxide, and ascorbate [Miller et al. (2002) J. Bioinorg. Chem. 91, 246-252]. Current results, in the absence of added hydrogen peroxide, were not completely consistent with the interpretation that strand breaks were produced by a Fenton type generation of reactive oxygen species. Data were also consistent with the interpretation that a uranyl ascorbate complex was catalyzing hydrolysis of the DNA-phosphate backbone, in a manner similar to that known for the lanthanides. These data suggest that uranium may be directly genotoxic and may, like chromium, react with DNA by more than one pathway. PMID

  6. Molecular dynamics simulations of uranyl adsorption and structure on the basal surface of muscovite

    DOE PAGESBeta

    Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Cygan, Randall T.

    2014-02-05

    Anthropogenic activities have led to an increased concentration of uranium on the Earth’s surface and potentially in the subsurface with the development of nuclear waste repositories. Uranium is soluble in groundwater, and its mobility is strongly affected by the presence of clay minerals in soils and in subsurface sediments. We use molecular dynamics simulations to probe the adsorption of aqueous uranyl (UO22+) ions onto the basal surface of muscovite, a suitable proxy for typically ultrafine-grained clay phases. Model systems include the competitive adsorption between potassium counterions and aqueous ions (0.1 M and 1.0 M UO2Cl2 , 0.1 M NaCl). Wemore » find that for systems with potassium and uranyl ions present, potassium ions dominate the adsorption phenomenon. Potassium ions adsorb entirely as inner-sphere complexes associated with the ditrigonal cavity of the basal surface. Uranyl ions adsorb in two configurations when it is the only ion species present, and in a single configuration in the presence of potassium. Finally, the majority of adsorbed uranyl ions are tilted less than 45° relative to the muscovite surface, and are associated with the Si4Al2 rings near aluminum substitution sites.« less

  7. Molecular dynamics simulations of uranyl adsorption and structure on the basal surface of muscovite

    SciTech Connect

    Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Cygan, Randall T.

    2014-02-05

    Anthropogenic activities have led to an increased concentration of uranium on the Earth’s surface and potentially in the subsurface with the development of nuclear waste repositories. Uranium is soluble in groundwater, and its mobility is strongly affected by the presence of clay minerals in soils and in subsurface sediments. We use molecular dynamics simulations to probe the adsorption of aqueous uranyl (UO22+) ions onto the basal surface of muscovite, a suitable proxy for typically ultrafine-grained clay phases. Model systems include the competitive adsorption between potassium counterions and aqueous ions (0.1 M and 1.0 M UO2Cl2 , 0.1 M NaCl). We find that for systems with potassium and uranyl ions present, potassium ions dominate the adsorption phenomenon. Potassium ions adsorb entirely as inner-sphere complexes associated with the ditrigonal cavity of the basal surface. Uranyl ions adsorb in two configurations when it is the only ion species present, and in a single configuration in the presence of potassium. Finally, the majority of adsorbed uranyl ions are tilted less than 45° relative to the muscovite surface, and are associated with the Si4Al2 rings near aluminum substitution sites.

  8. Solvent tuning of the substitution behavior of a seven-coordinate iron(III) complex.

    PubMed

    Ivanović-Burmazović, Ivana; Hamza, Mohamed S A; van Eldik, Rudi

    2006-02-20

    A detailed kinetic study of the substitution behavior of the seven-coordinate [Fe(dapsox)(L)2]ClO4 complex (H(2)dapsox = 2,6-diacetylpyridine-bis(semioxamazide), L = solvent or its deprotonated form) with thiocyanate as a function of the thiocyanate concentration, temperature, and pressure was undertaken in protic (EtOH and acidified EtOH and MeOH) and aprotic (DMSO) organic solvents. The lability and substitution mechanism depend strongly on the selected solvent (i.e., on solvolytic and protolytic processes). In the case of alcoholic solutions, substitution of both solvent molecules by thiocyanate could be observed, whereas in DMSO only one substitution step occurred. For both substitution steps, [Fe(dapsox)(L)2]ClO4 shows similar mechanistic behavior in methanol and ethanol, which is best reflected by the values of the activation volumes (MeOH DeltaV(I) = +15.0 +/- 0.3 cm(3) mol(-1), DeltaV(II) = +12.0 +/- 0.2 cm(3) mol(-1); EtOH DeltaV(I) = +15.8 +/- 0.7 cm(3) mol(-1), DeltaV(II) = +11.1 +/- 0.5 cm(3) mol(-1)). On the basis of the reported activation parameters, a dissociative (D) mechanism for the first substitution step and a D or dissociative interchange (I(d)) mechanism for the second substitution step are suggested for the reaction in MeOH and EtOH. This is consistent with the predominant existence of alcoxo [Fe(dapsox)(ROH)(OR)] species in alcoholic solutions. In comparison, the activation parameters for the substitution of the aqua-hydroxo [Fe(dapsox)(H2O)(OH)] complex by thiocyanate at pH 5.1 in MES were determined to be DeltaH = 72 +/- 3 kJ mol(-1), DeltaS = +38 +/- 11 J K(-1) mol(-1), and DeltaV = -3.0 +/- 0.1 cm(3) mol(-1), and the operation of a dissociative interchange mechanism was suggested, taking the effect of pressure on the employed buffer into account. The addition of triflic acid to the alcoholic solutions ([HOTf] = 10(-3) and 10(-2) M to MeOH and EtOH, respectively) resulted in a drastic changeover in mechanism for the first substitution

  9. Observation of Radiolytic Field Alteration of the Uranyl Cation in Bicarbonate Solution

    SciTech Connect

    Snow, Lanee; McNamara, Bruce; Sinkov, Sergei; Cho, Herman; Friese, Judah

    2007-07-01

    Auto radiolysis of uranium (VI) carbonate solutions between pH 5.9 and 7.2 is shown to alter the uranium speciation over relatively short periods of time and was followed by {sup 13}C NMR and visible spectrophotometry, using dissolved [({sup 233}UO{sub 2}){sub 3}(CO{sub 3}){sub 6}]{sup 6-} both as the radiolysis source (D 14.9 Gy/hr) and as a trap for the newly formed hydrogen peroxide. The speciation is different than the uranyl mixed peroxy carbonate species that have been reported for higher pH carbonate solutions. Direct addition of hydrogen peroxide to solutions of the uranyl-carbonate trimer is shown to reproduce the {sup 13}C, {sup 17}O NMR signatures of the complex(es) formed by radiolysis, but additionally a variety of new complexes are revealed. Ratios of H{sub 2}O{sub 2}/trimer <1.5 produced uranyl peroxo carbonate adducts that are shown to be common to the radiolytically produced species. Ratios of H{sub 2}O{sub 2}/trimer >1.5 resulted in formation of stable higher order peroxo carbonate complexes. The {sup 13}C, {sup 17}O NMR signatures and visible spectra of these complexes are described here. Rigorous characterization of the species is an ongoing effort. (authors)

  10. MnBr₂/18-crown-6 coordination complexes showing high room temperature luminescence and quantum yield.

    PubMed

    Hausmann, David; Kuzmanoski, Ana; Feldmann, Claus

    2016-04-21

    The reaction of manganese(ii) bromide and the crown ether 18-crown-6 in the ionic liquid [(n-Bu)3MeN][N(Tf)2] under mild conditions (80-130 °C) resulted in the formation of three different coordination compounds: MnBr2(18-crown-6) (), Mn3Br6(18-crown-6)2 () and Mn3Br6(18-crown-6) (). In general, the local coordination and the crystal structure of all compounds are driven by the mismatch between the small radius of the Mn(2+) cation (83 pm) and the ring opening of 18-crown-6 as a chelating ligand (about 300 pm). This improper situation leads to different types of coordination and bonding. MnBr2(18-crown-6) represents a molecular compound with Mn(2+) coordinated by two bromine atoms and only five oxygen atoms of 18-crown-6. Mn3Br6(18-crown-6)2 falls into a [MnBr(18-crown-6)](+) cation - with Mn(2+) coordinated by six oxygen atoms and Br - and a [MnBr(18-crown-6)MnBr4](-) anion. In this anion, Mn(2+) is coordinated by five oxygen atoms of the crown ether as well as by two bromine atoms, one of them bridging to an isolated (MnBr4) tetrahedron. Mn3Br6(18-crown-6), finally, forms an infinite, non-charged [Mn2(18-crown-6)(MnBr6)] chain. Herein, 18-crown-6 is exocyclically coordinated by two Mn(2+) cations. All compounds show intense luminescence in the yellow to red spectral range and exhibit remarkable quantum yields of 70% (Mn3Br6(18-crown-6)) and 98% (Mn3Br6(18-crown-6)2). The excellent quantum yield of Mn3Br6(18-crown-6)2 and its differentiation from MnBr2(18-crown-6) and Mn3Br6(18-crown-6) can be directly correlated to the local coordination. PMID:26956783

  11. Deciphering the Conformational Choreography of Zinc Coordination Complexes with Standard and Novel Proton NMR Techniques Combined with DFT Methods.

    PubMed

    Pucheta, Jose Enrique Herbert; Prim, Damien; Gillet, Jean Michel; Farjon, Jonathan

    2016-04-01

    The presence of water has been shown to deeply impact the stability and geometry of Zn complexes in solution. Evidence for tetra- and penta-coordinated species in a pyridylmethylamine-Zn(II) model complex is presented. Novel (1) H NMR tools such as T1 -filtered selective exchange spectroscopy and pure shifted gradient-encoded selective refocusing as well as classical 2D ((1) H-(1) H) exchange spectroscopy, diffusion-ordered spectroscopy and T1 ((1) H) measurements, in combination with density functional theory methods allow the full conformational dynamics of a pyridylmethylamine-Zn(II) complex to be revealed. Four conformers and two families of complexes depending on the hydration states are elucidated. PMID:26845749

  12. Stability of peroxide-containing uranyl minerals.

    PubMed

    Kubatko, Karrie-Ann Hughes; Helean, Katheryn B; Navrotsky, Alexandra; Burns, Peter C

    2003-11-14

    Minerals containing peroxide are limited to studtite, (UO2)O2(H2O)4, and metastudtite, (UO2)O2(H2O)2. High-temperature oxide-melt solution calorimetry and solubility measurements for studtite (standard enthalpy of formation at 298 kelvin is -2344.7 +/- 4.0 kilojoules per mole from the elements) establishes that these phases are stable in peroxide-bearing environments, even at low H2O2 concentrations. Natural radioactivity in a uranium deposit, or the radioactivity of nuclear waste, can create sufficient H2O2 by alpha radiolysis of water for studtite formation. Studtite and metastudtite may be important alteration phases of nuclear waste in a geological repository and of spent fuel under any long-term storage, possibly at the expense of the commonly expected uranyl oxide hydrates and uranyl silicates. PMID:14615533

  13. GRAPHITE PRODUCTION UTILIZING URANYL NITRATE HEXAHYDRATE CATALYST

    DOEpatents

    Sheinberg, H.; Armstrong, J.R.; Schell, D.H.

    1964-03-10

    ABS>The graphitizing of a mixture composed of furfuryl alcohol binder and uranyl nitrate hexahydrate hardener and the subsequent curing, baking, and graphitizing with pressure being initially applied prior to curing are described. The pressure step may be carried out by extrusion, methyl cellulose being added to the mixture before the completion of extrusion. Uranium oxide may be added to the graphitizable mixture prior to the heating and pressure steps. The graphitizable mixture may consist of discrete layers of different compositions. (AEC)

  14. Coordination and insertion of alkenes and alkynes in Au(III) complexes: nature of the intermediates from a computational perspective.

    PubMed

    Balcells, David; Eisenstein, Odile; Tilset, Mats; Nova, Ainara

    2016-04-01

    The contribution of Au(III) species to catalysis is still debated due to the limited number of characterized intermediates with this oxidation state. In particular, the coordination of alkenes and alkynes to Au(III) followed by insertion into Au(III)-X bonds has been suggested but rarely proven experimentally. Here, these reactions are explored by means of DFT and CCSD(T) calculations considering [AuX3(L)] and [AuX2(L)2](+) complexes. In these complexes, L = ethylene and acetylene have been chosen as substrates of high interest and representative of any unsaturated organic substrate, whereas X is Cl, Me or H, as found in metal salts and as model for intermediates involved in catalysis. Isoelectronic Pt(II) complexes are also considered for comparison. Ethylene coordination occurs preferentially perpendicular for all X except H, whereas for acetylene, coordination takes place in-plane for all X except Cl. These coordination isomers can represent either minima (intermediates) or saddle points (transition states) on the potential energy surface, depending on X. NBO analysis shows how this variety of structures results from the combination of electronic (M-L donation and back-donation) and steric (cis L-X repulsion) effects. With the sole exception of [AuMe2(ethylene)2](+), rotation of the unsaturated ligand and insertion into a cis Au-X bond involve low to moderate energy barriers, ΔG(‡) = 2.5 to 23.5 kcal mol(-1), and are thermodynamically feasible, ΔG = 4.3 to -47.2 kcal mol(-1). The paucity of experimental observations for such reactions should thus be caused by other factors, like the participation of the intermediates and products in competitive side reactions including the reductive elimination of XCHnCHnX (n = 1 or 2). PMID:26905649

  15. mTORC1 and CK2 coordinate ternary and eIF4F complex assembly

    PubMed Central

    Gandin, Valentina; Masvidal, Laia; Cargnello, Marie; Gyenis, Laszlo; McLaughlan, Shannon; Cai, Yutian; Tenkerian, Clara; Morita, Masahiro; Balanathan, Preetika; Jean-Jean, Olivier; Stambolic, Vuk; Trost, Matthias; Furic, Luc; Larose, Louise; Koromilas, Antonis E.; Asano, Katsura; Litchfield, David; Larsson, Ola; Topisirovic, Ivan

    2016-01-01

    Ternary complex (TC) and eIF4F complex assembly are the two major rate-limiting steps in translation initiation regulated by eIF2α phosphorylation and the mTOR/4E-BP pathway, respectively. How TC and eIF4F assembly are coordinated, however, remains largely unknown. We show that mTOR suppresses translation of mRNAs activated under short-term stress wherein TC recycling is attenuated by eIF2α phosphorylation. During acute nutrient or growth factor stimulation, mTORC1 induces eIF2β phosphorylation and recruitment of NCK1 to eIF2, decreases eIF2α phosphorylation and bolsters TC recycling. Accordingly, eIF2β mediates the effect of mTORC1 on protein synthesis and proliferation. In addition, we demonstrate a formerly undocumented role for CK2 in regulation of translation initiation, whereby CK2 stimulates phosphorylation of eIF2β and simultaneously bolsters eIF4F complex assembly via the mTORC1/4E-BP pathway. These findings imply a previously unrecognized mode of translation regulation, whereby mTORC1 and CK2 coordinate TC and eIF4F complex assembly to stimulate cell proliferation. PMID:27040916

  16. Toughening elastomers using mussel-inspired catechol-metal coordination complexes

    NASA Astrophysics Data System (ADS)

    Filippidi, Emmanouela; Christiani, Thomas; Valentine, Megan; Waite, J. Herbert; Israelachvili, Jacob; Ahn, Kollbe

    Amorphous, covalently-linked elastomers possess excellent reversible extensibility and high failure strain compared to other materials. However, by nature, the large deformability compromises the Young's modulus and the toughness of the elastomer to low values (< 2MPa) and imparts brittle fracture. We employ the mussel-inspired strategy of iron-catechol coordination bonding creating dynamic, reversible cross-links in addition to permanent chemical cross-links in an elastomer used in ambient, dry conditions. This simple additional energy dissipative mechanism results in increased modulus and toughness without affecting the network extensibility, which is based on the covalent network. Control of the chain relaxation time scales can be further tuned using the dynamic bonds, imparting mechanical rate dependent properties to the bulk material. The quantitative understanding of the time scales associated with the chain motion versus the metal coordination may provide another simple and independent control parameter in elastomeric material design.

  17. Coordination Polymer: Synthesis, Spectral Characterization and Thermal Behaviour of Starch-Urea Based Biodegradable Polymer and Its Polymer Metal Complexes

    PubMed Central

    Malik, Ashraf; Parveen, Shadma; Ahamad, Tansir; Alshehri, Saad M.; Singh, Prabal Kumar; Nishat, Nahid

    2010-01-01

    A starch-urea-based biodegradable coordination polymer modified by transition metal Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) was prepared by polycondensation of starch and urea. All the synthesized polymeric compounds were characterized by Fourier transform-infrared spectroscopy (FT-IR), 1H-NMR spectroscopy, 13C-NMR spectroscopy, UV-visible spectra, magnetic moment measurements, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). The results of electronic spectra and magnetic moment measurements indicate that Mn(II), Co(II), and Ni(II) complexes show octahedral geometry, while Cu(II) and Zn(II) complexes show square planar and tetrahedral geometry, respectively. The thermogravimetric analysis revealed that all the polymeric metal complexes are more thermally stable than the parental ligand. In addition, biodegradable studies of all the polymeric compounds were also carried out through ASTM standards of biodegradable polymers by CO2 evolution method. PMID:20414461

  18. Behaviors of acrylamide/itaconic acid hydrogels in uptake of uranyl ions from aqueous solutions

    SciTech Connect

    Karadag, E.; Saraydin, D.; Gueven, O.

    1995-12-01

    In this study, adsorptions of uranyl ions from two different aqueous uranyl solutions by acrylamide-itaconic acid hydrogels were investigated by a spectroscopic method. The hydrogels were prepared by irradiating with {gamma}-radiation. In the experiment of uranyl ions adsorption, Type II adsorption was found. One gram of acrylamide-itaconic acid hydrogels sorbed 178-219 mg uranyl ions from the solutions of uranyl acetate, 42-76 mg uranyl ions from the aqueous solutions of uranyl nitrate, while acrylamide hydrogel did not sorb any uranyl ion. For the hydrogel containing 40 mg of itaconic acid and irradiated to 3.73 kGy, swelling of the hydrogels was observed in water (1660%), in the aqueous solution of uranyl acetate (730%), and in the aqueous solution of uranyl nitrate (580%). Diffusions of water onto hydrogels were a non-Fickian type of diffusion, whereas diffusions of uranyl ions were a Fickian type of diffusion.

  19. A new role for RINT-1 in SNARE complex assembly at the trans-Golgi network in coordination with the COG complex

    PubMed Central

    Arasaki, Kohei; Takagi, Daichi; Furuno, Akiko; Sohda, Miwa; Misumi, Yoshio; Wakana, Yuichi; Inoue, Hiroki; Tagaya, Mitsuo

    2013-01-01

    Docking and fusion of transport vesicles/carriers with the target membrane involve a tethering factor–mediated initial contact followed by soluble N-ethylmaleimide–sensitive factor attachment protein receptor (SNARE)–catalyzed membrane fusion. The multisubunit tethering CATCHR family complexes (Dsl1, COG, exocyst, and GARP complexes) share very low sequence homology among subunits despite likely evolving from a common ancestor and participate in fundamentally different membrane trafficking pathways. Yeast Tip20, as a subunit of the Dsl1 complex, has been implicated in retrograde transport from the Golgi apparatus to the endoplasmic reticulum. Our previous study showed that RINT-1, the mammalian counterpart of yeast Tip20, mediates the association of ZW10 (mammalian Dsl1) with endoplasmic reticulum–localized SNARE proteins. In the present study, we show that RINT-1 is also required for endosome-to–trans-Golgi network trafficking. RINT-1 uncomplexed with ZW10 interacts with the COG complex, another member of the CATCHR family complex, and regulates SNARE complex assembly at the trans-Golgi network. This additional role for RINT-1 may in part reflect adaptation to the demand for more diverse transport routes from endosomes to the trans-Golgi network in mammals compared with those in a unicellular organism, yeast. The present findings highlight a new role of RINT-1 in coordination with the COG complex. PMID:23885118

  20. Heme-Copper/Dioxygen Complexes: Towards Understanding Ligand-Environmental Effects on Coordination Geometry, Electronic Structure and Reactivity

    PubMed Central

    Halime, Zakaria; Kieber-Emmons, Matthew T.; Qayyum, Munzarin F.; Mondal, Biplab; Puiu, Simona C.; Chufán, Eduardo E.; Sarjeant, Amy A. N.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.; Karlin, Kenneth D.

    2010-01-01

    The nature of the ligand is an important aspect of controlling structure and reactivity in coordination chemistry. In connection with our study of heme/copper/oxygen reactivity relevant to cytochrome c oxidase O2-reduction chemistry, we compare the molecular and electronic structure of two high-spin heme-peroxo-copper [FeIII-O22--CuII]+ complexes containing N4-tetradentate (1) or N3-tridentate (2) copper ligands. Combining previously reported and new resonance Raman and EXAFS data coupled to DFT calculations we report a geometric structure and more complete electronic description of the high-spin heme-peroxo-copper complexes 1 and 2, which establish μ-(O22-) side-on to the FeIII and end-on to CuII (μ-η2:η1) binding for the complex 1 but side-on/side-on (μ-η2:η2) μ-peroxo coordination for the complex 2. We also compare and summarize the differences and similarities of these two complexes in their reactivity toward CO, PPh3, acid and phenols. The comparison of a new X-ray structure of μ-oxo complex 2a with the previously reported 1a X-ray structure, two thermal decomposition products respectively of 2 and 1, reveals a considerable difference in the Fe-O-Cu angle between the two μ-oxo complexes (∠Fe-O-Cu = 178.2° in 1a, ∠Fe-O-Cu = 149.5° in 2a). The reaction of 2 with one equivalent of exogenous N-donor axial base leads to the formation of a distinctive low-temperature stable, low-spin heme-O2-Cu complex (2b), but under the same conditions the addition of an axial base to 1 leads to the dissociation of the heme-peroxo-Cu assembly and the release of O2. 2b reacts with phenols performing hydrogen-atom (e– + H+) abstraction resulting in O-O bond cleavage and the formation of high-valent ferryl [FeIV=O] complex (2c). The nature of 2c was confirmed by comparison of its spectroscopic features and reactivity with those of an independently prepared ferryl complex. The phenoxyl radical generated by the hydrogen-atom abstraction was either 1) directly detected

  1. Characterization of lanthanide(III) DOTP complexes: Thermodynamics, protonation, and coordination to alkali metal ions

    SciTech Connect

    Sherry, A.D.; Ren, J.; Huskens, J.

    1996-07-31

    The chemical and thermodynamic characterization of Lanthanide(III) DOTP complexes was performed. Spectrophotometry, potentiometry, osmometry, and NMR spectroscopy were used in this characterization. Stability constants, protonation equilibria, and interactions of the complexes with alkali metal ions were measured and summarized.

  2. Synthesis, spectroscopic, coordination and biological activities of some organometallic complexes derived from thio-Schiff base ligands

    PubMed Central

    Abou-Hussein, Azza A.; Linert, Wolfgang

    2014-01-01

    Two series of mono- and binuclear complexes cyclic or acyclic thio-ferocine Schiff base ligands, derived from the condensation of 2-aminobenzenthiol (L) with monoacetyl ferrocene in the molar ratio 1:1 or in the molar ratio 1:2 for diacetyl ferocine have been prepared. The condensation reactions yield the corresponding Schiff Base ligands, HLa-Maf and H2Lb-Daf. The chelation of the ligands to metal ions occurs through the sulfur of the thiol group as well as the nitrogen atoms of the azomethine group of the ligands. HLa-Maf acts as monobasic bidentate or dibasic tetradentate, while H2Lb-Daf behaves as twice negatively cargend tetradentate ligand. The structures of these ligands were elucidated by elemental analysis, infrared, ultraviolet–visible spectra, as well as 1H NMR spectra. Reactions of the Schiff bases ligands with ruthenium(III), oxovanadium(IV) and dioxouranium(VI) afforded the corresponding transition metal complexes. The properties of the newly prepared complexes were analyse by elemental analyses, infrared, electronic spectra, 1H NMR as well as the magnetic susceptibility and conductivity measurement. The metal complexes exhibits different geometrical arrangements such as octahedral and square pyramidal coordination. Schiff base ligands and their metal complexes were tested against two pathogenic bacteria as Gram-positive and Gram-negative bacteria as well as one kind of fungi to study their biological activity. All the complexes exhibit antibacterial and antifungal activities against these organisms. PMID:24070648

  3. Synthesis, spectroscopic, coordination and biological activities of some organometallic complexes derived from thio-Schiff base ligands

    NASA Astrophysics Data System (ADS)

    Abou-Hussein, Azza A.; Linert, Wolfgang

    2014-01-01

    Two series of mono- and binuclear complexes cyclic or acyclic thio-ferocine Schiff base ligands, derived from the condensation of 2-aminobenzenthiol (L) with monoacetyl ferrocene in the molar ratio 1:1 or in the molar ratio 1:2 for diacetyl ferocine have been prepared. The condensation reactions yield the corresponding Schiff Base ligands, HLa-Maf and H2Lb-Daf. The chelation of the ligands to metal ions occurs through the sulfur of the thiol group as well as the nitrogen atoms of the azomethine group of the ligands. HLa-Maf acts as monobasic bidentate or dibasic tetradentate, while H2Lb-Daf behaves as twice negatively cargend tetradentate ligand. The structures of these ligands were elucidated by elemental analysis, infrared, ultraviolet-visible spectra, as well as 1H NMR spectra. Reactions of the Schiff bases ligands with ruthenium(III), oxovanadium(IV) and dioxouranium(VI) afforded the corresponding transition metal complexes. The properties of the newly prepared complexes were analyse by elemental analyses, infrared, electronic spectra, 1H NMR as well as the magnetic susceptibility and conductivity measurement. The metal complexes exhibits different geometrical arrangements such as octahedral and square pyramidal coordination. Schiff base ligands and their metal complexes were tested against two pathogenic bacteria as Gram-positive and Gram-negative bacteria as well as one kind of fungi to study their biological activity. All the complexes exhibit antibacterial and antifungal activities against these organisms.

  4. Vibrational Spectroscopy of Mass-Selected [UO₂(ligand)n]²⁺ Complexes in the Gas Phase: Comparison with Theory

    SciTech Connect

    Groenewold, G. S.; Gianotto, Anita K.; Cossel, Kevin C.; Van Stipdonk, Michael J.; Moore, David T.; Polfer, Nick; Oomens, Jos; De Jong, Wibe A.; Visscher, Lucas

    2006-03-18

    The gas-phase infrared spectra of discrete uranyl ([UO₂]²⁺) complexes ligated with acetone and/or acetonitrile were used to evaluate systematic trends of ligation on the position of the O=U=O stretch, and to enable rigorous comparison with the results of computational studies. Ionic uranyl complexes isolated in a Fourier transform ion cyclotron resonance mass spectrometer were fragmented via infrared multiphoton dissociation using a free electron laser scanned over the mid-IR wavelengths. The asymmetric O=U=O stretching frequency was measured at 1017 cm⁻¹ for [UO₂(CH₃COCH₃)₂]²⁺ and was systematically red shifted to 1000 and 988 cm⁻¹ by the addition of a third and fourth acetone ligand, respectively, which was consistent with increased donation of electron density to the uranium center in complexes with higher coordination number. The values generated computationally using LDA, B3LYP, and ZORA-PW91 were in good agreement with experimental measurements. In contrast to the uranyl frequency shifts, the carbonyl frequencies of the acetone ligands were progressively blue shifted as the number of ligands increased from 2 to 4, and approached that of free acetone. This observation was consistent with the formation of weaker noncovalent bonds between uranium and the carbonyl oxygen as the extent of ligation increases. Similar trends were observed for [UO₂(CH₃CN)n]²⁺ complexes, although the magnitude of the red shift in the uranyl frequency upon addition of more acetonitrile ligands was smaller than for acetone, consistent with the more modest nucleophilic nature of acetonitrile. This conclusion was confirmed by the uranyl stretching frequencies measured for mixed acetone/acetonitrile complexes, which showed that substitution of one acetone for one acetonitrile produced a modest red shift of 3 to 6 cm⁻¹.

  5. Complex regulatory pathways coordinate cell cycle progression and development in Caulobacter crescentus

    PubMed Central

    Brown, Pamela J.B.; Hardy, Gail G.; Trimble, Michael J.; Brun, Yves V.

    2008-01-01

    Caulobacter crescentus has become the predominant bacterial model system to study the regulation of cell cycle progression. Stage specific processes such as chromosome replication and segregation, and cell division are coordinated with the development of four polar structures: the flagellum, pili, stalk, and holdfast. The production, activation, localization, and proteolysis of specific regulatory proteins at precise times during the cell cycle culminate in the ability of the cell to produce two physiologically distinct daughter cells. We examine the recent advances that have enhanced our understanding of the mechanisms of temporal and spatial regulation that occur during cell cycle progression. PMID:18929067

  6. An Unprecedented Two-Fold Nested Super-Polyrotaxane: Sulfate-Directed Hierarchical Polythreading Assembly of Uranyl Polyrotaxane Moieties.

    PubMed

    Mei, Lei; Wu, Qun-Yan; Yuan, Li-Yong; Wang, Lin; An, Shu-Wen; Xie, Zhen-Ni; Hu, Kong-Qiu; Chai, Zhi-Fang; Burns, Peter C; Shi, Wei-Qun

    2016-08-01

    The hierarchical assembly of well-organized submoieties could lead to more complicated superstructures with intriguing properties. We describe herein an unprecedented polyrotaxane polythreading framework containing a two-fold nested super-polyrotaxane substructure, which was synthesized through a uranyl-directed hierarchical polythreading assembly of one-dimensional polyrotaxane chains and two-dimensional polyrotaxane networks. This special assembly mode actually affords a new way of supramolecular chemistry instead of covalently linked bulky stoppers to construct stable interlocked rotaxane moieties. An investigation of the synthesis condition shows that sulfate can assume a vital role in mediating the formation of different uranyl species, especially the unique trinuclear uranyl moiety [(UO2 )3 O(OH)2 ](2+) , involving a notable bent [O=U=O] bond with a bond angle of 172.0(9)°. Detailed analysis of the coordination features, the thermal stability as well as a fluorescence, and electrochemical characterization demonstrate that the uniqueness of this super-polyrotaxane structure is mainly closely related to the trinuclear uranyl moiety, which is confirmed by quantum chemical calculations. PMID:27389048

  7. Dynamic Resectorization and Coordination Technology: An Evaluation of Air Traffic Control Complexity

    NASA Technical Reports Server (NTRS)

    Brinton, Christopher R.

    1996-01-01

    The work described in this report is done under contract with the National Aeronautics and Space Administration (NASA) to support the Advanced Air Transportation Technology (AATR) program. The goal of this program is to contribute to and accelerate progress in Advanced Air Transportation Technologies. Wyndemere Incorporated is supporting this goal by studying the complexity of the Air Traffic Specialist's role in maintaining the safety of the Air Transportation system. It is envisioned that the implementation of Free Flight may significantly increase the complexity and difficulty of maintaining this safety. Wyndemere Incorporated is researching potential methods to reduce this complexity. This is the final report for the contract.

  8. Specific capture of uranyl protein targets by metal affinity chromatography.

    PubMed

    Basset, Christian; Dedieu, Alain; Guérin, Philippe; Quéméneur, Eric; Meyer, Daniel; Vidaud, Claude

    2008-03-28

    To improve general understanding of biochemical mechanisms in the field of uranium toxicology, the identification of protein targets needs to be intensified. Immobilized metal affinity chromatography (IMAC) has been widely developed as a powerful tool for capturing metal binding proteins from biological extracts. However uranyl cations (UO2(2+)) have particular physico-chemical characteristics which prevent them from being immobilized on classical metal chelating supports. We report here on the first development of an immobilized uranyl affinity chromatography method, based on the cation-exchange properties of aminophosphonate groups for uranyl binding. The cation distribution coefficient and loading capacity on the support were determined. Then the stability of the uranyl-bonded phase under our chromatographic conditions was optimized to promote affinity mechanisms. The successful enrichment of uranyl binding proteins from human serum was then proven using proteomic and mass spectral analysis. PMID:18308325

  9. Pro-oxidative, genotoxic and cytotoxic properties of uranyl ions.

    PubMed

    Garmash, S A; Smirnova, V S; Karp, O E; Usacheva, A M; Berezhnov, A V; Ivanov, V E; Chernikov, A V; Bruskov, V I; Gudkov, S V

    2014-01-01

    It is demonstrated that hydroxyl radicals and hydrogen peroxide are formed under the action of uranyl ions in aqueous solutions containing no reducing agents. In the presence of uranyl ions, formation of 8-oxoguanine in DNA and long-lived protein radicals are observed in vitro. It is shown that the pro-oxidant properties of uranyl at micromolar concentrations mostly result from the physico-chemical nature of the compound rather than its radioactive decay. Uranyl ions lead to damage in DNA and proteins causing death of HEp-2 cells by necrotic pathway. It is revealed that the uranyl ions enhance radiation-induced oxidative stress and significantly increase a death rate of mice exposed to sublethal doses of X-rays. PMID:23312590

  10. A Highly Reactive Seven-Coordinate Osmium(V) Oxo Complex: [Os(V)(O)(qpy)(pic)Cl](2+).

    PubMed

    Liu, Yingying; Ng, Siu-Mui; Lam, William W Y; Yiu, Shek-Man; Lau, Tai-Chu

    2016-01-01

    Seven-coordinate ruthenium oxo species have been proposed as active intermediates in catalytic water oxidation by a number of highly active ruthenium catalysts, however such species have yet to be isolated. Reported herein is the first example of a seven-coordinate group 8 metal-oxo species, [Os(V)(O)(qpy)(pic)Cl](2+) (qpy = 2,2':6',2'':6'',2'''-quaterpyridine, pic = 4-picoline). The X-ray crystal structure of this complex shows that it has a distorted pentagonal bipyramidal geometry with an Os=O distance of 1.7375 Å. This oxo species undergoes facile O-atom and H-atom-transfer reactions with various organic substrates. Notably it can abstract H atoms from alkylaromatics with C-H bond dissociation energy as high as 90 kcal mol(-1). This work suggests that highly active oxidants may be designed based on group 8 seven-coordinate metal oxo species. PMID:26554748

  11. Pillared and open-framework uranyl diphosphonates

    SciTech Connect

    Adelani, Pius O.; Albrecht-Schmitt, Thomas E.

    2011-09-15

    The hydrothermal reactions of uranium trioxide, uranyl acetate, or uranyl nitrate with 1,4-benzenebisphosphonic acid in the presence of very small amount of HF at 200 deg. C results in the formation of three different uranyl diphosphonate compounds, [H{sub 3}O]{sub 2}{l_brace}(UO{sub 2}){sub 6}[C{sub 6}H{sub 4}(PO{sub 3})(PO{sub 2}OH)]{sub 2}[C{sub 6}H{sub 4}(PO{sub 2}OH){sub 2}]{sub 2}[C{sub 6}H{sub 4}(PO{sub 3}){sub 2}]{r_brace}(H{sub 2}O){sub 2} (Ubbp-1), [H{sub 3}O]{sub 4}{l_brace}(UO{sub 2}){sub 4}[C{sub 6}H{sub 4}(PO{sub 3}){sub 2}]{sub 2}F{sub 4}{r_brace}.H{sub 2}O (Ubbp-2), and {l_brace}(UO{sub 2})[C{sub 6}H{sub 2}F{sub 2}(PO{sub 2}OH){sub 2}(H{sub 2}O){r_brace}{sub 2}.H{sub 2}O (Ubbp-3). The crystal structures of these compounds were determined by single crystal X-ray diffraction experiments. Ubbp-1 consists of UO{sub 7} pentagonal bipyramids that are bridged by the phosphonate moieties to form a three-dimensional pillared structure. Ubbp-2 is composed of UO{sub 5}F{sub 2} pentagonal bipyramids that are bridged through the phosphonate oxygen atoms into one-dimensional chains that are cross-linked by the phenyl spacers into a pillared structure. The structure of Ubbp-3 is a three-dimensional open-framework with large channels containing water molecules with internal dimensions of approximately 10.9x10.9 A. Ubbp-1 and Ubbp-2 fluoresce at room temperature. - Graphical Abstract: Illustration of the three-dimensional open-framework structure of {l_brace}(UO{sub 2})[C{sub 6}H{sub 2}F{sub 2}(PO{sub 2}OH){sub 2}(H{sub 2}O){r_brace}{sub 2}.H{sub 2}O viewed along the c-axis. The structure is constructed from UO{sub 7} units, pentagonal bipyramids=green, oxygen=red, phosphorus=magenta, carbon=black, hydrogen=white. Highlights: > The influence of the uranyl salt anions and pH were critically examined in relation to structural variation. > The acetate and nitrate counter ions of uranyl may be acting as structure directing agents. > The use of rigid phenyl spacer yield

  12. Complexation of Lanthanides with Nitrate at Variable Temperatures: Thermodynamics and Coordination Modes

    SciTech Connect

    Rao, Linfeng; Tian, Guoxin

    2008-12-10

    Complexation of neodymium(III) with nitrate was studied at variable temperatures (25, 40, 55 and 70 C) by spectrophotometry and microcalorimetry. The NdNO{sub 3}{sup 2+} complex is weak and becomes slightly stronger as the temperature is increased. The enthalpy of complexation at 25 C was determined by microcalorimetry to be small and positive, (1.5 {+-} 0.2) kJ {center_dot} mol{sup -1}, in good agreement with the trend of the stability constant at variable temperatures. Luminescence emission spectra and lifetime of Eu(III) in nitrate solutions suggest that inner-sphere and bidentate complexes form between trivalent lanthanides (Nd{sup 3+} and Eu{sup 3+}) and nitrate in aqueous solutions. Specific Ion Interaction approach (SIT) was used to obtain the stability constants of NdNO{sub 3}{sup 2+} at infinite dilution and variable temperatures.

  13. SEPARATION OF URANYL NITRATE BY EXTRACTION

    DOEpatents

    Stoughton, R.W.; Steahly, F.L.

    1958-08-26

    A process is presented for obtaining U/sup 233/ from solutions containing Pa/sup 233/. A carrier precipitate, such as MnO/sub 2/, is formed in such solutions and carries with it the Pa/sup 233/ present. This precipitate is then dissolved in nitric acid and the solution is aged to allow decay of the Pa/ sup 233/ into U/sup 233/. After a sufficient length of time the U/sup 233/ bearing solution is made 2.5 to 4.5 Molar in manganese nitrate by addition thereof, and the solution is then treated with ether to obtain uranyl nitrate by solvent extraction techniques.

  14. Coordination of 1,4-Diazabutadiene Ligands to Decamethylytterbocene: Additional Examples of Spin Coupling in Ytterbocene Complexes

    SciTech Connect

    Andersen, Richard; Walter, Marc D.; Berg, David J.; Andersen, Richard A.

    2006-11-04

    The paramagnetic 1:1 coordination complexes of (C5Me5)2Yb with a series of diazabutadiene ligands, RN=C(R')C(R')=NR, where R= CMe3, CHMe2, adamantyl, p-tolyl, p-anisyl, and mesityl when R'=H, and R= p-anisyl when R'= Me, have been prepared. The complexes are paramagnetic, but their magnetic moments are less than expected for the two uncoupled spin carriers, (C5Me5)2Yb(III, 4f13) and the diazabutadiene radical anions (S=1/2), which implies exchange coupling between the spins. The variable temperature 1H NMR spectra show that rotation about the R-N bond is hindered and these barriers are estimated. The barriers are largely determined by steric effects but electronic effects are not unimportant.

  15. Role of the Uranyl Oxo Group as a Hydrogen Bond Acceptor

    SciTech Connect

    Watson, Lori A; Hay, Benjamin

    2011-01-01

    Density functional theory calculations have been used to evaluate the geometries and energetics of interactions between a number of uranyl complexes and hydrogen bond donor groups. The results reveal that although traditional hydrogen bond donors are repelled by the oxo group in the [UO{sub 2}(OH{sub 2}){sub 5}]{sup 2+} species, they are attracted to the oxo groups in [UO{sub 2}(OH{sub 2}){sub 2}(NO{sub 3}){sub 2}]{sup 0}, [UO{sub 2}(NO{sub 3}){sub 3}]{sup -}, and [UO{sub 2}Cl{sub 4}]{sup 2-} species. Hydrogen bond strength depends on the equatorial ligation and can exceed 15 kcal mol{sup -1}. The results also reveal the existence of directionality at the uranyl oxo acceptor, with a weak preference for linear U=O---H angles.

  16. Nitrite reduction by a pyridinediimine complex with a proton-responsive secondary coordination sphere.

    PubMed

    Kwon, Yubin M; Delgado, Mayra; Zakharov, Lev N; Seda, Takele; Gilbertson, John D

    2016-09-21

    The proton-responsive pyridinediimine ligand, (DEA)PDI (where (DEA)PDI = [(2,6-(i)PrC6H3)(N[double bond, length as m-dash]CMe)(N(Et)2C2H4)(N[double bond, length as m-dash]CMe)C5H3N]) was utilized for the reduction of NO2(-) to NO. Nitrite reduction is facilitated by the protonated secondary coordination sphere coupled with the ligand-based redox-active sites of [Fe(H(DEA)PDI)(CO)2](+) and results in the formation of the {Fe(NO)2}(9) DNIC, [Fe((DEA)PDI)(NO)2](+). PMID:27539064

  17. Synthesis, structures and properties of a series of manganese coordination complexes constructed from dicarboxylic fluorene derivatives

    SciTech Connect

    Li Xing; Zhao Xiuhua; Bing Yue; Zha Meiqin; Xie Hongzhen; Guo Zhiyong

    2013-01-15

    Assembly reactions of 9,9-diethylfluorene-2,7-dicarboxylic acid (H{sub 2}DFDC) and Mn(CH{sub 3}COO){sub 2}{center_dot}4H{sub 2}O or MnCl{sub 2}{center_dot}4H{sub 2}O by tuning of various secondary ligands such as 2,2 Prime -bipyridine (2,2 Prime -bpy), 4,4 Prime -bipyridine (4,4 Prime -bpy) or 1,3-bis(4-pyridyl)propane) (bpp), gave rise to four complexes {l_brace} [Mn{sub 2}(DFDC){sub 2}(DMF){sub 2}]{center_dot}H{sub 2}O{r_brace} {sub n} (1), [Mn(DFDC)(2,2 Prime -bpy)]{sub n} (2), {l_brace} [Mn{sub 2}(DFDC){sub 2}(4,4 Prime -bpy){sub 2}]{center_dot}2CH{sub 3}OH{r_brace} {sub n} (3), and {l_brace} [Mn{sub 4}(DFDC){sub 4}(bpp){sub 2}(CH{sub 3}OH){sub 3} (H{sub 2}O){sub 3}]{center_dot}3(CH{sub 3}OH){center_dot}3(H{sub 2}O){r_brace} {sub n} (4). Single crystal X-ray diffraction analysis reveal that complex 1 is three dimensional structure with rhombic channels filled by guest water molecules; 2 presents a close-packed structure with high thermal stability; 3 exhibits a three dimensional framework with micro-porous channels filled by guest methanol molecules and 4 is a two-dimensional structure. The photoluminescent properties of 1-4 have been studied, respectively, showing that the Mn(II) ions, accessorial organic ligands or crystal structures exert important influences on the photoluminescence emissions of H{sub 2}DFDC ligands. Thermogravimetric analysis show that the complexes have remarkably high thermal stability. Magnetic susceptibility measurements have been finished and discussed for the complexes. - Graphical abstract: Assembly of 9,9-diethylfluorene-2,7-dicarboxylic acid and Mn(II) salts by tuning of various accessorial ligands resulted in four manganese complexes with different topological frameworks. Highlights: Black-Right-Pointing-Pointer Four manganese complexes based on 9,9-diethylfluorene-2,7-dicarboxylic acid were obtained. Black-Right-Pointing-Pointer The complexes were structurally characterized by single-crystal X-ray diffraction. Black

  18. Aging induced loss of complexity and dedifferentiation: consequences for coordination dynamics within and between brain, muscular and behavioral levels

    PubMed Central

    Sleimen-Malkoun, Rita; Temprado, Jean-Jacques; Hong, S. Lee

    2014-01-01

    Growing evidence demonstrates that aging not only leads to structural and functional alterations of individual components of the neuro-musculo-skeletal system (NMSS) but also results in a systemic re-organization of interactions within and between the different levels and functional domains. Understanding the principles that drive the dynamics of these re-organizations is an important challenge for aging research. The present Hypothesis and Theory paper is a contribution in this direction. We propose that age-related declines in brain and behavior that have been characterized in the literature as dedifferentiation and the loss of complexity (LOC) are: (i) synonymous; and (ii) integrated. We argue that a causal link between the aforementioned phenomena exists, evident in the dynamic changes occurring in the aging NMSS. Through models and methods provided by a dynamical systems approach to coordination processes in complex living systems, we: (i) formalize operational hypotheses about the general principles of changes in cross-level and cross-domain interactions during aging; and (ii) develop a theory of the aging NMSS based on the combination of the frameworks of coordination dynamics (CD), dedifferentiation, and LOC. Finally, we provide operational predictions in the study of aging at neural, muscular, and behavioral levels, which lead to testable hypotheses and an experimental agenda to explore the link between CD, LOC and dedifferentiation within and between these different levels. PMID:25018731

  19. Structural Environment and Stability of the Complexes Formed Between Calmodulin and Actinyl Ions.

    PubMed

    Brulfert, Florian; Safi, Samir; Jeanson, Aurélie; Martinez-Baez, Ernesto; Roques, Jérôme; Berthomieu, Catherine; Solari, Pier-Lorenzo; Sauge-Merle, Sandrine; Simoni, Éric

    2016-03-21

    Because of their presence in the nuclear fuel cycle, neptunium and uranium are two actinides of main interest in case of internal contamination. Complexation of U(VI) and Np(V) by the target protein calmodulin (CaM(WT)) was therefore studied herein. Both actinides have two axial oxygen atoms, which, charge aside, makes them very similar structurally wise. This work combines spectroscopy and theoretical density functional theory (DFT) calculations. Structural characterization was performed by extended X-ray absorption fine structure (EXAFS) at the L(III)-edge for each studied actinide. Models for the binding site of the protein were developed and then refined by using DFT to fit the obtained experimental EXAFS data. The effect of hydrolysis was also considered for both actinides (the uranyl experiment was performed at pH 3 and 6, while the neptunyl experiment was conducted at pH 7 and 9). The effect of the pH variation was apparent on the coordination sphere of the uranyl complexes, while the neptunyl complex characteristics remained stable under both studied conditions. The DFT calculations showed that at near physiological pH the complex formed by CaM(WT) with the neptunium ion is more stable than the one formed with uranyl. PMID:26954703

  20. 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.

  1. Control of size in losartan/copper(II) coordination complex hydrophobic precipitate.

    PubMed

    Denadai, Ângelo M L; Da Silva, Jeferson G; Guimarães, Pedro P G; Gomes, Leonardo Bertolini S; Mangrich, Antonio S; de Rezende, Edivaltrys I P; Daniel, Izabela M P; Beraldo, Heloísa; Sinisterra, Rubén D

    2013-10-01

    Reaction of highly soluble orally active, non-peptide antihypertensive drug losartan with copper(II) leads to the spontaneous formation of a very insoluble 2:1 covalent complex, which self assembles in a hydrophobic supramolecular structure of nanometric dimensions. Thermal analysis showed that Los/Cu(II) complex presents intermediate stability in comparison with its precursors KLos and Cu(OAc)2·H2O. Isothermal titration calorimetry indicated complexation to be a stepwise process, driven by enthalpy and entropy. Zeta potential and DLS measurements showed that it is possible to control the size and charge of nanoprecipitates by adjusting the relative concentration of Los(-) and Cu(II). PMID:23910296

  2. Eight-coordinate stereochemistries of U(IV) catecholate and aquo complexes

    SciTech Connect

    Hay, Benjamin P.; Uddin, Jamal; Firman, Timothy K.

    2004-01-01

    An extended MM3 model has been used to identify all low energy configurations for U(IV) complexes with catecholate and aquo ligands. Both stochastic and systematic conformational analyses of[U(cat)n(OH2)8-n]4-2n complexes, n= 1 - 4, establish that 20 of the 67 possible stereochemistries are minima on the MM3 potential surface. The stable stereochemistries are reported for each stoichiometry and, where possible, the results are compared with experimental data and with the predictions from prior repulsion energy calculations.

  3. Physical and electrochemical interactions within hybrid nanocomposites of ruthenium coordination complexes and single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Alston, Jeffrey Resing

    The research presented in this dissertation is a study of the interaction of ruthenium coordination complexes with single-walled carbon nanotubes (SWCNTs), a pursuit ultimately leading to the development of composite SWCNT materials. The work comprising this dissertation includes three major accomplishments: the synthesis and characterization of two new dinuclear ruthenium coordination complexes, the development of isothermal titration calorimetry (ITC) to thermodynamically quantify interactions with SWCNTs, and the fabrication and characterization of ruthenium complex---SWCNT hybrid nanocomposite electrodes. The work leading to these major accomplishments is inspired by the goal of attaining control over assembly of nanoscale building blocks, i.e. SWCNTs. The first step towards this goal is the development of appropriate molecules that can nondestructively link two SWCNTs together without damaging the physical structure of the tube. [Cl(trpy)Ru(tpphz)Ru(trpy)Cl](PF6) 2 and [(phen)2Ru(tpphz)Ru(trpy)Cl](PF6)3 are the two ruthenium dimer molecules synthesized and discussed herein. They possess a rigid nanoscale pocket that contains conjugated pi-electron density capable of interacting with the walls of SWCNTs. During the work to synthesize these complexes significant improvements were made to synthetic procedures to produce important precursors. The synthesis of the two complexes and the new synthetic procedures were novel. The second step required the development of a new tool (ITC) to study the interaction thermodynamics of dispersions of SWCNTs. ITC is a well established tool to measure binding thermodynamics of biological proteins and enzymes. Based on the analogy that can drawn between SWCNTs in solution and proteins, I developed ITC methods and protocols for measuring interactions of solvents with SWCNTs as well as the binding of the ruthenium dimer complexes with SWCNTs. I have established that ITC can be an important nanoscale science and materials

  4. Functionally distinct Gata3/Chd4 complexes coordinately establish T helper 2 (Th2) cell identity

    PubMed Central

    Hosokawa, Hiroyuki; Tanaka, Tomoaki; Suzuki, Yutaka; Iwamura, Chiaki; Ohkubo, Shuichi; Endoh, Kanji; Kato, Miki; Endo, Yusuke; Onodera, Atsushi; Tumes, Damon John; Kanai, Akinori; Sugano, Sumio; Nakayama, Toshinori

    2013-01-01

    GATA binding protein 3 (Gata3) is a GATA family transcription factor that controls differentiation of naïve CD4 T cells into T helper 2 (Th2) cells. However, it is unknown how Gata3 simultaneously activates Th2-specific genes while repressing those of other Th lineages. Here we show that chromodomain helicase DNA-binding protein 4 (Chd4) forms a complex with Gata3 in Th2 cells that both activates Th2 cytokine transcription and represses the Th1 cytokine IFN-γ. We define a Gata3/Chd4/p300 transcriptional activation complex at the Th2 cytokine loci and a Gata3/Chd4–nucleosome remodeling histone deacetylase repression complex at the Tbx21 locus in Th2 cells. We also demonstrate a physiological role for Chd4 in Th2-dependent inflammation in an in vivo model of asthmatic inflammation. Thus, Gata3/Chd4 forms functionally distinct complexes, which mediate both positive and negative gene regulation to facilitate Th2 cell differentiation. PMID:23471993

  5. The DASH complex and Klp5/Klp6 kinesin coordinate bipolar chromosome attachment in fission yeast.

    PubMed

    Sanchez-Perez, Isabel; Renwick, Steven J; Crawley, Karen; Karig, Inga; Buck, Vicky; Meadows, John C; Franco-Sanchez, Alejandro; Fleig, Ursula; Toda, Takashi; Millar, Jonathan B A

    2005-08-17

    We identified a truncated allele of dam1 as a multicopy suppressor of the sensitivity of cdc13-117 (cyclin B) and mal3-1 (EB-1) cells to thiabendazole, a microtubule poison. We find that Dam1 binds to the plus end of spindle microtubules and kinetochores as cells enter mitosis and this is dependent on other components of the fission yeast DASH complex, including Ask1, Duo1, Spc34 and Dad1. By contrast, Dad1 remains bound to kinetochores throughout the cell cycle and its association is dependent on the Mis6 and Mal2, but not Mis12, Nuf2 or Cnp1, kinetochore proteins. In cells lacking Dam1, or other components of the DASH complex, anaphase is delayed due to activation of the spindle assembly checkpoint and lagging sister chromatids are frequently observed and occasionally sister chromatid pairs segregate to the same spindle pole. We find that the mitotic centromere-associated Klp5/Klp6 kinesin complex is essential in cells lacking components of the DASH complex. Cells lacking both Dam1 and Klp5 undergo a first cell cycle arrest in mitosis due to a failure to establish bipolar chromosome attachment. PMID:16079915

  6. School Nurses and Care Coordination for Children with Complex Needs: An Integrative Review

    ERIC Educational Resources Information Center

    McClanahan, Rachel; Weismuller, Penny C.

    2015-01-01

    Health care for students with chronic needs can be complex and specialized, resulting in fragmentation, duplication, and inefficiencies. Students who miss school due to chronic conditions lose valuable educational exposure that contributes to academic success. As health-related disabilities increase in prevalence so does the need for the…

  7. Synthesis and structure of [C 6H 14N 2][(UO 2) 4(HPO 4) 2(PO 4) 2(H 2O)]·H 2O: An expanded open-framework amine-bearing uranyl phosphate

    NASA Astrophysics Data System (ADS)

    Bray, Travis H.; Gorden, John D.; Albrecht-Schmitt, Thomas E.

    2008-09-01

    A new open-framework compound, [C 6H 14N 2][(UO 2) 4(HPO 4) 2(PO 4) 2(H 2O)]·H 2O, ( DUP-1) has been synthesized under mild hydrothermal conditions. The resulting structure consists of diprotonated DABCOH 22+ (C 6H 14N 22+) cations and occluded water molecules occupying the channels of a complex uranyl phosphate three-dimensional framework. The anionic lattice contains uranophane-like sheets connected by hydrated pentagonal bipyramidal UO 7 units. [C 6H 14N 2][(UO 2) 4(HPO 4) 2(PO 4) 2(H 2O)]·H 2O possesses five crystallographically unique U centers. U(VI) is present here in both six- and seven-coordinate environments. The DABCOH 22+ cations are held within the channels by hydrogen bonds to both two uranyl oxygen atoms and a μ2-O atom. Crystallographic data (193 K, Mo Kα, λ=0.71073 Å): DUP-1, monoclinic, P2 1/ n, a=7.017(1) Å, b=21.966(4) Å, c=17.619(3) Å, β=90.198(3)°, Z=4, R(F)=4.76% for 382 parameters with 6615 reflections with I>2 σ( I).

  8. pH-Dependent Assembly and Conversions of Six Cadmium(II)-Based Coordination Complexes

    SciTech Connect

    Fang, Hua-Cai; Zhu, Ji-Qin; Zhou, Li-Jiang; Jia, Hong-Yang; Li, Shan-Shan; Gong, Xue; Li, Shu-Bin; Cai, Yue-Peng; Thallapally, Praveen K.; Liu, Jun; Exarhos, Gregory J.

    2010-07-07

    Six cadmium(II) complexes containing N2O2 donor tetradentate asymmetrical Schiff base ligand 2-{[2-(dimethylamino)ethylimino]methyl}-6-methoxyphenol (HL5), namely, [(Cd3L52Cl4)2]•CH3OH•H2O (1), [Cd(L5)Cl]2•CH3OH (2), [Cd2(HL5)Cl4]n (3), {[Cd3(H2L5)2Cl8]•2H2O}n (4), [(H2L5)2]2+•[CdCl4]2-•H2O (5), and [(H2L5)2]2+•[CdCl4]2- (6), have been synthesized using cadmium(II) chloride and asymmetrical Schiff base ligand HL5 under different pH conditions at room temperature. The diverse structures show the marked sensitivity of the structural chemistry of the tetradentate asymmetrical Schiff base ligand HL5. Complex 1 formed at pH = 10 exhibits a rare zero- dimensional structure of trinuclear cadmium (II). At pH = 8-9, a dinuclear cadmium (II) complex 2 is formed. The reaction at pH = 5-7 leads to two one-dimensional structures of 3 and 4. A further decrease of the pH to 3-5 results in a zero-dimensional structure 5. Owing to the departure of lattice water molecules in the crystal, complex 5 at room temperature can gradually undergo single-crystal-to-single-crystal transformation to result complex 6. The results further show that conversions of complex 1 to 5 can also be achieved by adjusting the pH value of the reaction solution, 1→2pH=8→5pH=3 and 3→4pH=5. Comparing these experimental results, it is clear that the pH plays a crucial role in the formation of the resulting structures, which simultaneously provide very effective strategies for constructing the CdII compounds with N2O2 donor tetradentate asymmetrical Schiff base ligand. The strong fluorescent emissions of the six compounds (1-6) make them potentially useful photoactive materials. Furthermore, six Schiff base cadmium complexes (1–6), with DPPH (2,2-dipheny1-1-picrylhydrazy1) as a co-oxidant exhibited the stronger scavenging activity.

  9. Molecular orbital study of some eight-coordinate sulfur chelate complexes of molybdenum

    SciTech Connect

    Perkins, P.G.; Schultz, F.A.

    1983-03-30

    A number of molybdenum complexes involving the formal oxidation states Mo(IV) and Mo(V) have been studied by a self-consistent-field molecular orbital technique. All the complexes were of dodecahedral geometry and had eight sulfurs chelated to the central metal atom. In all, a series of five tetrakis complexes was studied, including the ligands dithiocarbamate (dtc), thioxanthate (txn), 1,1-dicyano-2,2-ethylenedithiolate (i-mnt), 1-cyano-1-carbethoxy-2,2-ethylenedithiolate (ced), and 1,1-dicarbethoxy-2,2-ethylenedithiolate (ded). The 4d orbitals were included on molybdenum, and the empty 3d levels on all sulfur atoms. The results show that the highest occupied molecular orbital in each case has over 90% metal d/sub xy/ character. Further, the energy of this orbital is linearly related to the reversible half-wave potentials for Mo(IV) ..-->.. Mo(V) and Mo(V) ..-->.. Mo(VI) oxidations of the complexes. A further irreversible oxidation observed experimentally also is closely related to the calculated energy levels. Relationships between the calculated results and Mo 3d/sub 5///sub 2/ X-ray photoelectron binding energies, EPR parameters, and charge-transfer absorption energies are discussed. Electrochemical and spectroscopic properties of these MoS/sub 8/ complexes can be understood in terms of a manifold of orbital energies that retain approximately constant spacings between one another and that move up or down in absolute energy in response to the charge donated or withdrawn by the ligands.

  10. Emission properties and Cu(i)-Cu(i) interaction in 2-coordinate dicopper(i)-bis(N-heterocyclic)carbene complexes.

    PubMed

    Nishikawa, Michihiro; Sano, Taichi; Washimi, Masaya; Takao, Koichiro; Tsubomura, Taro

    2016-07-26

    The synthesis, characterization, and emission properties of 2-coordinate dicopper(i) complexes bearing two trimethylene-bridged bis-NHC ligands, [Cu2(L3Me)2](PF6)2 (1), [Cu2(L3Et)2](PF6)2 (2), [Cu2(L3Bu)2](PF6)2 (3), [Cu2(L3MeOPh)2](PF6)2 (4) and [Cu2(L3Mes)2](PF6)2 (5), where L3R denotes trimethylene-bridged bis(N-heterocyclic)carbene (NHC) ligand substituted by two R groups at the nitrogen atoms of NHC, have been investigated. The quantum yield, Φ, and the lifetime, τ, of the emission of 2, are 0.21 and 25 μs, respectively in methanol, which is a well-known solvent for quenching the luminescence of many copper(i) complexes. The 8-shaped geometry of the dicopper(i) complexes brings a considerable copper(i)-copper(i) interaction which affects the luminescent properties. Additionally, we find that methoxyphenyl and mesityl groups substituted at the nitrogen atom of the NHC moiety drastically stabilize the bis(NHC) copper(i) complexes even in air-saturated acetone-d6. PMID:27399152

  11. Controllable assemblies of Cd(II) supramolecular coordination complexes based on a versatile tripyridyltriazole ligand and halide/pseduohalide anions

    NASA Astrophysics Data System (ADS)

    Wang, Xi; Guo, Wei; Guo, Ya-Mei

    2015-09-01

    Three Cd(II) complexes [Cd(L)(H2O)Cl2]n (1), [Cd(L)(H2O)Br2]n (2), and [Cd(L)I2]2 (3) have been assembled from CdX2 (1, X = Cl; 2, X = Br; 3, X = I) and a tripyridyltriazole ligand 3-(2-pyridyl)-4-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole (L). Complexes 1 and 2 are isostructural and exhibit 1-D loop-like chain, while complex 3 has a distinct dimeric macrocyclic motif. Interestingly, another 1-D chain [Cd(L)I(SCN)]n (4) can be achieved when NH4SCN is introduced into the assembled system of 3. Structural analysis of 1-4 illustrates that the halide and thiocyanate anions in these coordination complexes behave as not only the counteranions, but also the structure directing agents. The fluorescent and thermal properties of 1-4 have also been investigated.

  12. Coordination modes, spectral, thermal and biological evaluation of hetero-metal copper containing 2-thiouracil complexes

    NASA Astrophysics Data System (ADS)

    Masoud, Mamdouh S.; Soayed, Amina A.; El-Husseiny, Amel F.

    2012-12-01

    Mononuclear copper complex [CuL(NH3)4]Cl2·0.5H2O and three new hetero-metallic complexes: [Cu2Ni(L)2(NH3)2Cl2·6H2O] 2H2O, [Cu3Co(L)4·8H2O]Cl·4·5H2O, and [Cu4Co2Ni(L)3(OH)4(NH3)Cl4·3H2O]4H2O where L is 2-thiouracil, were prepared and characterized by elemental analyses, molar conductance, room-temperature magnetic susceptibility, spectral (IR, UV-Vis and ESR) studies and thermal analyses techniques (TG, DTG and DTA). The molar conductance data revealed that [CuL(NH3)4]Cl2·0.5H2O and [Cu3Co(L)4·8H2O]Cl·4.5H2O are electrolytes, while, [Cu2Ni(L)2(NH3)2Cl2·6H2O]·2H2O and [Cu4Co2Ni(L)3(OH)4(NH3)Cl4·3H2O]4H2O are non-electrolytes. IR spectra showed, that 2-thiouracil ligand behaves as a bidentate or tetradentate ligand. The geometry around the metal atoms is octahedral in all the prepared complexes except in [Cu4Co2Ni(L)3(OH)4(NH3)Cl4·3H2O]4H2O complex where square planar environment around Co(II), Ni(II) and Cu(II) were suggested. Thermal decomposition study of the prepared complexes was monitored by TG, DTG and DTA analyses under N2 atmosphere. The decomposition course and steps were analyzed. The order of chemical reactions (n) was calculated via the peak symmetry method and the activation parameters of the non- isothermal decomposition were computed from the thermal decomposition data. The negative values of ΔS∗ deduced the ordered structures of the prepared complexes compared to their starting reactants. The antimicrobial activity of the prepared complexes were screened in vitro against a Gram positive, a Gram negative bacteria, a filamentous fungi and a yeast. The antimicrobial screening data showed that the studied compounds exhibited a good level of activity against Escherichia coli, Staphylococcus aureus and Candida albicans but have no efficacy against Aspergillus flavus. It was observed that [Cu4Co2Ni(L)3(OH)4(NH3)Cl4·3H2O]4H2O complex showed the most intensive activity against the tested microorganisms. Trials to prepare single crystals from

  13. Evolving dynamics of trading behavior based on coordination game in complex networks

    NASA Astrophysics Data System (ADS)

    Bian, Yue-tang; Xu, Lu; Li, Jin-sheng

    2016-05-01

    This work concerns the modeling of evolvement of trading behavior in stock markets. Based on the assumption of the investors' limited rationality, the evolution mechanism of trading behavior is modeled according to the investment strategy of coordination game in network, that investors are prone to imitate their neighbors' activity through comprehensive analysis on the risk dominance degree of certain investment behavior, the network topology of their relationship and its heterogeneity. We investigate by mean-field analysis and extensive simulations the evolution of investors' trading behavior in various typical networks under different risk dominance degree of investment behavior. Our results indicate that the evolution of investors' behavior is affected by the network structure of stock market and the effect of risk dominance degree of investment behavior; the stability of equilibrium states of investors' behavior dynamics is directly related with the risk dominance degree of some behavior; connectivity and heterogeneity of the network plays an important role in the evolution of the investment behavior in stock market.

  14. An affinity-structure database of helix-turn-helix: DNA complexes with a universal coordinate system

    SciTech Connect

    AlQuraishi, Mohammed; Tang, Shengdong; Xia, Xide

    2015-11-19

    Molecular interactions between proteins and DNA molecules underlie many cellular processes, including transcriptional regulation, chromosome replication, and nucleosome positioning. Computational analyses of protein-DNA interactions rely on experimental data characterizing known protein-DNA interactions structurally and biochemically. While many databases exist that contain either structural or biochemical data, few integrate these two data sources in a unified fashion. Such integration is becoming increasingly critical with the rapid growth of structural and biochemical data, and the emergence of algorithms that rely on the synthesis of multiple data types to derive computational models of molecular interactions. We have developed an integrated affinity-structure database in which the experimental and quantitative DNA binding affinities of helix-turn-helix proteins are mapped onto the crystal structures of the corresponding protein-DNA complexes. This database provides access to: (i) protein-DNA structures, (ii) quantitative summaries of protein-DNA binding affinities using position weight matrices, and (iii) raw experimental data of protein-DNA binding instances. Critically, this database establishes a correspondence between experimental structural data and quantitative binding affinity data at the single basepair level. Furthermore, we present a novel alignment algorithm that structurally aligns the protein-DNA complexes in the database and creates a unified residue-level coordinate system for comparing the physico-chemical environments at the interface between complexes. Using this unified coordinate system, we compute the statistics of atomic interactions at the protein-DNA interface of helix-turn-helix proteins. We provide an interactive website for visualization, querying, and analyzing this database, and a downloadable version to facilitate programmatic analysis. Lastly, this database will facilitate the analysis of protein-DNA interactions and the

  15. An affinity-structure database of helix-turn-helix: DNA complexes with a universal coordinate system

    DOE PAGESBeta

    AlQuraishi, Mohammed; Tang, Shengdong; Xia, Xide

    2015-11-19

    Molecular interactions between proteins and DNA molecules underlie many cellular processes, including transcriptional regulation, chromosome replication, and nucleosome positioning. Computational analyses of protein-DNA interactions rely on experimental data characterizing known protein-DNA interactions structurally and biochemically. While many databases exist that contain either structural or biochemical data, few integrate these two data sources in a unified fashion. Such integration is becoming increasingly critical with the rapid growth of structural and biochemical data, and the emergence of algorithms that rely on the synthesis of multiple data types to derive computational models of molecular interactions. We have developed an integrated affinity-structure database inmore » which the experimental and quantitative DNA binding affinities of helix-turn-helix proteins are mapped onto the crystal structures of the corresponding protein-DNA complexes. This database provides access to: (i) protein-DNA structures, (ii) quantitative summaries of protein-DNA binding affinities using position weight matrices, and (iii) raw experimental data of protein-DNA binding instances. Critically, this database establishes a correspondence between experimental structural data and quantitative binding affinity data at the single basepair level. Furthermore, we present a novel alignment algorithm that structurally aligns the protein-DNA complexes in the database and creates a unified residue-level coordinate system for comparing the physico-chemical environments at the interface between complexes. Using this unified coordinate system, we compute the statistics of atomic interactions at the protein-DNA interface of helix-turn-helix proteins. We provide an interactive website for visualization, querying, and analyzing this database, and a downloadable version to facilitate programmatic analysis. Lastly, this database will facilitate the analysis of protein-DNA interactions and the

  16. Cationic terminal gallylene complexes by halide abstraction: coordination chemistry of a valence isoelectronic analogue of CO and N2.

    PubMed

    Coombs, Natalie D; Vidovic, Dragoslav; Day, Joanna K; Thompson, Amber L; Le Pevelen, Delphine D; Stasch, Andreas; Clegg, William; Russo, Luca; Male, Louise; Hursthouse, Michael B; Willock, David J; Aldridge, Simon

    2008-11-26

    While N(2) and CO have played central roles in developing models of electronic structure, and their interactions with transition metals have been widely investigated, the valence isoelectronic diatomic molecules EX (E = group 13 element, X = group 17 element) have yet to be isolated under ambient conditions, either as the "free" molecule or as a ligand in a simple metal complex. As part of a program designed to address this deficiency, together with wider issues of the chemistry of cationic systems [L(n)M(ER)](+) (E = B, Al, Ga; R = aryl, amido, halide), we have targeted complexes of the type [L(n)M(GaX)](+). Halide abstraction is shown to be a viable method for the generation of mononuclear cationic complexes containing gallium donor ligands. The ability to isolate tractable two-coordinate products, however, is strongly dependent on the steric and electronic properties of the metal/ligand fragment. In the case of complexes containing ancillary pi-acceptor ligands such as CO, cationic complexes can only be isolated as base-trapped adducts, even with bulky aryl substituents at gallium. Base-free gallylene species such as [Cp*Fe(CO)(2)(GaMes)](+) can be identified only in the vapor phase by electrospray mass spectrometry experiments. With bis(phosphine) donor sets at the metal, the more favorable steric/electronic environment allows for the isolation of two-coordinate ligand systems, even with halide substituents at gallium. Thus, [Cp*Fe(dppe)(GaI)](+)[BAr(f)(4)](-) (9) can be synthesized and shown crystallographically to feature a terminally bound GaI ligand; 9 represents the first experimental realization of a complex containing a valence isoelectronic group 13/group 17 analogue of CO and N(2). DFT calculations reveal a relatively weakly bound GaI ligand, which is confirmed experimentally by the reaction of 9 with CO to give [Cp*Fe(dppe)(CO)](+)[BAr(f)(4)](-). In the absence of such reagents, 9 is stable for weeks in fluorobenzene solution, presumably reflecting (i

  17. Coordinated aqua vs methanol substitution kinetics in fac-Re(I) tricarbonyl tropolonato complexes.

    PubMed

    Schutte, Marietjie; Roodt, Andreas; Visser, Hendrik G

    2012-11-01

    Water-soluble fac-[Re(CO)(3)(L,L'-Bid)(X)] (L,L'-Bid = tropolonato, X = H(2)O, methanol) complexes have been synthesized, and the aqua and methanol substitution reactions were investigated in water (pH range 6.3-10.0) and methanol, respectively, and compared. Thiocyanate ions were used as monodentate entering ligand. The complexes were characterized by UV-vis, IR, and NMR spectroscopy. The crystal structures of the complexes [NEt(4)] fac-[Re(Trop)(CO)(3)(H(2)O)].NO(3).H(2)O (reactant) and fac-[Re(CO)(3)(Trop)(Py)], a substitution product, are reported. Overall it was found that the aqua substitution of fac-[Re(CO)(3)(Trop)(H(2)O)] is about 10 times faster than the methanol substitution reaction for fac-[Re(CO)(3)(Trop)(MeOH)], with forward and reverse rate and stability constants [k(1) (M(-1) s(-1)), k(-1) (s(-1)), K(1), (M(-1))] for thiocyanate as monodentate entering ligand as follows: fac-[Re(CO)(3)(Trop)(H(2)O)] = 2.54 ± 0.03, 0.0077 ± 0.0005, 330 ± 22/207 ± 14 and fac-[Re(CO)(3)(Trop)(MeOH)] = 0.268 ± 0.002, 0.0044 ± 0.0002, (61 ± 3)/(52 ± 4). The activation parameters [ΔH(‡)(k1) (kJ mol(-1)), ΔS(‡)(k1) (J K(-1) mol(-1))] for the aqua and methanol complex respectively are 56.1 ± 0.7, -49 ± 2 and 64 ± 1, -43 ± 5. PMID:23088314

  18. Spontaneous Partitioning of Californium from Curium: Curious Cases from the Crystallization of Curium Coordination Complexes

    SciTech Connect

    Cary, Samantha K.; Silver, Mark A.; Liu, Guokui; Wang, Jamie C.; Bogart, Justin A.; Stritzinger, Jared T.; Arico, Alexandra A.; Hanson, Kenneth; Schelter, Eric J.; Albrecht-Schmitt, Thomas E.

    2015-12-07

    The reaction of 248CmCl3 with excess 2,6-pyridinedicarboxylic acid (DPA) under mild solvothermal conditions results in crystallization of the tris-chelate complex Cm(HDPA)3·H2O. Approximately half of the curium remains in solution at the end of this process, and evaporation of the mother liquor results in crystallization of the bis-chelate complex [Cm(HDPA)- (H2DPA)(H2O)2Cl]Cl·2H2O. 248Cm is the daughter of the α decay of 252Cf and is extracted in high purity from this parent. However, trace amounts of 249,250,251Cf are still present in all samples of 248Cm. During the crystallization of Cm(HDPA)3·H2O and [Cm(HDPA)(H2DPA)(H2O)2Cl]Cl·2H2O, californium(III) spontaneously separates itself from the curium complexes and is found doped within crystals of DPA in the form of Cf(HDPA)3. These results add to the growing body of evidence that the chemistry of californium is fundamentally different from that of earlier actinides.

  19. Iron Complexes for the Electrocatalytic Oxidation of Hydrogen: Tuning Primary and Secondary Coordination Spheres

    SciTech Connect

    Darmon, Jonathan M.; Raugei, Simone; Liu, Tianbiao L.; Hulley, Elliott B.; Weiss, Charles J.; Bullock, R. Morris; Helm, Monte L.

    2014-04-04

    A series of iron hydride complexes featuring PRNR'PR (PRNR'PR = R2PCH2N(R')CH2PR2 where R = Ph, R' = Me; R = Et, R' = Ph, Bn, Me, tBu) and cyclopentadienyl (CpX = C5H4X where X = H, C5F4N) ligands has been synthesized, characterized by NMR spectroscopy, X-ray diffraction and cyclic voltammetry, and examined by quantum chemistry calculations. Each compound was tested for the electrocatalytic oxidation of H2 and the most active complex, (CpC5F4N)Fe(PEtNMePEt)(H), exhibited a turnover frequency of 8.6 s-1 at 1 atm of H2 with an overpotential of 0.41 V, as measured from the half peak potential of the catalytic wave. Control complexes that do not contain pendant amine groups were also prepared and characterized, but no catalysis was observed. This work demonstrates the importance of the pendant amine in facilitating heterolytic H2 cleavage and subsequent proton movement necessary for electrocatalytic H2 oxidation. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  20. Physical Interactions and Functional Coordination between the Core Subunits of Set1/Mll Complexes and the Reprogramming Factors

    PubMed Central

    Yang, Zhenhua; Augustin, Jonathan; Hu, Jing; Jiang, Hao

    2015-01-01

    Differentiated cells can be reprogrammed to the pluripotent state by overexpression of defined factors, and this process is profoundly influenced by epigenetic mechanisms including dynamic histone modifications. Changes in H3K4 methylation have been shown to be the predominant activating response in the early stage of cellular reprogramming. Mechanisms underlying such epigenetic priming, however, are not well understood. Here we show that the expression of the reprogramming factors (Yamanaka factors, Oct4, Sox2, Klf4 and Myc), especially Myc, directly promotes the expression of certain core subunits of the Set1/Mll family of H3K4 methyltransferase complexes. A dynamic recruitment of the Set1/Mll complexes largely, though not sufficiently in its own, explains the dynamics of the H3K4 methylation during cellular reprogramming. We then demonstrate that the core subunits of the Set1/Mll complexes physically interact with mainly Sox2 and Myc among the Yamanaka factors. We further show that Sox2 directly binds the Ash2l subunit in the Set1/Mll complexes and this binding is mediated by the HMG domain of Sox2. Functionally, we show that the Set1/Mll complex core subunits are required for efficient cellular reprogramming. We also show that Dpy30, one of the core subunits in the complexes, is required for the efficient target binding of the reprogramming factors. Interestingly, such requirement is not necessarily dependent on locus-specific H3K4 methylation. Our work provides a better understanding of how the reprogramming factors physically interact and functionally coordinate with a key group of epigenetic modulators to mediate transitions of the chromatin state involved in cellular reprogramming. PMID:26691508

  1. Physical Interactions and Functional Coordination between the Core Subunits of Set1/Mll Complexes and the Reprogramming Factors.

    PubMed

    Yang, Zhenhua; Augustin, Jonathan; Hu, Jing; Jiang, Hao

    2015-01-01

    Differentiated cells can be reprogrammed to the pluripotent state by overexpression of defined factors, and this process is profoundly influenced by epigenetic mechanisms including dynamic histone modifications. Changes in H3K4 methylation have been shown to be the predominant activating response in the early stage of cellular reprogramming. Mechanisms underlying such epigenetic priming, however, are not well understood. Here we show that the expression of the reprogramming factors (Yamanaka factors, Oct4, Sox2, Klf4 and Myc), especially Myc, directly promotes the expression of certain core subunits of the Set1/Mll family of H3K4 methyltransferase complexes. A dynamic recruitment of the Set1/Mll complexes largely, though not sufficiently in its own, explains the dynamics of the H3K4 methylation during cellular reprogramming. We then demonstrate that the core subunits of the Set1/Mll complexes physically interact with mainly Sox2 and Myc among the Yamanaka factors. We further show that Sox2 directly binds the Ash2l subunit in the Set1/Mll complexes and this binding is mediated by the HMG domain of Sox2. Functionally, we show that the Set1/Mll complex core subunits are required for efficient cellular reprogramming. We also show that Dpy30, one of the core subunits in the complexes, is required for the efficient target binding of the reprogramming factors. Interestingly, such requirement is not necessarily dependent on locus-specific H3K4 methylation. Our work provides a better understanding of how the reprogramming factors physically interact and functionally coordinate with a key group of epigenetic modulators to mediate transitions of the chromatin state involved in cellular reprogramming. PMID:26691508

  2. A new chiral uranyl phosphonate framework consisting of achiral building units generated from ionothermal reaction: structure and spectroscopy characterizations.

    PubMed

    Zheng, Tao; Gao, Yang; Chen, Lanhua; Liu, Zhiyong; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2015-11-01

    The ionothermal reactions of uranyl nitrate and 1,3-pbpH4 (1,3-pbpH4 = 1,3-phenylenebis(phosphonic acid) ligand in ionic liquids of [C4mim][Dbp], [C4mpyr][Br], and [Etpy][Br], respectively, afforded three new uranyl phosphonates, namely [C4mim][(UO2)2(1,3-pbpH)(1,3-pbpH)·Hmim] (1), [UO2(1,3-pbpH2)H2O·mpr] (2), and [Etpy][UO2(1,3-pbpH2)F] (3). Compound 1 exhibits a rare example of a chiral uranyl phosphonate 3D framework structure built from achiral building units of tetragonal bipyramidal uranium polyhedra and 1,3-pbp ligands. The structure adopts a network with channels extending along the b axis, which are filled with C4mim(+) and protonated 1-methylimidazole. In sharp contrast, compounds 2 & 3 both show pillared topology composed of uranyl pentagonal bipyramid polyhedra and phosphonate ligands. The layers are neutral in compound 2 with N-methylpyrrole molecules in the interlayer space, while compound 3 adopts anionic layer, and the charge is compensated with N-ethyl-pyridinium cations between the layers. Although compounds 1, 2, and 3 were synthesized under identical conditions with sole variation of the ionic liquid species, the resulting structures show a rich diversity in the local coordination environment of uranyl ions, the protonation of the phosphonate ligand, the conformation of ionic liquid ions, and the overall arrangement of the structure. All compounds were characterized by absorption, temperature dependent fluorescence, as well as infrared and Raman spectroscopies. PMID:26419426

  3. EB1-recruited microtubule +TIP complexes coordinate protrusion dynamics during 3D epithelial remodeling

    PubMed Central

    Gierke, Sarah; Wittmann, Torsten

    2012-01-01

    SUMMARY Background Epithelial remodeling, in which apical-basal polarized cells switch to a migratory phenotype, plays a central role in development and disease of multicellular organisms. Although dynamic microtubules (MTs) are required for directed migration on flat surfaces, how MT dynamics are controlled or contribute to epithelial remodeling in a more physiological three-dimensional (3D) environment is not understood. We use confocal live cell imaging to analyze MT function and dynamics during 3D epithelial morphogenesis and remodeling of polarized Madin-Darby canine kidney (MDCK) epithelial cells that undergo partial epithelial-to-mesenchymal transition (EMT) in response to hepatocyte growth factor (HGF). Results We find that HGF treatment increases MT growth rate before morphological changes are evident, and that large numbers of MTs grow into HGF-induced cell extensions independent of centrosome reorientation. Using lentivirus-mediated shRNA, we demonstrate that EB1, an adaptor protein that mediates recruitment of numerous other +TIP proteins to growing MT plus ends, is required for this HGF-induced MT reorganization. We further show that protrusion and adhesion dynamics are disorganized, and that vesicular trafficking to the tip of HGF-induced cell extensions is disrupted in EB1-depleted cells. Conclusions We conclude that EB1-mediated interactions with growing MTs are important to coordinate cell shape changes and directed migration into the surrounding extracellular matrix during epithelial remodeling in a physiological 3D environment. In contrast, EB1 is not required for the establishment or maintenance of apical-basal cell polarity, suggesting different functions of +TIPs and MTs in different types of cell polarity. PMID:22483942

  4. Spin Crossover in Fe(II) Complexes with N4S2 Coordination.

    PubMed

    Arroyave, Alejandra; Lennartson, Anders; Dragulescu-Andrasi, Alina; Pedersen, Kasper S; Piligkos, Stergios; Stoian, Sebastian A; Greer, Samuel M; Pak, Chongin; Hietsoi, Oleksandr; Phan, Hoa; Hill, Stephen; McKenzie, Christine J; Shatruk, Michael

    2016-06-20

    Reactions of Fe(II) precursors with the tetradentate ligand S,S'-bis(2-pyridylmethyl)-1,2-thioethane (bpte) and monodentate NCE(-) coligands afforded mononuclear complexes [Fe(bpte)(NCE)2] (1, E = S; 2, E = Se; 3, E = BH3) that exhibit temperature-induced spin crossover (SCO). As the ligand field strength increases from NCS(-) to NCSe(-) to NCBH3(-), the SCO shifts to higher temperatures. Complex 1 exhibits only a partial (15%) conversion from the high-spin (HS) to the low-spin (LS) state, with an onset around 100 K. Complex 3 exhibits a complete SCO with T1/2 = 243 K. While the γ-2 polymorph also shows the complete SCO with T1/2 = 192 K, the α-2 polymorph exhibits a two-step SCO with the first step leading to a 50% HS → LS conversion with T1/2 = 120 K and the second step proceeding incompletely in the 80-50 K range. The amount of residual HS fraction of α-2 that remains below 60 K depends on the cooling rate. Fast flash-cooling allows trapping of as much as 45% of the HS fraction, while slow cooling leads to a 14% residual HS fraction. The slowly cooled sample of α-2 was subjected to irradiation in the magnetometer cavity resulting in a light-induced excited spin state trapping (LIESST) effect. As demonstrated by Mössbauer spectroscopy, an HS fraction of up to 85% could be achieved by irradiation at 4.2 K. PMID:27280361

  5. METHOD OF INHIBITING CORROSION IN URANYL SULFATE SOLUTIONS

    DOEpatents

    Bohlmann, E.G.; Griess, J.C. Jr.

    1960-08-23

    A method is given for treating a uranyl sulfate solution to inhibit the corrosiveness of the solution and elevate the phase separation temperature of the solution. Lithium sulfate is added to the solution in an amount ranging from 0.25 to 1.3 times the uranyl sulfate concentration. The corrosiveness of the solution with respect to stainless steel is substantially decreased by this means. This treatment also serves to raise the phase separation temperature of the solution (above 250 deg C), at which time the uranyl sulfate solution separates into two liquid phases of unequal uranium concentration and thus becomes unsuitable as nuclear reactor fuel.

  6. Incorporation of neptunium(VI) into a uranyl selenite.

    PubMed

    Meredith, Nathan A; Polinski, Matthew J; Lin, Jian; Simonetti, Antonio; Albrecht-Schmitt, Thomas E

    2012-10-15

    The incorporation of neptunium(VI) into the layered uranyl selenite Cs[(UO(2))(HSeO(3))(SeO(3))] has yielded the highest level of neptunium uptake in a uranyl compound to date with an average of 12(±3)% substitution of Np(VI) for U(VI). Furthermore, this is the first case in nearly 2 decades of dedicated incorporation studies in which the oxidation state of neptunium has been determined spectroscopically in a doped uranyl compound and also the first time in which neptunium incorporation has resulted in a structural transformation. PMID:23030830

  7. Cobalt Complexes Containing Pendant Amines in the Second Coordination Sphere as Electrocatalysts for H2 Production

    SciTech Connect

    Fang, Ming; Wiedner, Eric S.; Dougherty, William G.; Kassel, W. S.; Liu, Tianbiao L.; DuBois, Daniel L.; Bullock, R. Morris

    2014-10-27

    A series of heteroleptic 17e- cobalt complexes, [CpCoII(PtBu2NPh2)](BF4), [CpC6F5CoII(PtBu2NPh2)](BF4), [CpC5F4NCoII(PtBu2NPh2)](BF4), [where P2tBuN2Ph = 1,5-diphenyl-3,7-di(tert-butyl)-1,5-diaza-3,7-diphosphacyclooctane, CpC6F5 = C5H4(C6F5), and CpC5F4N = C5H4(C5F4N)] were synthesized, and structures of all three were determined by X-ray crystallography. Electrochemical studies showed that the CoIII/II couple of [CpC5F4NCoII(PtBu2NPh2)]+ appears 250 mV positive of the CoIII/II couple of [CpCoII(PtBu2NPh2)] as a result of the strongly electron-withdrawing perfluorpyridyl substituent on the Cp ring. Reduction of these paramagnetic CoII complexes by KC8 led to the diamagnetic 18e- complexes CpICo(PtBu2NPh2), CpC6F5CoI(PtBu2NPh2), CpC5F4NCoI(PtBu2NPh2), which were also characterized by crystallography. Protonation of these neutral CoI complexes led to the cobalt hydrides [CpCoIII(PtBu2NPh2)H](BF4), [CpC6F5CoIII(PtBu2NPh2)H](BF4), and [CpC5F4NCoIII(PtBu2NPh2)H](BF4). The cobalt hydride with the most electron-withdrawing Cp ligand, [CpC5F4NCoIII(PtBu2NPh2)H]+ is an electrocatalyst for production of H2 using 4-MeOC6H4NH3BF4 (pKaMeCN = 11.86) with a turnover frequency of 350 s-1 and an overpotential of 0.75 V. Experimental measurement of thermochemical data provided further insights into the thermodynamics of H2 elimination. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  8. Electrocatalytic reduction of CO2 using Mn complexes with unconventional coordination environments.

    PubMed

    Rao, Gyandshwar Kumar; Pell, Wendy; Korobkov, Ilia; Richeson, Darrin

    2016-06-28

    New complexes, Mn{κ(3)-[2,6-{Ph2PNMe}2(NC5H3)]}(CO)3(+)Br(-) (1(+)Br(-)) and MnBr{κ(2)-(Ph2P)NMe(NC5H4)}(CO)3 (2), are reported and present new ligand environments for CO2 electrocatalytic reduction to CO. Compound 1(+) presents a unique metal geometry for CO production (96%) in the absence of added water while 2 required addition of water and generated both CO and H2 products. PMID:27264057

  9. Determination of uranyl incorporation into biogenic manganese oxides using X-ray absorption spectroscopy and scattering

    USGS Publications Warehouse

    Webb, S.M.; Fuller, C.C.; Tebo, B.M.; Bargar, J.R.

    2006-01-01

    Biogenic manganese oxides are common and an important source of reactive mineral surfaces in the environment that may be potentially enhanced in bioremediation cases to improve natural attenuation. Experiments were performed in which the uranyl ion, UO22+ (U(VI)), at various concentrations was present during manganese oxide biogenesis. At all concentrations, there was strong uptake of U onto the oxides. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) studies were carried out to determine the molecular-scale mechanism by which uranyl is incorporated into the oxide and how this incorporation affects the resulting manganese oxide structure and mineralogy. The EXAFS experiments show that at low concentrations (2 mol % U, >4 ??M U(VI) in solution), the presence of U(VI) affects the stability and structure of the Mn oxide to form poorly ordered Mn oxide tunnel structures, similar to todorokite. EXAFS modeling shows that uranyl is present in these oxides predominantly in the tunnels of the Mn oxide structure in a tridentate complex. Observations by XRD corroborate these results. Structural incorporation may lead to more stable U(VI) sequestration that may be suitable for remediation uses. These observations, combined with the very high uptake capacity of the Mn oxides, imply that Mn-oxidizing bacteria may significantly influence dissolved U(VI) concentrations in impacted waters via sorption and incorporation into Mn oxide biominerals. ?? 2006 American Chemical Society.

  10. Coordination complexes of niobium and tantalum pentahalides with a bulky NHC ligand.

    PubMed

    Bortoluzzi, Marco; Ferretti, Eleonora; Marchetti, Fabio; Pampaloni, Guido; Zacchini, Stefano

    2016-04-28

    The 1 : 1 molar reactions of niobium and tantalum pentahalides with the monodentate NHC ligand 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (Ipr), in toluene (or benzene) at ca. 80 °C, afforded the complexes NbX5(Ipr) (X = F, ; Br, ) and TaX5(Ipr) (X = F, ; Cl, ; Br, ), in generally good yields. Complexes represent uncommon cases of stable NHC adducts of metal halides with the metal in an oxidation state higher than +4, and also rare examples of Nb-NHC and Ta-NHC bonding systems. In particular, the X-ray molecular structure determined for provides the unprecedented crystallographic characterization of a tantalum compound with a monodentate NHC ligand. DFT results indicate that the metal-carbon bond in is a purely σ one. According to NMR studies ((1)H, (13)C, (93)Nb), the formation of , , , as well as the previously communicated NbCl5(Ipr), , proceeded with the intermediacy of [MX6](-) salts, presumably due to steric reasons. On the other hand, the intermediate formation of MF6(-) in the pathways to and was not observed, according to (19)F (and (93)Nb in the case of ) NMR. DFT calculations were carried out in order to shed light on structural and mechanistic aspects, and allowed to trace possible reaction routes. PMID:26982241

  11. Chemistry of ion coordination and hydration revealed by a K+ channel-Fab complex at 2.0Å resolution

    NASA Astrophysics Data System (ADS)

    Zhou, Yufeng; Morais-Cabral, João H.; Kaufman, Amelia; MacKinnon, Roderick

    2001-11-01

    Ion transport proteins must remove an ion's hydration shell to coordinate the ion selectively on the basis of its size and charge. To discover how the K+ channel solves this fundamental aspect of ion conduction, we solved the structure of the KcsA K+ channel in complex with a monoclonal Fab antibody fragment at 2.0Å resolution. Here we show how the K+ channel displaces water molecules around an ion at its extracellular entryway, and how it holds a K+ ion in a square antiprism of water molecules in a cavity near its intracellular entryway. Carbonyl oxygen atoms within the selectivity filter form a very similar square antiprism around each K+ binding site, as if to mimic the waters of hydration. The selectivity filter changes its ion coordination structure in low K+ solutions. This structural change is crucial to the operation of the selectivity filter in the cellular context, where the K+ ion concentration near the selectivity filter varies in response to channel gating.

  12. Complex Coordination of Cell Plasticity by a PGC-1α-controlled Transcriptional Network in Skeletal Muscle

    PubMed Central

    Kupr, Barbara; Handschin, Christoph

    2015-01-01

    Skeletal muscle cells exhibit an enormous plastic capacity in order to adapt to external stimuli. Even though our overall understanding of the molecular mechanisms that underlie phenotypic changes in skeletal muscle cells remains poor, several factors involved in the regulation and coordination of relevant transcriptional programs have been identified in recent years. For example, the peroxisome proliferator-activated receptor γ coactivator-1α (PGC-1α) is a central regulatory nexus in the adaptation of muscle to endurance training. Intriguingly, PGC-1α integrates numerous signaling pathways and translates their activity into various transcriptional programs. This selectivity is in part controlled by differential expression of PGC-1α variants and post-translational modifications of the PGC-1α protein. PGC-1α-controlled activation of transcriptional networks subsequently enables a spatio-temporal specification and hence allows a complex coordination of changes in metabolic and contractile properties, protein synthesis and degradation rates and other features of trained muscle. In this review, we discuss recent advances in our understanding of PGC-1α-regulated skeletal muscle cell plasticity in health and disease. PMID:26617528

  13. Uranyl Solvation by a Three-Dimensional Reference Interaction Site Model.

    PubMed

    Matveev, Alexei; Li, Bo; Rösch, Notker

    2015-08-13

    We report an implementation of the three-dimensional reference interaction site model (3D RISM) that in particular addresses the treatment of the long-range Coulomb field of charged species, represented by point charges and/or a distributed charge density. A comparison of 1D and 3D results for atomic ions demonstrates a reasonable accuracy, even for a moderate size of the unit cell and a moderate grid resolution. In an application to uranyl complexes with 4-6 explicit aqua ligands and an implicit bulk solvent modeled by RISM, we show that the 3D technique is not susceptible to the deficiencies of the 1D technique exposed in our previous work [Li, Matveev, Krüger, Rösch, Comp. Theor. Chem. 2015, 1051, 151]. The 3D method eliminates the artificial superposition of explicit aqua ligands and the RISM medium and predicts essentially the same values for uranyl and uranyl-water bond lengths as a state-of-the-art polarizable continuum model. With the first solvation shell treated explicitly, the observables are nearly independent of the order of the closure relationship used when solving the set of integral equations for the various distribution functions. Furthermore, we calculated the activation barrier of water exchange with a hybrid approach that combines the 3D RISM model for the bulk aqueous solvent and a quantum mechanical description (at the level of electronic density functional theory) of uranyl interacting with explicitly represented water molecules. The calculated result agrees very well with experiment and the best theoretical estimates. PMID:26167741

  14. Thermodynamic properties of autunite, uranyl hydrogen phosphate, and uranyl orthophosphate from solubility and calorimetric measurements

    SciTech Connect

    Gorman-Lewis, Drew; Shareva, Tatiana; kubatko, Karrie-Ann; burns, Peter; Wellman, Dawn M.; McNamara, Bruce K.; szymanowski, jennifer; Navrotsky, Alexandra; Fein, Jeremy B.

    2009-10-01

    In this study, we use solubility and oxide melt solution calorimetry measurements to determine the thermodynamic properties of the uranyl phosphate phases autunite (abbreviated: CaUP), uranyl hydrogen phosphate (HUP), and uranyl orthophosphate (UP). Solubility measurements from both supersaturated and undersaturated conditions, as well as under different pH conditions, rigorously demonstrate attainment of equilibrium and yield well-constrained solubility product values of -48.36 (-0.03 /+ 0.03), -13.17 (-0.11 / +0.07), and -49.36 (-0.04 / +0.02) for CaUP, HUP, and UP, respectively. We use the solubility data to calculate standard state Gibbs free energies of formation for all phases (-7630.61 ± 9.69, -3072.27 ± 4.76, and -6138.95 ± 12.24 kJ mol-1 for CaUP, HUP, and UP, respectively), and calorimetry data to calculate standard state enthalpies of formation of -3223.22 ± 4.00 and -7001.01 ± 15.10 kJ mol-1 for HUP and UP, respectively. Combining these results allows us also to calculate the standard state entropies of formation of -506.54 ± 10.48 and -2893.12 ± 19.44 kJ mol-1 K-1 for HUP and UP phases, respectively. The results from this study are part of a combined effort to develop reliable and internally consistent thermodynamic data for environmentally relevant uranyl minerals. Data such as these are required in order to optimize and quantitatively assess the effect of phosphate amendment remediation technologies for uranium contaminated systems.

  15. Mononuclear and dinuclear peroxotungsten complexes with co-ordinated dipeptides as potent inhibitors of alkaline phosphatase activity.

    PubMed

    Hazarika, Pankaj; Kalita, Diganta; Islam, Nashreen S

    2008-08-01

    New molecular peroxotungstate(VI) complexes with dipeptides as ancillary ligands of the type, [WO(O(2))(2)(dipeptide)(H(2)O)].3H(2)O, dipeptide = glycyl-glycine or glycyl-leucine, have been synthesized and characterized by elemental analysis, spectral and physico-chemical methods including thermal analysis. The complexes contain side-on bound peroxo groups and a peptide zwitterion bonded to the metal centre unidentately through an O(carboxylate) atom. Investigations on certain biologically important key properties of these compounds and a set of dimeric compounds in analogous co-ligand environment, Na(2)[W(2)O(3)(O(2))(4)(dipeptide)(2)].3H(2)O, dipeptide = glycyl-glycine and glycyl-leucine, reported previously by us revealed interesting features of the compounds. Each of the compounds despite having a 7 co-ordinated metal centre exerts a strong inhibitory effect on alkaline phosphatase activity with a potency higher than that of the free dipeptide, tungstate or peroxotungstate. The compounds exhibit remarkable stability in solutions of acidic as well as physiological pH and are weaker as substrate to the enzyme catalase, compared to H(2)O(2). The mononuclear and dinuclear peroxotungsten compounds are efficient oxidants of reduced glutathione (GSH), a reaction in which only one of the peroxo groups of a diperoxotungsten moiety of the complexes was found to be active. PMID:18665997

  16. Hybrid Organic-Inorganic Coordination Complexes as Tunable Optical Response Materials.

    PubMed

    Travis, Will; Knapp, Caroline E; Savory, Christopher N; Ganose, Alex M; Kafourou, Panagiota; Song, Xingchi; Sharif, Zainab; Cockcroft, Jeremy K; Scanlon, David O; Bronstein, Hugo; Palgrave, Robert G

    2016-04-01

    Novel lead and bismuth dipyrido complexes have been synthesized and characterized by single-crystal X-ray diffraction, which shows their structures to be directed by highly oriented π-stacking of planar fully conjugated organic ligands. Optical band gaps are influenced by the identity of both the organic and inorganic component. Density functional theory calculations show optical excitation leads to exciton separation between inorganic and organic components. Using UV-vis, photoluminescence, and X-ray photoemission spectroscopies, we have determined the materials' frontier energy levels and show their suitability for photovoltaic device fabrication by use of electron- and hole-transport materials such as TiO2 and spiro-OMeTAD respectively. Such organic/inorganic hybrid materials promise greater electronic tunability than the inflexible methylammonium lead iodide structure through variation of both the metal and organic components. PMID:26974692

  17. MicroRNA-128 coordinately targets Polycomb Repressor Complexes in glioma stem cells

    PubMed Central

    Peruzzi, Pierpaolo; Bronisz, Agnieszka; Nowicki, Michal O.; Wang, Yan; Ogawa, Daisuke; Price, Richard; Nakano, Ichiro; Kwon, Chang-Hyuk; Hayes, Josie; Lawler, Sean E.; Ostrowski, Michael C.; Chiocca, E. Antonio; Godlewski, Jakub

    2013-01-01

    Background The Polycomb Repressor Complex (PRC) is an epigenetic regulator of transcription whose action is mediated by 2 protein complexes, PRC1 and PRC2. PRC is oncogenic in glioblastoma, where it is involved in cancer stem cell maintenance and radioresistance. Methods We used a set of glioblastoma patient samples, glioma stem cells, and neural stem cells from a mouse model of glioblastoma. We characterized gene/protein expression and cellular phenotypes by quantitative PCR/Western blotting and clonogenic, cell-cycle, and DNA damage assays. We performed overexpression/knockdown studies by lentiviral infection and microRNA/small interfering RNA oligonucleotide transfection. Results We show that microRNA-128 (miR-128) directly targets mRNA of SUZ12, a key component of PRC2, in addition to BMI1, a component of PRC1 that we previously showed as a target as well. This blocks the partially redundant functions of PRC1/PRC2, thereby significantly reducing PRC activity and its associated histone modifications. MiR-128 and SUZ12/BMI1 show opposite expression in human glioblastomas versus normal brain and in glioma stemlike versus neural stem cells. Furthermore, miR-128 renders glioma stemlike cells less radioresistant by preventing the radiation-induced expression of both PRC components. Finally, miR-128 expression is significantly reduced in neural stem cells from the brain of young, presymptomatic mice in our mouse model of glioblastoma. This suggests that loss of miR-128 expression in brain is an early event in gliomagenesis. Moreover, knockdown of miR-128 expression in nonmalignant mouse and human neural stem cells led to elevated expression of PRC components and increased clonogenicity. Conclusions MiR-128 is an important suppressor of PRC activity, and its absence is an early event in gliomagenesis. PMID:23733246

  18. Adjustable coordination of a hybrid phosphine-phosphine oxide ligand in luminescent Cu, Ag and Au complexes.

    PubMed

    Dau, Thuy Minh; Asamoah, Benjamin Darko; Belyaev, Andrey; Chakkaradhari, Gomathy; Hirva, Pipsa; Jänis, Janne; Grachova, Elena V; Tunik, Sergey P; Koshevoy, Igor O

    2016-09-28

    A potentially tridentate hemilabile ligand, PPh2-C6H4-PPh(O)-C6H4-PPh2 (P(3)O), has been used for the construction of a family of bimetallic complexes [MM'(P(3)O)2](2+) (M = M' = Cu (1), Ag (2), Au (3); M = Au, M' = Cu (4)) and their mononuclear halide congeners M(P(3)O)Hal (M = Cu (5-7), Ag (8-10)). Compounds 1-10 have been characterized in the solid state by single-crystal X-ray diffraction analysis to reveal a variable coordination mode of the phosphine-oxide group of the P(3)O ligand depending on the preferable number of coordination vacancies on the metal center. According to the theoretical studies, the interaction of the hard donor P[double bond, length as m-dash]O moiety with d(10) ions becomes less effective in the order Cu > Ag > Au. 1-10 exhibit room temperature luminescence in the solid state, and the intensity and energy of emission are mostly determined by the nature of metal atoms. The photophysical characteristics of the monometallic species were compared with those of the related compounds M(P(3))Hal (11-16) with the non-oxidized ligand P(3). It was found that in the case of the copper complexes 5-7 the P(3)O hybrid ligand introduces effective non-radiative pathways of the excited state relaxation leading to poor emission, while for the silver luminophores the P[double bond, length as m-dash]O group leads mainly to the modulation of luminescence wavelength. PMID:27530362

  19. Assessment of accidental intakes of uranyl acetylacetonate (UAA)

    SciTech Connect

    Fisher, D.R.; Briant, J.K.

    1993-12-01

    Uranyl acetylacetonate (UAA) is an organic complex of uranium used for military applications as a chemical catalyst in high explosives. It is prepared from depleted uranium metal (in lots of 5 kg to 7 kg) by dissolution in nitric acid, neutralization, and complexation with 2,4-pentanedione; the precipitate is dissolved in benzene and recrystallized, dried, ground, and packaged. About six workers at a small chemical company were exposed over a period of time to UAA powders during routine preparation and packaging of the uranium catalyst. The dissolution characteristics of the inhaled material were unknown and could not be determined from the published scientific literature. A 1.05-g sample of UAA powder was obtained from the responsible regulatory authority for further study to determine its chemical composition, and for dissolution in simulated lung fluid. We found the solubility of UAA to be equivalent to a mixture of 52% ICRP class D and 48% ICRP class W material. The annual limit on intake and the derived air concentration for radiological protection were estimated from this result for airborne exposure to UAA. A recycling biokinetic model was used to estimate both material-specific variations in urinary excretion rates and lung retention with time after accidental intakes. This study provides new information for evaluating future exposures to UAA.

  20. Syntheses and structures of dinuclear gold(I) dithiophosphonate complexes and the reaction of the dithiophosphonate complexes with phosphines: diverse coordination types.

    PubMed

    Maspero, Angelo; Kani, Ibrahim; Mohamed, Ahmed A; Omary, Mohammad A; Staples, Richard J; Fackler, John P

    2003-08-25

    The dinuclear gold(I) dithiophosphonate complex, [Au(2)(dtp)(2)] (1), where dtp = [S(2)P(R)(OR')](-) with R = p-C(6)H(4)OCH(3); R'= c-C(5)H(9), has been synthesized and its reaction studied with the phosphine ligands PPh(3) and Ph(2)P(CH(2))(n)PPh(2) (n = 1-4). Compound 1 contains two gold atoms homobridged by the anionic dithiophosphonate ligand, forming an eight-membered ring complex in a chair form. After the reaction of 1 with diphosphine ligands, the dinuclear open-ring complexes Au(2)(dppm)(dtp)(2) (2), Au(2)(dppe)(dtp)(2) (3), Au(2)(dppp)(dtp)(2) (4), Au(2)(dppb)(dtp)(2) (5) were formed (dppm = diphenylphosphinomethane; dppe = diphenylphosphinoethane; dppp = diphenylphosphinopropane; dppb = diphenylphosphinobutane). The reaction with dppm is stoichiometry-dependent. Thus, when 1 reacts with 2 equiv of dppm, the ionic complex [Au(2)(dppm)(2)(dtp)]dtp forms. This dtp counterion was exchanged with tetrafluoroborate to yield [Au(2)(dppm)(2)(dtp)]BF(4), the crystallization of which afforded two interconvertible isomers, 6-yellow and 7-white. Reaction of 1 with PPh(3) affords the tetracoordinate mononuclear complex [Au(dtp)(PPh(3))(2)] (8). The molecular structures of 1-8 were confirmed by X-ray crystallography and show multiple coordination modes and geometries. The crystal structures of 1 and its reaction products with dppm (2, 6, 7) show short intramolecular Au.Au aurophilic bonding interactions of 2.95-3.10 A while no intermolecular interactions were discernible. However, reaction products of 1 with longer-chain Ph(2)P(CH(2))(n)PPh(2) ligands, n = 2-4, exhibit structures that lack both intra- and intermolecular Au.Au interactions. PMID:12924903

  1. Macrocyclic lanthanide complexes as artificial nucleases and ribonucleases: effects of pH, metal ionic radii, number of coordinated water molecules, charge, and concentrations of the metal complexes.

    PubMed

    Chang, C Allen; Wu, Bo Hong; Kuan, Bu Yuan

    2005-09-19

    We have been interested in the design, synthesis, and characterization of artificial nucleases and ribonucleases by employing macrocyclic lanthanide complexes because their high thermodynamic stability, low kinetic lability, high coordination number, and charge density (Lewis acidity) allow more design flexibility and stability. In this paper, we report the study of the use of the europium(III) complex, EuDO2A+ (DO2A is 1,7-dicarboxymethyl-1,4,7,10-tetraazacyclododecane) and other lanthanide complexes (i.e., LaDO2A+, YbDO2A+, EuK21DA+, EuEDDA+, and EuHEDTA where K21DA is 1,7-diaza-4,10,13-trioxacyclopentadecane-N,N'-diacetic acid, EDDA is ethylenediamine-N,N'-diacetic acid, and HEDTA is N-hydroxyethyl-ethylenediamine-N,N',N'-triacetic acid), as potential catalysts for the hydrolysis of the phosphodiester bond of BNPP (sodium bis(4-nitrophenyl)-phosphate). For the pH range 7.0-11.0 studied, EuDO2A+ promotes BNPP hydrolysis with the quickest rates among LaDO2A+, EuDO2A+, and YbDO2A+. This indicates that charge density is not the only factor affecting the reaction rates. Among the four complexes, EuDO2A+, EuK21DA+, EuEDDA+, and EuHEDTA, with their respective number of inner-sphere coordinated water molecules three, two, five, and three, EuEDDA+, with the greatest number of inner-sphere coordinated water molecules and a positive charge, promotes BNPP hydrolysis more efficiently at pH below 8.4, and the observed rate trend is EuEDDA+ > EuDO2A+ > EuK21DA+ > EuHEDTA. At pH > 8.4, the EuEDDA+ solution becomes misty and precipitates form. At pH 11.0, the hydrolysis rate of BNPP in the presence of EuDO2A+ is 100 times faster than that of EuHEDTA, presumably because the positively charged EuDO2A+ is more favorable for binding with the negatively charged phosphodiester compounds. The logarithmic hydrolysis constants (pKh) were determined, and are reported in the parentheses, by fitting the kinetic k(obs) data vs pH for EuDO2A+ (8.4), LaDO2A+ (8.4), YbDO2A+ (9.4), EuK21DA+ (7

  2. Ammonia Binding in the Second Coordination Sphere of the Oxygen-Evolving Complex of Photosystem II.

    PubMed

    Vinyard, David J; Askerka, Mikhail; Debus, Richard J; Batista, Victor S; Brudvig, Gary W

    2016-08-01

    Ammonia binds to two sites in the oxygen-evolving complex (OEC) of Photosystem II (PSII). The first is as a terminal ligand to Mn in the S2 state, and the second is at a site outside the OEC that is competitive with chloride. Binding of ammonia in this latter secondary site results in the S2 state S = (5)/2 spin isomer being favored over the S = (1)/2 spin isomer. Using electron paramagnetic resonance spectroscopy, we find that ammonia binds to the secondary site in wild-type Synechocystis sp. PCC 6803 PSII, but not in D2-K317A mutated PSII that does not bind chloride. By combining these results with quantum mechanics/molecular mechanics calculations, we propose that ammonia binds in the secondary site in competition with D1-D61 as a hydrogen bond acceptor to the OEC terminal water ligand, W1. Implications for the mechanism of ammonia binding via its primary site directly to Mn4 in the OEC are discussed. PMID:27433995

  3. Dynamic interplay between uranyl phosphate precipitation, sorption, and phase evolution

    SciTech Connect

    Munasinghe, P. Sumudu; Elwood Madden, Megan E.; Brooks, Scott C.; Elwood Madden, Andrew S.

    2015-04-17

    We report that natural examples demonstrate uranyl-phosphate minerals can maintain extremely low levels of aqueous uranium in groundwaters due to their low solubility. Thus, greater understanding of the geochemical factors leading to uranyl phosphate precipitation may lead to successful application of phosphate-based remediation methods. However, the solubility of uranyl phosphate phases varies over >3 orders of magnitude, with the most soluble phases typically observed in lab experiments. To understand the role of common soil/sediment mineral surfaces in the nucleation and transformation of uranyl phosphate minerals under environmentally relevant conditions, we carried out batch experiments with goethite and mica at pH 6 in mixed electrolyte solutions ranging from 1–800 μM U and 1–800 μM P. All experiments ended with uranium concentrations below the USEPA MCL for U, but with 2–3 orders of magnitude difference in uranium concentrations.

  4. Dynamic interplay between uranyl phosphate precipitation, sorption, and phase evolution

    DOE PAGESBeta

    Munasinghe, P. Sumudu; Elwood Madden, Megan E.; Brooks, Scott C.; Elwood Madden, Andrew S.

    2015-04-17

    We report that natural examples demonstrate uranyl-phosphate minerals can maintain extremely low levels of aqueous uranium in groundwaters due to their low solubility. Thus, greater understanding of the geochemical factors leading to uranyl phosphate precipitation may lead to successful application of phosphate-based remediation methods. However, the solubility of uranyl phosphate phases varies over >3 orders of magnitude, with the most soluble phases typically observed in lab experiments. To understand the role of common soil/sediment mineral surfaces in the nucleation and transformation of uranyl phosphate minerals under environmentally relevant conditions, we carried out batch experiments with goethite and mica at pHmore » 6 in mixed electrolyte solutions ranging from 1–800 μM U and 1–800 μM P. All experiments ended with uranium concentrations below the USEPA MCL for U, but with 2–3 orders of magnitude difference in uranium concentrations.« less

  5. Uranyl phthalocyanines show promise in the treatment of brain tumors

    NASA Technical Reports Server (NTRS)

    Frigerio, N. A.

    1967-01-01

    Processes synthesize sulfonated and nonsulfonated uranyl phthalocyanines for application in neutron therapy of brain tumors. Tests indicate that the compounds are advantageous over the previously used boron and lithium compounds.

  6. Structures and syntheses of layered and framework amine-bearing uranyl phosphate and uranyl arsenates

    NASA Astrophysics Data System (ADS)

    Locock, Andrew J.; Burns, Peter C.

    2004-08-01

    Two hydrated uranyl arsenates and a uranyl phosphate were synthesized by hydrothermal methods in the presence of amine structure-directing agents and their structures determined: (N 2C 6H 14)[(UO 2)(AsO 4)] 2(H 2O) 3, DabcoUAs, {NH(C 2H 5) 3}[(UO 2) 2(AsO 4)(AsO 3OH)], TriethUAs, and (N 2C 4H 12)(UO 2)[(UO 2)(PO 4)] 4(H 2O) 2, PiperUP. Intensity data were collected at room temperature using Mo Kα X-radiation and a CCD-based area detector. The crystal structures were refined by full-matrix least-squares techniques on the basis of F2 to agreement indices ( DabcoUAs, TriethUAs, PiperUP) w R2=5.6%, 8.3%, 7.2% for all data, and R1=2.9%, 3.3%, 4.0%, calculated for 1777, 5822, 9119 unique observed reflections (| Fo|⩾4 σF), respectively. DabcoUAs is monoclinic, space group C2/ m, Z=2, a=18.581(1), b=7.1897(4), c=7.1909(4) Å, β=102.886(1)°, V=936.43(9) Å 3, Dcalc=3.50 g/cm 3. TriethUAs is monoclinic, space group P2 1/ n, Z=4, a=9.6359(4), b=18.4678(7), c=10.0708(4) Å, β=92.282(1)°, V=1790.7(1) Å 3, Dcalc=3.41 g/cm 3. PiperUP is monoclinic, space group Pn, Z=2, a=9.3278(4), b=15.5529(7), c=9.6474(5) Å, β=93.266(1)°, V=1397.3(1) Å 3, Dcalc=4.41 g/cm 3. The structure of DabcoUAs contains the autunite-type sheet formed by the sharing of vertices between uranyl square bipyramids and arsenate tetrahedra. The triethylenediammonium cations are located in the interlayer along with two H 2O groups and are disordered. Both TriethUAs and PiperUP contain sheets formed of uranyl pentagonal bipyramids and tetrahedra (arsenate and phosphate, respectively) with the uranophane sheet-anion topology. In TriethUAs, triethlyammonium cations are located in the interlayer. In PiperUP, the sheets are connected by a uranyl pentagonal bipyramid that shares corners with phosphate tetrahedra of adjacent sheets, resulting in a framework with piperazinium cations and H 2O groups in the cavities of the structure.

  7. Association of uranyl with the cell wall of Pseudomonas fluorescens inhibits metabolism

    NASA Astrophysics Data System (ADS)

    Bencheikh-Latmani, Rizlan; Leckie, James O.

    2003-11-01

    Citric acid is found along with uranyl in the subsurface of former nuclear facilities because of its use as a decontamination agent in the nuclear industry. Citrate's metal chelating properties affect the mobility of uranyl in the subsurface and consequently, citrate biodegradation may significantly impact uranyl fate and transport. Under the non-growth conditions considered, low (micromolar) uranyl concentrations inhibit the biodegradation of citrate by Pseudomonas fluorescens, a common subsurface denitrifying bacterium. Additionally, uranyl is found readily associated with the cell envelope of P. fluorescens. The observed inhibition appears to be linked to the binding of uranyl to the cell surface and is reversible by desorbing cell-bound uranyl. This study establishes a link between uranyl association with the cell surface and the observed inhibitory effect of uranyl on cell metabolism.

  8. Parametric investigation of laser-induced fluorescence of solid-state uranyl compounds.

    PubMed

    Wang, Guangjun; Su, Yi; Monts, David L

    2008-10-23

    The combination of remote/standoff sensing and laser-induced fluorescence (LIF) spectroscopy shows potential for detection of uranyl (UO2(2+)) compounds. Uranyl compounds exhibit characteristic emission in the 450-600 nm (22,200 to 16,700 cm(-1)) spectral region when excited by wavelengths in the ultraviolet or in the short-wavelength portion of the visible spectrum. We report a parametric study of the effects of excitation wavelength [including 532 nm (18,797 cm(-1)), 355 nm (28,169 cm(-1)), and 266 nm (37,594 cm(-1))] and excitation laser power on solid-state uranium compounds. The uranium compounds investigated include uranyl nitrate, uranyl sulfate, uranyl oxalate, uranium dioxide, triuranium octaoxide, uranyl acetate, uranyl formate, zinc uranyl acetate, and uranyl phosphate. We observed the characteristic uranyl fluorescence spectrum from the uranium compounds except for uranium oxide compounds (which do not contain the uranyl moiety) and for uranyl formate, which has a low fluorescence quantum yield. Relative uranyl fluorescence intensity is greatest for 355 nm excitation, and the order of decreasing fluorescence intensity with excitation wavelength (relative intensity/laser output) is 355 nm > 266 nm > 532 nm. For 532 nm excitation, the emission spectrum is produced by two-photon excitation. Uranyl fluorescence intensity increases linearly with increasing laser power, but the rate of fluorescence intensity increase is different for different emission bands. PMID:18823105

  9. Complexation of Mercury(II) in Soil Organic Matter: EXAFS Evidence for Linear Two-Coordination with Reduced Sulfur Groups

    SciTech Connect

    Skyllberg,U.; Bloom, P.; Qian, J.; Lin, C.; Bleam, W.

    2006-01-01

    The chemical speciation of inorganic mercury (Hg) is to a great extent controlling biologically mediated processes, such as mercury methylation, in soils, sediments, and surface waters. Of utmost importance are complexation reactions with functional groups of natural organic matter (NOM), indirectly determining concentrations of bioavailable, inorganic Hg species. Two previous extended X-ray absorption fine structure (EXAFS) spectroscopic studies have revealed that reduced organic sulfur (S) and oxygen/nitrogen (O/N) groups are involved in the complexation of Hg(II) to humic substances extracted from organic soils. In this work, covering intact organic soils and extending to much lower concentrations of Hg than before, we show that Hg is complexed by two reduced organic S groups (likely thiols) at a distance of 2.33 Angstroms in a linear configuration. Furthermore, a third reduced S (likely an organic sulfide) was indicated to contribute with a weaker second shell attraction at a distance of 2.92-3.08 Angstroms. When all high-affinity S sites, corresponding to 20-30% of total reduced organic S, were saturated, a structure involving one carbonyl-O or amino-N at 2.07 Angstroms and one carboxyl-O at 2.84 Angstroms in the first shell, and two second shell C atoms at an average distance of 3.14 Angstroms, gave the best fit to data. Similar results were obtained for humic acid extracted from an organic wetland soil. We conclude that models that are in current use to describe the biogeochemistry of mercury and to calculate thermodynamic processes need to include a two-coordinated complexation of Hg(II) to reduced organic sulfur groups in NOM in soils and waters.

  10. Engineering and Coordination of Regulatory Networks and Intracellular Complexes to Maximize Hydrogen Production by Phototrophic Microorganisms

    SciTech Connect

    James C. Liao

    2012-05-22

    This project is a collaboration with F. R. Tabita of Ohio State. Our major goal is to understand the factors and regulatory mechanisms that influence hydrogen production. The organisms to be utilized in this study, phototrophic microorganisms, in particular nonsulfur purple (NSP) bacteria, catalyze many significant processes including the assimilation of carbon dioxide into organic carbon, nitrogen fixation, sulfur oxidation, aromatic acid degradation, and hydrogen oxidation/evolution. Our part of the project was to develop a modeling technique to investigate the metabolic network in connection to hydrogen production and regulation. Organisms must balance the pathways that generate and consume reducing power in order to maintain redox homeostasis to achieve growth. Maintaining this homeostasis in the nonsulfur purple photosynthetic bacteria is a complex feat with many avenues that can lead to balance, as these organisms possess versatile metabolic capabilities including anoxygenic photosynthesis, aerobic or anaerobic respiration, and fermentation. Growth is achieved by using H{sub 2} as an electron donor and CO{sub 2} as a carbon source during photoautotrophic and chemoautotrophic growth, where CO{sub 2} is fixed via the Calvin-Benson-Bassham (CBB) cycle. Photoheterotrophic growth can also occur when alternative organic carbon compounds are utilized as both the carbon source and electron donor. Regardless of the growth mode, excess reducing equivalents generated as a result of oxidative processes, must be transferred to terminal electron acceptors, thus insuring that redox homeostasis is maintained in the cell. Possible terminal acceptors include O{sub 2}, CO{sub 2}, organic carbon, or various oxyanions. Cells possess regulatory mechanisms to balance the activity of the pathways which supply energy, such as photosynthesis, and those that consume energy, such as CO{sub 2} assimilation or N{sub 2} fixation. The major route for CO{sub 2} assimilation is the CBB

  11. Low valent and hydride complexes of NHC coordinated gallium and indium.

    PubMed

    Ball, Graham E; Cole, Marcus L; McKay, Alasdair I

    2012-01-21

    The reactions of the N-heterocyclic carbene 1,3-dimesitylimidazol-2-ylidene (IMes) with Ga[GaCl(4)], "GaI", InCl(2) and GaBr(3) have been examined. All reactions using a low valent gallium or indium starting material led to species of the form [{MX(2)(IMes)}(2)], where M = Ga, X = Cl (1), I (2); M = In, X = Cl (3), with disproportionation and loss of gallium metal in the case of 2. Reaction of IMes with gallium tribromide yields the air and moisture stable complex [GaBr(3)(IMes)] (4), which has been used as a precursor to the mixed bromohydrides [GaBrH(2)(IMes)] (5) and [GaBr(2)H(IMes)] (6) by (i) ligand redistribution with [GaH(3)(IMes)], (ii) hydride-bromide exchange with triethylsilane, and (iii) alkylation with (n)butyllithium followed by β-hydride elimination (6 only). Attempts to prepare 1, or monovalent analogues such as [{GaCl(IMes)}(n)], by thermally induced reductive elimination of dihydrogen from the chlorohydride congeners of 5 and 6 resulted in isolation of the known compounds [IMesCl][Cl] (IMesCl = 1,3-dimesityl-2-chloroimidazolium), and/or 1,3-dimesityl-2-dihydroimidazole, and gallium metal. Preliminary photochemical NMR spectroscopy and catalytic studies of 5 and 6 aimed at reductive dehydrogenation under milder conditions are reported. Compounds 1 and 4 have been characterised by single crystal X-ray structure determination. PMID:22080333

  12. Uranyl Precipitation by Pseudomonas aeruginosa via Controlled Polyphosphate Metabolism

    PubMed Central

    Renninger, Neil; Knopp, Roger; Nitsche, Heino; Clark, Douglas S.; Keasling, Jay D.

    2004-01-01

    The polyphosphate kinase gene from Pseudomonas aeruginosa was overexpressed in its native host, resulting in the accumulation of 100 times the polyphosphate seen with control strains. Degradation of this polyphosphate was induced by carbon starvation conditions, resulting in phosphate release into the medium. The mechanism of polyphosphate degradation is not clearly understood, but it appears to be associated with glycogen degradation. Upon suspension of the cells in 1 mM uranyl nitrate, nearly all polyphosphate that had accumulated was degraded within 48 h, resulting in the removal of nearly 80% of the uranyl ion and >95% of lesser-concentrated solutions. Electron microscopy, energy-dispersive X-ray spectroscopy, and time-resolved laser-induced fluorescence spectroscopy (TRLFS) suggest that this removal was due to the precipitation of uranyl phosphate at the cell membrane. TRLFS also indicated that uranyl was initially sorbed to the cell as uranyl hydroxide and was then precipitated as uranyl phosphate as phosphate was released from the cell. Lethal doses of radiation did not halt phosphate secretion from polyphosphate-filled cells under carbon starvation conditions. PMID:15574942

  13. Analysis of unsaturated compounds by Ag+ coordination ionspray mass spectrometry: studies of the formation of the Ag+/lipid complex.

    PubMed

    Seal, Jennifer R; Havrilla, Christine M; Porter, Ned A; Hachey, David L

    2003-08-01

    Coordination ionspray mass spectrometry (CIS-MS) is a useful tool in the detection and identification of cholesterol ester and phospholipid hydroperoxides and diacyl peroxides. Extensive studies of a series of cholesterol esters using CIS-MS revealed the following: (1) Cholesterol esters with equal number of double bonds as the internal standard showed a linear relative response in the mass spectrometer while compounds with non-equal numbers of double bonds gave a nonlinear relative response. (2) Complex adducts containing cholesterol ester, silver ion, AgF, AgBF(4), and 2-propanoxide form when silver is in molar excess of cholesterol esters, reducing the [M + Ag](+) signal. (3) In a mixture of cholesterol esters where silver is limiting, Ch22:6 and Ch20:4 bind to silver at the expense of Ch18:2 and have a higher signal in the mass spectrometer. (4) In a mixture of cholesterol esters where silver concentration is twofold greater than total cholesterol ester concentration, Ch22:6 and Ch20:4 form large complex adducts more frequently than Ch18:2 and have a lower signal in the mass spectrometer. PMID:12892911

  14. New mechanism for the ring-opening polymerization of lactones? Uranyl aryloxide-induced intermolecular catalysis.

    PubMed

    Walshe, Aurora; Fang, Jian; Maron, Laurent; Baker, Robert J

    2013-08-01

    The uranyl aryloxide [UO2(OAr)2(THF)2] (Ar = 2,6-(t)Bu2-C6H2) is an active catalyst for the ring-opening cyclo-oligomerization of ε-caprolactone and δ-valerolactone but not for β-butyrolactone, γ-butyrolactone, and rac-lactide. (1)H EXSY measurements give the thermodynamic parameters for exchange of monomer and coordinated THF, and rates of polymerization have been determined. A comprehensive theoretical examination of the mechanism is discussed. From both experiment and theory, the initiation step is intramolecular and in keeping with the accepted mechanism, while computational studies indicate that propagation can go via an intermolecular pathway, which is the first time this has been observed. The lack of polymerization for the inactive monomers has been investigated theoretically and C-H···π interactions stabilize the coordination of the less rigid monomers. PMID:23879703

  15. Significant influence of coligands toward varying coordination modes of 2,2'-bipyridine-3,3'-diol in ruthenium complexes.

    PubMed

    Ghosh, Prabir; Mondal, Prasenjit; Ray, Ritwika; Das, Ankita; Bag, Sukdev; Mobin, Shaikh M; Lahiri, Goutam Kumar

    2014-06-16

    The varying coordination modes of the ambidentate ligand 2,2'-bipyridine-3,3'-diol (H2L) in a set of ruthenium complexes were demonstrated with special reference to the electronic features of the coligands, including σ-donating acac(-) (= acetylacetonate) in Ru(III)(acac)2(HL(-)) (1), strongly π-accepting pap (= 2-phenylazopyridine) in Ru(II)(pap)2(L(2-)) (2)/[(pap)2Ru(II)(μ-L(2-))Ru(II)(pap)2](ClO4)2 ([4](ClO4)2), and reported moderately π-accepting bpy (= 2,2'-bypiridine) in [Ru(II)(bpy)2(HL(-))]PF6 ([5]PF6)/[(bpy)2Ru(μ-L(2-))Ru(bpy)2](PF6)2 ([7](PF6)2). The single-crystal X-ray structures reveal that, in paramagnetic and electron paramagnetic resonance active 1 and reported diamagnetic [5]PF6, nearly planar monoanionic HL(-) coordinates to the metal ion via the N,N donors forming a five-membered chelate ring with hydrogen-bonded O-H···O function at the backbone of the ligand framework, as has also been reported in other metal complexes. However, structurally characterized diamagnetic 2 represents O(-),O(-) bonded seven-membered chelate of fully deprotonated but twisted L(2-). The nonplanarity of the coordinated L(2-) in 2 does not permit the second metal fragment {Ru(pap)2} or {Ru(bpy)2} or {Ru(acac)2} to bind with the available N,N donors at the back face of L(2-). Further, the deprotonated form of the model ligand 2,2'-biphenol (H2L') yields Ru(II)(pap)2(L'(2-)) (3); its crystal structure establishes the expected O(-),O(-) bonded seven-membered chelate of nonplanar L'(2-) as in reported Ru(II)(bpy)2(L'(2-)) (6), although {Ru(acac)2} metal precursor altogether fails to react with H2L'. All attempts to make diruthenium complex from {Ru(acac)2} and H2L failed; however, the corresponding {Ru(pap)2(2+)} derived dimeric [4](ClO4)2 was structurally characterized. It establishes the symmetric N,O(-)/N,O(-) bridging mode of nonplanar L(2-) as in reported [7](PF6)2. Besides structural and spectroscopic characterization of the newly developed complexes, the

  16. Structural evolution of a uranyl peroxide nano-cage fullerene: U60, at elevated pressures

    NASA Astrophysics Data System (ADS)

    Turner, K. M.; Lin, Y.; Zhang, F.; McGrail, B.; Burns, P. C.; Mao, W. L.; Ewing, R. C.

    2015-12-01

    U60 is a uranyl peroxide nano-cage that adopts a highly symmetric fullerene topology; it is topologically identical to C60. Several studies on the aqueous-phase of U60 clusters, [UO2(O2)(OH)]6060-, have shown its persistence in complex solutions and over lengthy time scales. Peroxide enhances corrosion of nuclear fuel in a reactor accident-uranyl peroxides often form near contaminated sites. U60 (Fm-3) crystallizes with approximate formula: Li68K12(OH)20[UO2(O2)(OH)]60(H2O)310. Here, we have used the diamond anvil cell (DAC) to examine U60 to understand the stability of this cluster at high pressures. We used a symmetric DAC with 300 μm culet diamonds and two different pressure-transmitting media: a mixture of methanol+ethanol and silicone oil. Using a combination of in situ Raman spectroscopy and synchrotron XRD, and electrospray ionization mass spectroscopy (ESI-MS) ex situ, we have determined the pressure-induced evolution of U60. Crystalline U60 undergoes an irreversible phase transition to a tetragonal structure at 4.1 GPa, and irreversibly amorphizes at 13 GPa. The amorphous phase likely consists of clusters of U60. Above 15 GPa, the U60 cluster is irreversibly destroyed. ESI-MS shows that this phase consists of species that likely have between 10-20 uranium atoms. Raman spectroscopy complements the diffraction measurements. U60 shows two dominant vibrational modes: a symmetric stretch of the uranyl U-O triple bond (810 cm-1), and a symmetric stretch of the U-O2-U peroxide bond (820 cm-1). As pressure is increased, these modes shift to higher wavenumbers, and overlap at 4 GPa. At 15 GPa, their intensity decreases below detection. These experiments reveal several novel behaviors including a new phase of U60. Notably, the amorphization of U60 occurs before the collapse of its cluster topology. This is different from the behavior of solvated C60 at high pressure, which maintains a hcp structure up to 30 GPa, while the clusters disorder. These results suggest

  17. Crystal structures of copper(II) complexes of 2-formylpyridine substituted thiosemicarbazones; the first example of a coordinated thiosemicarbazone with a thiol function

    NASA Astrophysics Data System (ADS)

    West, D. X.; Swearingen, J. K.; Romack, T. J.; Billeh, I. S.; Jasinski, J. P.; Li, Y.; Staples, R. J.

    2001-08-01

    The crystal structures of two 5-coordinate copper(II) complexes containing neutral, tridentate 2-formylpyridine N(4)-substituted thiosemicarbazones have been determined. 2-Formylpyridine N(4)-cyclohexylthiosemicarbazone, HFo4CHex coordinates via the pyridine nitrogen, imine nitrogen and thione sulfur with two chloro ligands to produce [Cu(HFo4CHex)Cl 2]. Similarly, 2-formylpyridine 3-(4-methylpiperazine)thiosemicarbazone, HFoppz4M, produces [Cu(HFoppz4M)Cl 2] with one major difference; rather than the expected thione form of the thiosemicarbazone moiety, it coordinates as the thiol isomer. Both complexes are close to a square pyramid structure with axial and equatorial chloro ligands and the thiosemicarbazone moieties of both ligands nearly planar. Also included is the crystal structure of N-cyclohexylthiosemicarbazide, CHextsc.

  18. A Complex Regulatory Network Coordinating Cell Cycles During C. elegans Development Is Revealed by a Genome-Wide RNAi Screen

    PubMed Central

    Roy, Sarah H.; Tobin, David V.; Memar, Nadin; Beltz, Eleanor; Holmen, Jenna; Clayton, Joseph E.; Chiu, Daniel J.; Young, Laura D.; Green, Travis H.; Lubin, Isabella; Liu, Yuying; Conradt, Barbara; Saito, R. Mako

    2014-01-01

    The development and homeostasis of multicellular animals requires precise coordination of cell division and differentiation. We performed a genome-wide RNA interference screen in Caenorhabditis elegans to reveal the components of a regulatory network that promotes developmentally programmed cell-cycle quiescence. The 107 identified genes are predicted to constitute regulatory networks that are conserved among higher animals because almost half of the genes are represented by clear human orthologs. Using a series of mutant backgrounds to assess their genetic activities, the RNA interference clones displaying similar properties were clustered to establish potential regulatory relationships within the network. This approach uncovered four distinct genetic pathways controlling cell-cycle entry during intestinal organogenesis. The enhanced phenotypes observed for animals carrying compound mutations attest to the collaboration between distinct mechanisms to ensure strict developmental regulation of cell cycles. Moreover, we characterized ubc-25, a gene encoding an E2 ubiquitin-conjugating enzyme whose human ortholog, UBE2Q2, is deregulated in several cancers. Our genetic analyses suggested that ubc-25 acts in a linear pathway with cul-1/Cul1, in parallel to pathways employing cki-1/p27 and lin-35/pRb to promote cell-cycle quiescence. Further investigation of the potential regulatory mechanism demonstrated that ubc-25 activity negatively regulates CYE-1/cyclin E protein abundance in vivo. Together, our results show that the ubc-25-mediated pathway acts within a complex network that integrates the actions of multiple molecular mechanisms to control cell cycles during development. PMID:24584095

  19. Metal coordination study at Ag and Cd sites in crown thioether complexes through DFT calculations and hyperfine parameters.

    PubMed

    do Nascimento, Rafael R; Lima, Filipe C D A; Gonçalves, Marcos B; Errico, Leonardo A; Rentería, Mario; Petrilli, Helena M

    2015-04-01

    Structural and electronic properties of [C12H24S6X], [C13H26S6OX], and [C14H28S6OX] (X: Ag(+), Cd(2+)) crown thioether complexes were investigated within the framework of the density functional theory (DFT) using the projector augmented wave (PAW) method. The theoretical results were compared with time-differential perturbed γ-γ angular correlations (TDPAC) experiments reported in the literature using the (111)Ag→(111)Cd probe. In the case of X=Ag(+), a refinement of the structure was performed and the predicted equilibrium structures compared with available X-ray diffraction experimental data. Structural distortions induced by replacing Ag(+) with Cd(2+) were investigated as well as the electric-field gradient (EFG) tensor at the Cd(2+) sites. Our results suggest that the EFG at Cd(2+) sites corresponds to the Ag(+) coordination sphere structure, i.e., before the structural relaxations of the molecule with X=Cd(2+) are completed. The results are discussed in terms of the characteristics of the TDPAC (111)Ag→(111)Cd probe and the time window of the measurement, and provide an interesting tool with which to probe molecular relaxations. PMID:25814377

  20. Tetrapositive plutonium, neptunium, uranium, and thorium coordination complexes: chemistry revealed by electron transfer and collision induced dissociation.

    PubMed

    Gong, Yu; Tian, Guoxin; Rao, Linfeng; Gibson, John K

    2014-04-17

    The Pu(4+), Np(4+), and U(4+) ions, which have large electron affinities of ∼34.6, ∼33.6, and ∼32.6 eV, respectively, were stabilized from solution to the gas phase upon coordination by three neutral tetramethyl-3-oxa-glutaramide ligands (TMOGA). Both collision induced dissociation (CID) and electron transfer dissociation (ETD) of Pu(TMOGA)3(4+) reveal the propensity for reduction of Pu(IV) to Pu(III), by loss of TMOGA(+) in CID and by simple electron transfer in ETD. The reduction of Pu(IV) is in distinct contrast to retention of Th(IV) in both CID and ETD of Th(TMOGA)3(4+), where only the C-Oether bond cleavage product was observed. U(TMOGA)3(4+) behaves similarly to Th(TMOGA)3(4+) upon CID and ETD, while the fragmentation patterns of Np(TMOGA)3(4+) lie between those of Pu(TMOGA)3(4+) and U(TMOGA)3(4+). It is notable that the gas-phase fragmentation behaviors of these exceptional tetrapositive complexes parallel fundamental differences in condensed phase chemistry within the actinide series, specifically the tendency for reduction from the IV to III oxidation states. PMID:24660979

  1. Radical anionic versus neutral 2,2'-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands.

    PubMed

    Diaconescu, Paula L; Cummins, Christopher C

    2015-02-14

    The synthesis and characterization of (bipy)(2)U(N[t-Bu]Ar)(2) (1-(bipy)(2), bipy = 2,2'-bipyridyl, Ar = 3,5-C(6)H(3)Me(2)), (bipy)U(N[(1)Ad]Ar)(3) (2-bipy), (bipy)(2)U(NC[t-Bu]Mes)(3) (3-(bipy)(2), Mes = 2,4,6-C(6)H(2)Me(3)), and IU(bipy)(NC[t-Bu]Mes)(3) (3-I-bipy) are reported. X-ray crystallography studies indicate that bipy coordinates as a radical anion in 1-(bipy)(2) and 2-bipy, and as a neutral ligand in 3-I-bipy. In 3-(bipy)(2), one of the bipy ligands is best viewed as a radical anion, the other as a neutral ligand. The electronic structure assignments are supported by NMR spectroscopy studies of exchange experiments with 4,4'-dimethyl-2,2'-bipyridyl and also by optical spectroscopy. In all complexes, uranium was assigned a +4 formal oxidation state. PMID:25510329

  2. Ipl1/Aurora B kinase coordinates synaptonemal complex disassembly with cell cycle progression and crossover formation in budding yeast meiosis

    PubMed Central

    Jordan, Philip; Copsey, Alice; Newnham, Louise; Kolar, Elizabeth; Lichten, Michael; Hoffmann, Eva

    2009-01-01

    Several protein kinases collaborate to orchestrate and integrate cellular and chromosomal events at the G2/M transition in both mitotic and meiotic cells. During the G2/M transition in meiosis, this includes the completion of crossover recombination, spindle formation, and synaptonemal complex (SC) breakdown. We identified Ipl1/Aurora B kinase as the main regulator of SC disassembly. Mutants lacking Ipl1 or its kinase activity assemble SCs with normal timing, but fail to dissociate the central element component Zip1, as well as its binding partner, Smt3/SUMO, from chromosomes in a timely fashion. Moreover, lack of Ipl1 activity causes delayed SC disassembly in a cdc5 as well as a CDC5-inducible ndt80 mutant. Crossover levels in the ipl1 mutant are similar to those observed in wild type, indicating that full SC disassembly is not a prerequisite for joint molecule resolution and subsequent crossover formation. Moreover, expression of meiosis I and meiosis II-specific B-type cyclins occur normally in ipl1 mutants, despite delayed formation of anaphase I spindles. These observations suggest that Ipl1 coordinates changes to meiotic chromosome structure with resolution of crossovers and cell cycle progression at the end of meiotic prophase. PMID:19759266

  3. Photochemical Reduction of Low Concentrations of CO2 in a Porous Coordination Polymer with a Ruthenium(II)-CO Complex.

    PubMed

    Kajiwara, Takashi; Fujii, Machiko; Tsujimoto, Masahiko; Kobayashi, Katsuaki; Higuchi, Masakazu; Tanaka, Koji; Kitagawa, Susumu

    2016-02-18

    Direct use of low pressures of CO2 as a C1 source without concentration from gas mixtures is of great interest from an energy-saving viewpoint. Porous heterogeneous catalysts containing both adsorption and catalytically active sites are promising candidates for such applications. Here, we report a porous coordination polymer (PCP)-based catalyst, PCP-Ru(II) composite, bearing a Ru(II) -CO complex active for CO2 reduction. The PCP-Ru(II) composite showed improved CO2 adsorption behavior at ambient temperature. In the photochemical reduction of CO2 the PCP-Ru(II) composite produced CO, HCOOH, and H2 . Catalytic activity was comparable with the corresponding homogeneous Ru(II) catalyst and ranks among the highest of known PCP-based catalysts. Furthermore, catalytic activity was maintained even under a 5 % CO2 /Ar gas mixture, revealing a synergistic effect between the adsorption and catalytically active sites within the PCP-Ru(II) composite. PMID:26800222

  4. Separation performance of cucurbit[8]uril and its coordination complex with cadmium (II) in capillary gas chromatography.

    PubMed

    Sun, Tao; Ji, Ningning; Qi, Meiling; Tao, Zhu; Fu, Ruonong

    2014-05-23

    Here we report the investigation of using cucurbit[8]uril (CB8) and its coordination complex with cadmium (II) (CB8-Cd) as stationary phases for capillary gas chromatography (GC). The prepared capillary columns of CB8 and CB8-Cd stationary phases achieved column efficiency of 2200plates/m and 1508plates/m, respectively, and showed weak polarity based on the measured McReynolds constants. Their separation performance was investigated by GC separation of mixtures of different types while a commercial column was used for comparison. The CB8 stationary phase achieved high resolution for a wide range of analytes from nonpolar to polar while the CB8-Cd stationary phase exhibited good separation mainly for nonpolar to weak polar analytes. The CB stationary phases differ from the commercial one in terms of retention behaviors and resolving ability due to their different molecular interactions with analytes. Moreover, energy effect on the retention of analytes on CB8 and CB8-Cd stationary phases was examined, showing that retention on CB8 column was determined mainly by enthalpy change for polar analytes and by both enthalpy change and entropy change for weak polar analytes whereas retention on CB8-Cd column was mainly controlled by entropy change. This work demonstrates the great potential of CB8 and CB8-Cd stationary phases as a new type of GC stationary phases in GC analysis. PMID:24745846

  5. 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

  6. ESI-MS and theoretical study on the coordination structures and reaction modes of the diperoxovanadate complexes containing histidine-like ligands

    NASA Astrophysics Data System (ADS)

    Yu, Xian-Yong; Xu, Xin; Chen, Zhong

    2008-01-01

    In order to study the coordination structures and the reaction modes of diperoxovanadate complexes in the gas phase, the interaction between K3[OV(O2)2(C2O4)]·H2O and a series of histidine-like ligands has been investigated by the combination of the electrospray ionization-mass spectrometry (ESI-MS) and the density functional theory (DFT) calculations. The experimental results proved the formation of both [OV(O2)2L]- (L = all histidine-like ligands) and [OV(O2)2L'2]- (L' = histidine and carnosine only) species. DFT calculations at the level of B3LYP/6-31+G* showed that [OV(O2)2L'2]- is a hexa-coordinated complex, instead of a hepta-coordinated complex as proposed before. The unique coordination mode in the gas phase is for one ligand to bind to the oxygen atoms via hydrogen binding, rather than both ligands to the metal center. The L'2 dimer formation and the maintenance of the hydrogen bonding within the dimer during the complex formation are two important factors that enhance the abundance of the [OV(O2)2L'2]- species. The calculated bonding enthalpy and free energy changes provided an explanation on the reaction modes of the interaction systems, in agreement with the observations of the ESI-MS experiments.

  7. Physicochemical properties and theoretical modeling of actinide complexes with a para-tert-Butylcalix[6]arene bearing phosphinoyl pendants. Extraction capability of the calixarene toward f elements.

    PubMed

    Ramírez, Flor de María; Varbanov, Sabi; Padilla, Juan; Bünzli, Jean-Claude G

    2008-09-01

    The coordination ability of the hexaphosphinoylated p-tert-butylcalix[6]arene B6bL6 toward actinides is established, as well as its good separation ability of the actinide ions UO2 2+ and Th(IV) over trivalent rare earths such as La(III), Eu(III), and Y(III). Spectrophotometric titration of uranyl with B6bL6 in CH 3CN yields log beta 11 = 7.1 and log beta 12 = 12.5 for the 1:1 and 1:2 (UO2 2+/B 6bL6) species, respectively. Actinide complexes with 1:1 and 1:2 (M/L) stoichiometries are isolated and characterized by elemental analysis, IR, and UV-vis. Compounds 1 and 3 fulfill their CN = 8 just with B 6bL (6), while compounds 2 and 4 require coordinated nitrates and/or water molecules. The luminescence spectra of the uranyl complexes and the parameters such as FWMH, vibronic spacing (upsilon sp), and the U-O bond length, as well as the luminescence lifetimes, permit the understanding of the coordination chemistry of these actinide calixarene complexes. Energy transfer from the B6bL6 ligand to the uranyl ion is demonstrated to be relevant in compound 1 with Q abs = 2.0%. The uranyl complex emission reveals a biexponential decay with tau s from 210 to 220 micros and tau L from 490 to 650 micros for compounds 1 and 3, respectively. The liquid-liquid extraction results demonstrate the good extraction capability of B 6bL (6) toward actinides but not for rare earths at room temperature. The extracted species keeps the 1(cation)/1(calixarene) ratio for the UO2 2+, Th 4+, and Eu 3+ ions. A good capacity of B6bL 6 toward Th4+ ions using aqueous phase 2 containing even up to 0.3 M thorium nitrate and an organic phase of 2.47 x 10 (-4) M B6bL6 in chloroform is found. The spectroscopic properties of the isolated uranyl complexes and the extraction studies reveal a uranophilic nature of B6bL6. The molecular modeling results are in good agreement with the experimental findings. PMID:18686994

  8. Synthesis, crystal structures, and urease inhibition of an acetohydroxamate-coordinated oxovanadium(V) complex derived from N'-(3-bromo-2-hydroxybenzylidene)-4-methoxybenzohydrazide.

    PubMed

    Qu, Dan; Niu, Fang; Zhao, Xinlu; Yan, Ke-Xiang; Ye, Yu-Ting; Wang, Jia; Zhang, Mei; You, Zhonglu

    2015-05-01

    A new benzohydrazone compound N'-(3-bromo-2-hydroxybenzylidene)-4-methoxybenzohydrazide (H₂L) was prepared. Reaction of H₂L and acetohydroxamic acid (HAHA) with VO(acac)₂ in methanol gave the complex [VOL(AHA)]. Both H₂L and the oxovanadium complex were characterized by elemental analysis, IR, UV-vis and (1)H NMR spectra, and single crystal X-ray diffraction. H₂L was also characterized by high-resolution mass spectrum. Thermal analysis of the oxovanadium complex was carried out. The benzohydrazone ligand, in its dianionic form, coordinates to V atom through the phenolate oxygen, imino nitrogen and enolate oxygen. The acetohydroxamic acid coordinates to V atom through the carbonyl oxygen and deprotonated hydroxyl oxygen. The V atom is in octahedral coordination. H₂L, HAHA and the oxovanadium complex were tested for their urease inhibitory activities. The percent inhibition at concentration of 100 μmol·L(-1) on Helicobacter pylori urease is 78% for the oxovanadium complex. The IC₅₀ value for the complex is 36.5 μmol·L(-1). Molecular docking study was performed to study the inhibition. PMID:25840795

  9. A new coordination mode of (E)-3-(3-hydroxyl-phenyl)-acrylic acid in copper complex: Crystal structure and magnetic properties

    SciTech Connect

    Jin, Xin; Zhou, Pei; Zheng, Chunying; Li, Hui

    2015-05-15

    A copper complex ([Cu(py){sub 2}(L){sub 2}]·2CH{sub 3}OH){sub n} (HL=(E)-3-(3-hydroxyl-phenyl)-acrylic acid) (1) with acrylic acid ligand was synthesized and structurally analyzed by IR, elemental analysis, TGA and the single-crystal X-ray diffraction methods. It is the first time to find that phenolic hydroxyl of L coordinates to Cu(II). Complex 1 exhibits 1D chain by a double-bridge of ligands, and the 3D supramolecular framework in complex 1 is constructed by π–π stacking interactions and van der Waals Contacts among the 1D chains. The magnetic properties of complex 1 have been studied. - Graphical abstract: A copper complex based on (E)-3-(3-hydroxyl-phenyl)-acrylic acid in a novel coordinated way was synthesized and a ferromagnetic exchange interactions between neighboring Cu(II) ions has be achieved. - Highlights: • A new copper complex with acrylic acid ligand was synthesized and analyzed. • We find the phenolic hydroxyl of MCA ligand coordinates to metal ion firstly. • A ferromagnetic exchange interactions between Cu(II) ions has been achieved.

  10. Water exchange on seven-coordinate Mn(II) complexes with macrocyclic pentadentate ligands: insight in the mechanism of Mn(II) SOD mimetics.

    PubMed

    Dees, Anne; Zahl, Achim; Puchta, Ralph; Hommes, Nico J R van Eikema; Heinemann, Frank W; Ivanović-Burmazović, Ivana

    2007-04-01

    Seven-coordinate manganese(II) complexes [Mn(L)(H2O)2]2+, where L represents an equatorial pentadentate macrocyclic ligand with five nitrogen donor atoms, were studied with regard to their acid-base properties, water-exchange rate constants, and corresponding activation parameters (DeltaH, DeltaS, and DeltaV). Three of the studied complexes without imine bonds in the macrocyclic ligand are proven superoxide dismutase (SOD) mimetics. Their water-exchange parameters were compared with those of the imino groups containing complex [Mn(L1)(Cl)2] (dichloro-2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12.3.1]-octadeca-1(18),2,12,14,16-pentaenemanganese(II)), which does not show SOD activity. In addition the X-ray crystal structure of a new complex, dichloro-2,6-bis[1-(2-(N-methylamino)ethylimino)ethyl]pyridine-manganese(II) [Mn(L2)(Cl)2], which is the acyclic analog of [Mn(L1)(Cl)2], is reported. Stability constants of the complexes and the pKa values of the ligands were measured by potentiometric titration. The titrations of [Mn(L1)(H2O)2]2+ and [Mn(L2)(H2O)2]2+ led to complicated species distribution curves because of their ligands containing imine bonds. Water exchange was measured by temperature- and pressure-dependent 17O NMR techniques. In addition to the measurements on [Mn(EDTA)(H2O)]2- and its derivatives, this is the only study of water exchange on seven-coordinate manganese complexes. The water exchange rate constants vary between 1.6 x 107 s-1 and 5.8 x 107 s-1 at 25 degrees C and are mainly controlled by the pi-acceptor abilities of the ligands. The exchange rate constant of the diaqua-1,4,7,10,13-pentaazacyclopentadecanemanganese(II) [Mn([15]aneN5)(H2O)2]2+ complex seems to be even higher but could not be exactly determined. On the basis of the obtained activation parameters, the exchange mechanism of the studied seven-coordinate manganese(II) complexes follows a dissociative pathway (Id mechanism). DFT calculations (UB3LYP/LANL2DZp) were performed to obtain

  11. A novel binuclear copper complex incorporating a nalidixic acid derivative displaying a one-dimensional coordination polymeric structure.

    PubMed

    Bergamini, F R G; Ribeiro, M A; Miranda, P C M L; Formiga, A L B; Corbi, P P

    2016-07-01

    The identification of the antibacterial action of nalidixic acid (nx) was central to the development of the quinolone antibacterial compounds. The ability of the nx naphthyridyl ring to interact with and inhibit some proteins has encouraged the investigation of similar structures in the search for more active compounds with less adverse effects. The possibility of structural modification by attachment of other biologically active moieties to the naphthyridyl ring of nx allowed the development of new active antimicrobial molecules. Hydrazone derivatives of nx can be synthesized easily based on the condensation of the hydrazide derivative of nx with the desired aldehyde or ketone. Only a few complexes with nx hydrazone derivatives have been described but for none were the crystal structures elucidated. The synthesis of a new one-dimensional Cu(II) coordination polymer, namely catena-poly[[copper(II)-di-μ-chlorido-copper(II)-{μ-1-ethyl-N'-[(1H-imidazol-4-yl)methylidene]-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazidato}-[dimethanolcopper(II)]-{μ-1-ethyl-N'-[(1H-imidazol-3-yl)methylidene]-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazidato}] dichloride methanol tetrasolvate], {[Cu3(C16H15N6O2)2Cl2(CH3OH)2]Cl2·4CH3OH}n, with the (1H-imidazol-4-yl)methylidene carbohydrazide derivative of nalidixic acid (denoted h4imi), is presented and its structure is compared to the density functional theory (DFT) optimized structure of free h4imi. The title structure presents an octahedral Cu(II) ion on an inversion centre alternating along a polymer chain with a square-pyramidal Cu(II) ion, with the two Cu(II) centres bridged by two chloride ligands. Hydrogen bonds involving chloride counter-ions and methanol solvent molecules mediate the three-dimensional packing of the polymer. Comparison of the geometrical results from the structure analysis with those derived from a DFT study of the free ligand reveal the differences that arise upon coordination

  12. Control of self-assembly through the influence of terminal hydroxymethyl groups on the metal coordination of pyrimidine-hydrazone Cu(II) complexes.

    PubMed

    Hutchinson, Daniel J; Hanton, Lyall R; Moratti, Stephen C

    2010-07-01

    The synthesis and characterization of 6-hydroxymethylpyridine-2-carboxaldehyde (2-methyl-pyrimidine-4,6-diyl)bis(1-methylhydrazone) (1) is reported. Ligand 1 was designed as a ditopic pyrimidine-hydrazone molecular strand with hydroxymethyl groups attached to the terminal pyridine rings. Coordination of 1 with Cu(ClO(4))(2) x 6 H(2)O or Cu(SO(3)CF(3))(2) x 4 H(2)O in a 1:2 molar ratio resulted in the dinuclear Cu(II) complexes [Cu(2)1(CH(3)CN)(4)](ClO(4))(4) x CH(3)CN (4) and [Cu(2)1(SO(3)CF(3))(2)(CH(3)CN)(2)](SO(3)CF(3))(2) x CH(3)CN (5). X-ray crystallography and (1)H NMR NOESY experiments showed that 1 adopted a horseshoe shape with both pyrimidine-hydrazone (pym-hyz) bonds in a transoid conformation, while 4 and 5 were linear in shape, with both pym-hyz bonds in a cisoid conformation. Coordination of 1 with Cu(ClO(4))(2) x 6 H(2)O or Cu(SO(3)CF(3))(2) x 4 H(2)O in a 1:1 molar ratio resulted in three different bent complexes, [Cu(1H)(ClO(4))(2)](ClO(4)) (6), [Cu(1H)(CH(3)CN)](ClO(4))(3) x 0.5 H(2)O (7), and [Cu1(SO(3)CF(3))](2)(SO(3)CF(3))(2) x CH(3)CN (8), where the pym-hyz bond of the occupied coordination site adopted a cisoid conformation, while the pym-hyz bond of the unoccupied site retained a transoid conformation. Both 6 and 7 showed protonation of the pyridine nitrogen donor in the empty coordination site; complex 8, however, was not protonated. A variety of Cu(II) coordination geometries were seen in structures 4 to 8, including distorted octahedral, trigonal bipyramidal, and square pyramidal geometries. Coordination of the hydroxymethyl arm in the mononuclear Cu(II) complexes 6, 7, and 8 appeared to inhibit the formation of a [2 x 2] grid by blocking further access to the Cu(II) coordination sphere. In addition, the terminal hydroxymethyl groups contributed to the supramolecular structures of the complexes through coordination to the Cu(II) ions and hydrogen bonding. PMID:20509604

  13. Solvothermal synthesis of uranium(VI) phases with aromatic carboxylate ligands: A dinuclear complex with 4-hydroxybenzoic acid and a 3D framework with terephthalic acid

    NASA Astrophysics Data System (ADS)

    Zhang, Yingjie; Karatchevtseva, Inna; Bhadbhade, Mohan; Tran, Toan Trong; Aharonovich, Igor; Fanna, Daniel J.; Shepherd, Nicholas D.; Lu, Kim; Li, Feng; Lumpkin, Gregory R.

    2016-02-01

    With the coordination of dimethylformamide (DMF), two new uranium(VI) complexes with either 4-hydroxybenzoic acid (H2phb) or terephthalic acid (H2tph) have been synthesized under solvothermal conditions and structurally characterized. [(UO2)2(Hphb)2(phb)(DMF)(H2O)3]·4H2O (1) has a dinuclear structure constructed with both pentagonal and hexagonal bipyramidal uranium polyhedra linked through a μ2-bridging ligand via both chelating carboxylate arm and alcohol oxygen bonding, first observation of such a coordination mode of 4-hydroxybenzoate for 5 f ions. [(UO2)(tph)(DMF)] (2) has a three-dimensional (3D) framework built with pentagonal bipyramidal uranium polyhedra linked with μ4-terephthalate ligands. The 3D channeled structure is facilitated by the unique carboxylate bonding with nearly linear C-O-U angles and the coordination of DMF molecules. The presence of phb ligands in different coordination modes, uranyl ions in diverse environments and DMF in complex 1, and tph ligand, DMF and uranyl ion in complex 2 has been confirmed by Raman spectroscopy. In addition, their thermal stability and photoluminescence properties have been investigated.

  14. Hydrothermal Phase Relations Among Uranyl Minerals at the Nopal I Analog Site

    SciTech Connect

    Murphy, William M.

    2007-07-01

    Uranyl mineral paragenesis at Nopal I is an analog of spent fuel alteration at Yucca Mountain. Petrographic studies suggest a variety of possible hydrothermal conditions for uranium mineralization at Nopal I. Calculated equilibrium phase relations among uranyl minerals show uranophane stability over a broad range of realistic conditions and indicate that uranyl mineral variety reflects persistent chemical potential heterogeneity. (author)

  15. Preparation and Reactions of the 1,1-Dithiolato Complexes of Ni(II). An Undergraduate Coordination Chemistry Experiment.

    ERIC Educational Resources Information Center

    Ballester, L.; Perpinan, M. F.

    1988-01-01

    Described is an undergraduate coordination chemistry experiment that enables students to relate concepts developed in class about the stereochemistry and coordination numbers to the interpretation of the electronic and infrared spectra and their magnetic behavior. Indicates that thermal decomposition and x-ray diffraction studies can also be…

  16. The investigation of the solvent effect on coordination of nicotinato ligand with cobalt(II) complex containing tris(2-benzimidazolylmethyl)amine: A computational study

    NASA Astrophysics Data System (ADS)

    Sayin, Koray; Karakaş, Duran

    2014-11-01

    The electronic structure of [Co(ntb)(nic)]+ complex ion are optimized by using density functional theory (DFT) method with mix basis set. Where (ntb) represents tris(2-benzimidazolylmethyl)amine ligand and (nic) is the anion of nicotinic acids. Six different fields, vacuum, chloroform, butanonitrile, methanol, water and formamide solvents are used in these calculations. The calculated structural parameters indicate that (nic) ligand coordinates to cobalt(II) containing (ntb) ligand with one oxygen atom in butanonitrile, methanol, water and formamide solvents but coordinates with two oxygen atoms in vacuum. These results are supported with IR, UV and 1H NMR spectra. According to the calculated results, the geometry of [Co(ntb)(nic)]+ complex ion is distorted octahedral in vacuum while the geometry is distorted square pyramidal in the all other solvents. Distorted octahedral [Co(ntb)(nic)]+ complex ion have not been synthesized as experimentally and it is predicted with computational chemistry methods.

  17. Solution chemistry of a water-soluble eta2-H2 ruthenium complex: evidence for coordinated H2 acting as a hydrogen bond donor.

    PubMed

    Szymczak, Nathaniel K; Zakharov, Lev N; Tyler, David R

    2006-12-13

    The ability of an eta2-H2 ligand to participate in intermolecular hydrogen bonding in solution has long been an unresolved issue. Such species are proposed to be key intermediates in numerous important reactions such as the proton-transfer pathway of H2 production by hydrogenase enzymes. We present the synthesis of several new water-soluble ruthenium coordination complexes including an eta2-H2 complex that is surprisingly inert to substitution by water. The existence of dihydrogen hydrogen bonding (DHHB) was experimentally probed by monitoring the chemical shift of H-bonded Ru-(H2) complexes using NMR spectroscopy, by UV-visible spectroscopy, and by monitoring the rotational dynamics of a hydrogen-bonding probe molecule. The results provide strong evidence that coordinated H2 can indeed participate in intermolecular hydrogen bonding to bulk solvent and other H-bond acceptors. PMID:17147394

  18. First examples of ternary lanthanide 5-aminoisophthalate complexes: Hydrothermal syntheses and structures of lanthanide coordination polymers with 5-aminoisophthalate and oxalate

    NASA Astrophysics Data System (ADS)

    Liu, Chong-Bo; Wen, Hui-Liang; Tan, Sheng-Shui; Yi, Xiu-Guang

    2008-05-01

    Two new lanthanide coordination polymers with mixed-carboxylates, [Ln(OX)(HAPA)(H 2O)] n[Ln = Eu ( 1), Ho ( 2); H 2APA = 5-aminoisophthalic acid; OX = oxalate] were obtained by hydrothermal reactions, and characterized by single crystal X-ray diffraction, elemental analysis and IR spectra. Complexes 1 and 2 are both 3-D supramolecular structure, in which lanthanide ions are bridged by oxalate and 5-aminoisophthalate ligands forming 2-D metal-organic framework, and 2-D networks are further architectured to form 3-D supramolecular structures by hydrogen bonds. The two carboxylate groups of H 2APA ligand are all deprotonated and exhibit chelating and bridging bidentate coordination modes, respectively, and the amino group in HAPA presents - NH3+ in the titled complexes. The thermogravimetric analysis was carried out to examine the thermal stability of the titled complexes. And the photoluminescence property of 1 was investigated.

  19. Thiocyanate-Ligated Heterobimetallic {PtM} Lantern Complexes Including a Ferromagnetically Coupled 1D Coordination Polymer.

    PubMed

    Guillet, Jesse L; Bhowmick, Indrani; Shores, Matthew P; Daley, Christopher J A; Gembicky, Milan; Golen, James A; Rheingold, Arnold L; Doerrer, Linda H

    2016-08-15

    A series of heterobimetallic lantern complexes with the central unit {PtM(SAc)4(NCS)} have been prepared and thoroughly characterized. The {Na(15C5)}[PtM(SAc)4(NCS)] series, 1 (Co), 2 (Ni), 3 (Zn), are discrete compounds in the solid state, whereas the {Na(12C4)2)}[PtM(SAc)4(NCS)] series, 4 (Co), 5 (Ni), 6 (Zn), and 7 (Mn), are ion-separated species. Compound 7 is the first {PtMn} lantern of any bridging ligand (carboxylate, amide, etc.). Monomeric 1-7 have M(2+), necessitating counter cations that have been prepared as {(15C5)Na}(+) and {(12C4)2Na}(+) variants, none of which form extended structures. In contrast, neutral [PtCr(tba)4(NCS)]∞ 8 forms a coordination polymer of {PtCr}(+) units linked by (NCS)(-) in a zigzag chain. All eight compounds have been thoroughly characterized and analyzed in comparison to a previously reported family of compounds. Crystal structures are presented for compounds 1-6 and 8, and solution magnetic susceptibility measurements are presented for compounds 1, 2, 4, 5, and 7. Further structural analysis of dimerized {PtM} units reinforces the empirical observation that greater charge density along the Pt-M vector leads to more Pt···Pt interactions in the solid state. Four structural classes, one new, of {MPt}···{PtM} units are presented. Solid state magnetic characterization of 8 reveals a ferromagnetic interaction in the {PtCr(NCS)} chain between the Cr centers of J/kB = 1.7(4) K. PMID:27486841

  20. Extended chain conformational preference of solid films of poly(2,6-benzoxazole) processed from Lewis acid coordination complexes

    SciTech Connect

    Chen, X.L.; Jenekhe, S.A.

    1996-12-31

    Polybenzoxazoles such as poly(2,6-benzoxazole)(2,6-PBO), poly(2,6-benzothiazole)(2,6-PBT) and poly(2,5(6)-benzimidazole) are semi-flexible, high temperature, and high modulus polymers which have been of wide interest as the matrix components of molecular composites. These polymers and their rigid-rod relatives polybenzobisazoles(PBZT, PBO, etc) also exhibit interesting electroactive and photoactive properties. As previously shown for rigid-rod polybenzobisazoles, we have found that the semi-flexible polybenzoazoles are soluble in Lewis acid (e.g. GaCl{sub 3}, AlCl{sub 3})/nitromethane solvent systems from which films and fibers could be processed. Remarkably, 2,6-PBO films prepared by complexation mediated processing from Lewis acid/nitromethane solutions of the polymer exhibit the extended chain (trans) conformation as evidenced by optical absorption and photoluminescence spectroscopies. In contrast, 2,6-PBO films prepared from formic acid/methanesulfonic acid(FA/MSA) solvent am predominantly of cis-conformation. The origin of this extended chain conformation preference of 2,6-PBO films prepared from Lewis acid/nitromethane solutions lies in the stereochemical control exerted by Lewis(MX{sub 3}) coordination to the imine nitrogens of 2,6-PBO resulting in an all-trans conformation after film processing and decomplexation. Since the trans- and cis-(2,6-PBO) have dramatically different solid state properties such as optical absorption and luminescence, our results demonstrate how a high degree of control of solid state structure and properties can be achieved by novel polymer processing.

  1. Long-term safety evaluation of a novel oxygen-coordinated niacin-bound chromium (III) complex.

    PubMed

    Shara, Michael; Kincaid, Anthony E; Limpach, Aimee L; Sandstrom, Robert; Barrett, Laura; Norton, Neil; Bramble, J D; Yasmin, Taharat; Tran, Janet; Chatterjee, Archana; Bagchi, Manashi; Bagchi, Debasis

    2007-07-01

    Chromium (III) is an essential micronutrient required for normal protein, fat and carbohydrate metabolism, as well as helps insulin metabolize fat, turn protein into muscle and convert sugar into energy. A broad spectrum of research investigations including in vitro, in vivo and clinical studies demonstrated the beneficial effects of novel oxygen- coordinated niacin-bound chromium (III) complex (NBC) in promoting glucose-insulin sensitivity, lipid profile, cardioprotective ability and lean body mass. This study examined the long-term safety of NBC by orally administering either 0 or 25 ppm or the human equivalency dose of 1000 microg elemental chromium (III) as NBC per day for 52 consecutive weeks to male and female Sprague-Dawley rats. Animals of each group and each gender were sacrificed on 26, 39, or 52 weeks of treatment. Body weight, physical and ocular health, feed and water intake, selected organ weights as such and as a percentage of liver and brain weight, hepatic lipid peroxidation and DNA fragmentation, hematology and clinical chemistry, and histopathological evaluations were conducted. At 26, 39, or 52 weeks of treatment, body weight gain was significantly reduced by 7.7%, 8.1% and 14.9% in male rats, and 5.5%, 11.4% and 9.6% in female rats, respectively, in the NBC treatment groups. No significant changes were observed in hepatic lipid peroxidation and DNA fragmentation, hematology and clinical chemistry, and histopathological evaluation between control and NBC groups at these time points. These findings, thus far, are in agreement with the subchronic studies in terms of the safety of NBC. PMID:17555823

  2. Nonoxido V(IV) Complexes: Prediction of the EPR Spectrum and Electronic Structure of Simple Coordination Compounds and Amavadin.

    PubMed

    Sanna, Daniele; Sciortino, Giuseppe; Ugone, Valeria; Micera, Giovanni; Garribba, Eugenio

    2016-08-01

    Density functional theory (DFT) calculations of the (51)V hyperfine coupling (HFC) tensor A have been completed for 20 "bare" V(IV) complexes with different donor sets, electric charges, and coordination geometries. Calculations were performed with ORCA and Gaussian software, using functionals BP86, TPSS0, B1LYP, PBE0, B3LYP, B3P, B3PW, O3LYP, BHandHLYP, BHandH, and B2PLYP. Among the basis sets, 6-311g(d,p), 6-311++g(d,p), VTZ, cc-pVTZ, def2-TZVPP, and the "core properties" CP(PPP) were tested. The experimental Aiso and Ai (where i = x or z, depending on the geometry and electronic structure of V(IV) complex) were compared with the values calculated by DFT methods. The results indicated that, based on the mean absolute percentage deviation (MAPD), the best functional to predict Aiso or Ai is the double hybrid B2PLYP. With this functional and the basis set VTZ, it is possible to predict the Aiso and Az of the EPR spectrum of amavadin with deviations of -1.1% and -2.0% from the experimental values. The results allowed us to divide the spectra of nonoxido V(IV) compounds in three types-called "type 1", "type 2", and "type 3", characterized by different composition of the singly occupied molecular orbital (SOMO) and relationship between the values of Ax, Ay, and Az. For "type 1" spectra, Az ≫ Ax ≈ Ay and Az is in the range of (135-155) × 10(-4) cm(-1); for "type 2" spectra, Ax ≈ Ay ≫ Az and Ax ≈ Ay are in the range of (90-120) × 10(-4) cm(-1); and for the intermediate spectra of "type 3", Az > Ay > Ax or Ax > Ay > Az, with Az or Ax values in the range of (120-135) × 10(-4) cm(-1). The electronic structure of the V(IV) species was also discussed, and the results showed that the values of Ax or Az are correlated with the percent contribution of V-dxy orbital in the SOMO. Similarly to V(IV)O species, for amavadin the SOMO is based mainly on the V-dxy orbital, and this accounts for the large experimental value of Az (153 × 10(-4) cm(-1)). PMID:27399275

  3. The metal complexes of amino acids and their N-substituted derivatives—VI. The physical properties, i.r. spectra and normal coordinate analysis of bivalent metal complexes with DL-threonine

    NASA Astrophysics Data System (ADS)

    Inomata, Yoshie; Takeuchi, Toshio; Moriwaki, Takao

    Complexes of five bivalent metals with DL-threonine have been prepared and characterized by means of i.r. absorption, powder diffuse reflection, and electronic spectra, X-ray diffraction and magnetic susceptibility. The complexes appear to be of three distinct types. The first type includes ML 2· nH 2O (M = Ni, Cu, Zn; L = DL-threoninato anion), in which the ligand chelates metal ions through the nitrogen atom and the oxygen atom of the carboxylato group. Three species of copper(II) complexes have been prepared. They seem to be two trans forms and one cis form. MnCl 2(HL) 4·H 2O is a second type in which the metal is coordinated through the oxygen atom of the carboxyl group and chloride ions, but is not coordinated through the nitrogen atom. 2CdCl 2·HL·HCl·2H 2O is a third type, in which the metal is coordinated through only chloride ions. In order to assign the observed frequencies of i.r. absorption spectra in detail, a normal coordinate analysis has been accomplished for the complexes of the first type as a 33-body problem. Copper(II) and zinc(II) complexes with L-threonine have been prepared for comparison.

  4. Optimization of a uranyl nitrate passive neutron counter

    SciTech Connect

    Rauch, Eric Benton; Bracken, David; West, James; Freeman, Corey; Newell, Matthew R; Bourret, Steven C; Rothrock, Richard B; Ladd - Lively, Jennifer L; Schuh, Denise

    2010-01-01

    Safeguarding natural uranium as it enters the fuel cycle has become a priority for the safeguards community in recent years. Uranyl nitrate is a material of interest in this endeavor because it is normally a step in the process from converting uranium ores to more concentrated forms like UO{sub 2} and U{sub 3}O{sub 8}. This paper will detail the improvements and design optimizations made for a uranyl nitrate neutron detector. The original design of the detector was based on standard neutron counter designs and featured 2 rings of He-3 tubes fully moderated and shielded from background. Several areas for enhancement were identified after months of testing in three different locations. An operating uranyl nitrate facility was included as one of the test locations. Three significant upgrades to the counter addressed in the redesign were: real time background detection, counter reliability improvements, and optimization of the detector design for the detection of neutrons emitted by the uranyl nitrate flowing through the monitored process pipe. The optimized detector design includes significant electronics upgrades, the ability to detect neutrons (background and signal) with 36 degree spatial resolution around the process pipe for signal and 45 degree spatial resolution for background, inner and outer rings of He-3 tubes for real time background corrections, and notably more reliable cabling. Monte Carlo N-Particle (MCNP) modeling was used to optimize the signal (neutrons from uranyl nitrate in the monitored process pipe) to noise (background neutrons from all sources) ratio of the inner ring of He-3 tubes. Additionally, MCNP modeling maximized noise to signal on the outer ring of He-3 tubes. Details of the detector optimization as well as all the additional detector enhancements will be discussed. The neutron counter will be field tested on the Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility at Oak Ridge National Laboratory (ORNL).

  5. Analysis of Novel Soluble Chromate and Uranyl Reductases and Generation of an Improved Enzyme by Directed Evolution

    SciTech Connect

    Barak,Y.; Ackerley, D.; Dodge, C.; Banwari, L.; Alex, C.; Francis, A.; Matin, A.

    2006-01-01

    Most polluted sites contain mixed waste. This is especially true of the U.S. Department of Energy (DOE) waste sites which hold a complex mixture of heavy metals, radionuclides, and organic solvents. In such environments enzymes that can remediate multiple pollutants are advantageous. We report here evolution of an enzyme, ChrR6 (formerly referred to as Y6), which shows a markedly enhanced capacity for remediating two of the most serious and prevalent DOE contaminants, chromate and uranyl. ChrR6 is a soluble enzyme and reduces chromate and uranyl intracellularly. Thus, the reduced product is at least partially sequestered and nucleated, minimizing the chances of reoxidation. Only one amino acid change, Tyr128Asn, was responsible for the observed improvement. We show here that ChrR6 makes Pseudomonas putida and Escherichia coli more efficient agents for bioremediation if the cellular permeability barrier to the metals is decreased.

  6. Uranyl peroxide enhanced nuclear fuel corrosion in seawater

    PubMed Central

    Armstrong, Christopher R.; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E.; Burns, Peter C.; Navrotsky, Alexandra

    2012-01-01

    The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances. PMID:22308442

  7. Rapid Self-Assembly of Uranyl Polyhedra into Crown Clusters

    SciTech Connect

    Sigmon, Ginger E.; Burns, Peter C.

    2011-06-22

    Clusters built from 32 uranyl peroxide polyhedra self-assemble and crystallize within 15 min after combining uranyl nitrate, ammonium hydroxide, and hydrogen peroxide in aqueous solution under ambient conditions. These novel crown-shaped clusters are remarkable in that they form so quickly, have extraordinarily low aqueous solubility, form with at least two distinct peroxide to hydroxyl ratios, and form in very high yield. The clusters, which have outer diameters of 23 Å, topologically consist of eight pentagons and four hexagons. Their rapid formation and low solubility in aqueous systems may be useful properties at various stages in an advanced nuclear energy system.

  8. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    SciTech Connect

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660{plus_minus}0.092 at 25 C, and extraction enthalpy is -5. 46{plus_minus}0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 {times} 10{sup 6}{plus_minus}3.56 {times} 10{sup 4} at 25 C; reaction enthalpy was -9.610{plus_minus}0.594 kcal/mol. Nitration complexation constant is 8.412{plus_minus}0.579, with an enthalpy of -10.72{plus_minus}1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured.

  9. Adsorption of Uranyl on Gibbsite: A Time-Resolved Laser-Induced Fluorescence Spectroscopy Study

    SciTech Connect

    Chang, Hyun-shik; Korshin, Gregory V.; Wang, Zheming; Zachara, John M.

    2006-02-15

    Uranyl adsorbed on gibbsite at pH 4.0-8.0 and ionic strengths (ISs) 0.001-0.4 M (NaClO4) in the absence of carbonate was studied using time-resolved laser-induced fluorescence spectroscopy (TRLIFS) under cryogenic conditions. TRLIFS data showed the presence of several distinct emission components. Their contributions were determined using the evolving factor analysis approach. Four components denoted as species A, B, C, and D were discerned. Each of them was characterized by a characteristic response to pH and IS changes and also by a unique combination of the values of the fundamental transition energy E0,0, vibronic spacing E, and half-width of the vibronic lines W. Species A and B were major contributors to the overall emission. They were mainly affected by the pH and predominated below and above pH 5.0, respectively. In contrast with that, the contribution of species C was noticeable only at IS = 0.001 M, while it was suppressed or absent at high IS values. It was concluded that species A and B are likely to correspond to inner-sphere surface aluminol complexes AlO-(UO2)+ and AlO-(UO2)OH, while species C was hypothesized to correspond to electrostatically bound uranyl complexes (predominantly [UO2(OH)3]-).

  10. Higher coordinate gold(I) complexes with the weak Lewis base tri(4-fluorophenyl) phosphine. Synthesis, structural, luminescence, and DFT studies

    NASA Astrophysics Data System (ADS)

    Agbeworvi, George; Assefa, Zerihun; Sykora, Richard E.; Taylor, Jared; Crawford, Carlos

    2016-03-01

    The structures and spectroscopic properties of two high coordinate gold(I) phosphine complexes with the TFFPP=tri(4-fluorophenyl)phosphine ligand are reported. Synthesis in a 1:3 metal to ligand ratio provided the compound [AuCl(TFFPP)3] (2) that crystallize in the P 1 bar space group, where the asymmetric unit consists of three independent molecules. In all three sites, two sets of bond angles display distinctly different ranges. The three P-Au-P angles have average values of 117.92°, 117.57°, and 114.78° for sites A, B, and C, with the corresponding P-Au-Cl angles of 98.31°, 99.05°, and 103.38°, respectively. The chloride ion coordinates as the fourth ligand, at the corresponding Au-Cl distance of 2.7337, 2.6825, and 2.6951 Å for the three sites. This distance is longer by 0.40-0.45 Å than the Au-Cl distance found in the mono TFFPP complex 1 (2.285 Å) indicating a weakening of the Au-Cl interaction as the coordination number increases. In compound 3, [Au(TFFPP)3]Cl·½CH2Cl2·H2O, the structure consists of three phosphine ligands bound to the gold(I) atom, but the Cl- exists as uncoordinated counter anion. The structural differences observed in the two complexes are attributable to crystal-packing effects caused by the introduction of H-bonding as well as enhanced intra and inter-molecular π-interaction in 3. The photoluminescence of the complexes compared with that of the ligand show ligand centered emission perturbed by the metal coordination. Theoretical DFT studies conducted on these complexes supports assignments of the electronic transitions observed in these systems.

  11. New Type of Coordinatively Unsaturated Zirconium(IV) Complexes: (N,N,N'-Tris(trimethylsilyl)diamido -N''-(trimethylsilyl)-P-methylphosphonimidato)--trichlorozirconium(IV). Molecular Structure of the Product of Its Reaction with Tetrahydrofuran

    SciTech Connect

    Markovskii, L.N.; Chernege, A.N.; Romanenko, V.D.; Ruban, A.V.; Shul'gin, V.F.

    1986-01-01

    The authors use phosphenodiimidic amides for the preparation of coordinatively unsaturated complexes of transition metals. The synthesis of a stable complex of 5-coordinate zirconium stabilized with a phosphonimidic diamide ligand is described; up to now compounds such as these have been known only for some cyclopentadienyl derivatives.

  12. Substrate binding preferences and pKa determinations of a nitrile hydratase model complex: Variable solvent coordination to [(bmmp-TASN)Fe]OTf

    PubMed Central

    O’Toole, Martin G.; Bennett, Brian; Mashuta, Mark S.; Grapperhaus, Craig A.

    2009-01-01

    The five-coordinate iron-dithiolate complex (N,N′-4,7-bis-(2′-methyl-2′-mercatopropyl)-1-thia-4,7-diazacyclononane)iron(III), [LFe]+, has been isolated as the triflate salt from reaction of the previously reported LFeCl with thallium triflate. Spectroscopic characterization confirms an S = 1/2 ground state in non-coordinating solvents with room temperature µeff = 1.78 µB and EPR derived g-values of g1 = 2.06, g2 = 2.03 and g3 = 2.02. [LFe]+ binds a variety of coordinating solvents resulting in six-coordinate complexes [LFe-solvent]+. In acetonitrile the low-spin [LFe-NCMe]+ (g1 = 2.27, g2 = 2.18 and g3 = 1.98) is in equilibrium with [LFe]+ with a binding constant of Keq = 4.03 at room temperature. Binding of H2O, DMF, methanol, DMSO and pyridine to [LFe]+ yields high-spin six-coordinate complexes with EPR spectra that display significant strain in the rhombic zero-field splitting term E/D. Addition of one equivalent of triflic acid to the previously reported diiron species (LFe)2O results in the formation of [(LFe)2OH]OTf, which has been characterized by x-ray crystallography. The aqueous chemistry of [LFe]+ reveals three distinct species as a function of pH: [LFe-OH2]+, [(LFe)2OH]OTf, and (LFe)2O. The pKa values for [LFe-OH2]+ and [(LFe)2OH]OTf are 5.4 ± .1 and 6.52 ± .05 respectively. PMID:19166306

  13. Copper(II) tetrafluoroborate complexes with the N(3),N(4)-bridging coordination of 1-(tert-butyl)-1H-tetrazole: synthesis, crystal structure and magnetic properties.

    PubMed

    Degtyarik, Mikhail M; Lyakhov, Alexander S; Ivashkevich, Ludmila S; Matulis, Vitaly E; Matulis, Vadim E; Gruschinski, Sina; Voitekhovich, Sergei V; Kersting, Berthold; Ivashkevich, Oleg A

    2015-11-14

    1-(tert-Butyl)-1H-tetrazole (L) reacts with copper(ii) tetrafluoroborate hexahydrate to give the complexes [Cu2L8(H2O)2](BF4)4 (1) or [Cu3L6(H2O)6](BF4)6 (2) depending on the reaction conditions. These complexes, as well as compound L, were characterized using single crystal X-ray analysis. Complex 1 was found to comprise a dinuclear complex cation [Cu2L8(H2O)2](4+) (the Ci symmetry point group), with six tetrazole ligands L showing monodentate N(4)-coordination, and two ligands L providing two tetrazole ring N(3),N(4) bridges between the copper(ii) cations; water molecules complete the distorted octahedral coordination of the metal ions. Complex 2 includes a linear trinuclear complex cation [Cu3L6(H2O)6](6+) (the S6 symmetry point group), in which neighbouring copper(ii) cations are linked by three ligands L via tetrazole ring N(3),N(4) bridges; central and terminal metal ions show octahedral CuN6 and CuN3O3 coordination cores, respectively. The temperature-dependent magnetic susceptibility measurements of complex 2 revealed that the copper(ii) ions were weakly ferromagnetically coupled showing a coupling constant J of 2.2 cm(-1) {H = -2J(S1S2 + S2S3)}. The quantum-chemical investigation of the electronic structure and basicity of ligand L was carried out. PMID:26442910

  14. Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

    SciTech Connect

    K. Kubatko; K. Helean; A. Navrotsky; P.C. Burns

    2005-05-11

    The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO{sub 2}){sub 4}O(OH){sub 6}](H{sub 2}O){sub 5}, metaschoepite; {beta}-UO{sub 2}(OH){sub 2}; CaUO{sub 4}; Ca(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 8}, becquerelite; Ca(UO{sub 2}){sub 4}O{sub 3}(OH){sub 4}(H{sub 2}O){sub 2}; Na(UO{sub 2})O(OH), clarkeite; Na{sub 2}(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 7}, the sodium analogue of compreignacite and Pb{sub 3}(UO{sub 2}){sub 8}O{sub 8}(OH){sub 6}(H{sub 2}O){sub 2}, curite. The enthalpy of formation from the binary oxides, {Delta}H{sub f-ox}, at 298 K was calculated for each compound from the respective drop solution enthalpy, {Delta}H{sub ds}. The standard enthalpies of formation from the elements, {Delta}H{sub f}{sup o}, at 298 K are -1791.0 {+-} 3.2, -1536.2 {+-} 2.8, -2002.0 {+-} 3.2, -11389.2 {+-} 13.5, -6653.1 {+-} 13.8, -1724.7 {+-} 5.1, -10936.4 {+-} 14.5 and -13163.2 {+-} 34.4 kJ mol{sup -1}, respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments.

  15. Coordination behavior of ligand based on NNS and NNO donors with ruthenium(III) complexes and their catalytic and DNA interaction studies

    NASA Astrophysics Data System (ADS)

    Manikandan, R.; Viswnathamurthi, P.

    2012-11-01

    Reactions of 2-acetylpyridine-thiosemicarbazone HL1, 2-acetylpyridine-4-methyl-thiosemicarbazone HL2, 2-acetylpyridine-4-phenyl-thiosemicarbazone HL3 and 2-acetylpyridine-semicarbazone HL4 with ruthenium(III) precursor complexes were studied and the products were characterized by analytical and spectral (FT-IR, electronic, EPR and EI-MS) methods. The ligands coordinated with the ruthenium(III) ion via pyridine nitrogen, azomethine nitrogen and thiolate sulfur/enolate oxygen. An octahedral geometry has been proposed for all the complexes based on the studies. All the complexes are redox active and display an irreversible and quasireversible metal centered redox processes. Further, the catalytic activity of the new complexes has been investigated for the transfer hydrogenation of ketones in the presence of isopropanol/KOH and the Kumada-Corriu coupling of aryl halides with aryl Grignard reagents. The DNA cleavage efficiency of new complexes has also been tested.

  16. Coordination behavior of ligand based on NNS and NNO donors with ruthenium(III) complexes and their catalytic and DNA interaction studies.

    PubMed

    Manikandan, R; Viswnathamurthi, P

    2012-11-01

    Reactions of 2-acetylpyridine-thiosemicarbazone HL(1), 2-acetylpyridine-4-methyl-thiosemicarbazone HL(2), 2-acetylpyridine-4-phenyl-thiosemicarbazone HL(3) and 2-acetylpyridine-semicarbazone HL(4) with ruthenium(III) precursor complexes were studied and the products were characterized by analytical and spectral (FT-IR, electronic, EPR and EI-MS) methods. The ligands coordinated with the ruthenium(III) ion via pyridine nitrogen, azomethine nitrogen and thiolate sulfur/enolate oxygen. An octahedral geometry has been proposed for all the complexes based on the studies. All the complexes are redox active and display an irreversible and quasireversible metal centered redox processes. Further, the catalytic activity of the new complexes has been investigated for the transfer hydrogenation of ketones in the presence of isopropanol/KOH and the Kumada-Corriu coupling of aryl halides with aryl Grignard reagents. The DNA cleavage efficiency of new complexes has also been tested. PMID:22902929

  17. High-temperature, high-pressure hydrothermal synthesis, characterization, and structural relationships of layered uranyl arsenates.

    PubMed

    Liu, Hsin-Kuan; Ramachandran, Eswaran; Chen, Yi-Hsin; Chang, Wen-Jung; Lii, Kwang-Hwa

    2014-09-01

    Five new uranyl arsenates, Na14[(UO2)5(AsO4)8]·2H2O (1), K6[(UO2)5O5(AsO4)2] (2a), K4[(UO2)3O2(AsO4)2] (2b), Rb4[(UO2)3O2(AsO4)2] (3), and Cs6[(UO2)5O2(AsO4)4] (4), were synthesized by high-temperature, high-pressure hydrothermal reactions at about 560 °C and 1440 bar and were characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and photoluminescence spectroscopy. Crystal data for compound 1: triclinic, P1, a = 7.0005(3) Å, b = 12.1324(4) Å, c = 13.7428(5) Å, α = 64.175(2)°, β = 89.092(2)°, γ = 85.548(2)°, V = 1047.26(7) Å(3), Z = 1, R1 = 0.0185; compound 2a: monoclinic, P2₁/c, a = 6.8615(3) Å, b = 24.702(1) Å, c = 7.1269(3) Å, β = 98.749(2)°, V = 1193.89(9) Å(3), Z = 2, R1 = 0.0225; compound 2b: monoclinic, P2₁/c, a = 6.7852(3) Å, b = 17.3640(8) Å, c = 7.1151(3) Å, β = 98.801(3)°, V = 828.42(6) Å(3), Z = 2, R1 = 0.0269; compound 3: monoclinic, P2₁/m, a = 6.9783(3) Å, b = 17.4513(8) Å, c = 7.0867(3) Å, β = 90.808(3)°, V = 862.94(7) Å(3), Z = 2, R1 = 0.0269; compound 4: triclinic, P1, a = 7.7628(3) Å, b = 9.3324(4) Å, c = 11.9336(4) Å, α = 75.611(2)°, β = 73.136(2)°, γ = 86.329(2)°, V = 801.37(5) Å(3), Z = 1, R1 = 0.0336. The five compounds have layer structures consisting of uranyl square, pentagonal, and hexagonal bipyramids as well as AsO4 tetrahedra. Compound 1 contains chains of discrete uranyl square and pentagonal bipyramids, 2a contains three-polyhedron-wide ribbons of edge- and corner-sharing uranyl square and pentagonal bipyramids, 2b and 3 contain dimers of edge-shairing pentagonal bipyramids that share edges with hexagonal bipyramids to form chains, and 4 contains one-polyhedron-wide zigzag chains of edge-sharing uranyl polyhedra. The double sheet structure of 1 is new, but the chain topology has been observed in an organically templated uranyl sulfate. Compound 2b is a new geometrical isomer of the phosphuranylite group. The sheet anion topologies of 2a and 4 can be obtained by

  18. Synthesis, spectroscopic studies, thermal analyses, biological activity of tridentate coordinated transition metal complexes of bi(pyridyl-2-ylmethyl)amine]ligand

    NASA Astrophysics Data System (ADS)

    Abd El-Halim, Hanan F.; Mohamed, Gehad G.

    2016-01-01

    A new tridentate acyclic pincer ligand, [bi(pyridin-2-methyl)amine] (bpma, HL), was synthesized and reacted to form complexes with copper(II), nickel(II), iron(II), cobalt(II) and zinc(II) ions. Both the ligand and its complexes were characterized using elemental analysis, molar conductance, infrared, 1H-NMR-spectroscopy, mass and thermal analyses. According to the spectroscopic data, all of the complexes share the same coordination environment around the metal atoms, consisting two nitrogen-pyridine entities, one nitrogen-methylamine entity, one/two water molecules and/or one/two chloride or bromide ions. Complexes also showed molar conductivity according to the presence of two halide anions outer the coordination sphere except Co(II) and Zn(II) complexes are non electrolytes. Analysis indicates that the metal ions have trigonal bipyramidal structure. Cu(II), Ni(II), Fe(II), Co(II), and Zn(II) metal complexes were screened for their antibacterial activity against Bacillus subtilis, Staphylococcus aureus (G+) and Escherichia coli, and Pseudomonas aeruginosa (G-) bacteria. They showed remarkable antimicrobial activity.

  19. Non-oxo 5-coordinate and 6-coordinate vanadium(IV) complexes with their precursor [LV(III)(CH3OH)](0), where L = a trianionic aminetris(phenolate)-[N,O,O,O] donor ligand: a magnetostructural and EPR study.

    PubMed

    Kajiwara, Takashi; Wagner, Rita; Bill, Eckhard; Weyhermüller, Thomas; Chaudhuri, Phalguni

    2011-12-21

    Ligating properties of a tripodal, potentially tetradentate aminetris(phenol) ligand, tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine, H(3)L, containing [N,O,O,O] donor atoms toward the vanadium ions in +III and IV oxidation states have been studied. The structures of complexes 1 [LV(III)(CH(3)OH)](0), 2 [LV(IV)(OCH(3))](0) and 3 [LV(IV)(acac)](0) were determined by X-ray diffraction methods as having five-coordinate V(III), 1, five-coordinate non-oxo-vanadium(IV), 2, and six-coordinate non-oxo-vanadium(iv) 3, respectively. Compounds 1-3 were also studied with electrochemical methods, variable-temperature (2-295 K) magnetic susceptibility measurements and X-band electron paramagnetic resonance (EPR) spectroscopy. The electrochemical results of 2 and 3 suggest metal-centered oxidation, i.e. the generation of a V(V)-phenolate species. EPR investigations indicate a (d(xy))(1) ground state showing a considerable increase in the in-plane π-bonding, as is expected for a phenolate ligand. PMID:22005800

  20. Seven-coordinate anion complex with a tren-based urea: Binding discrepancy of hydrogen sulfate in solid and solution states

    SciTech Connect

    Pramanik, Avijit; Thompson, Bethtrice; Hayes, Trina; Tucker, Kimberly; Powell, Douglas R.; Bonnesen, Peter V; Ellis, Erick D; Lee, Ken S.; Yu, Hongtau; Hossain, Md. Alamgir

    2011-01-01

    Structural characterization of a hydrogen sulfate complex with a tren-based urea suggests that the anion is coordinated with sixNH Obonds (dN O = 2.857 (3) to 3.092 (3)A ) and one OH O bond (dO O = 2.57 (2) A ) from three receptors; however, in solution the anion is bound within the pseudocavity of one receptor.

  1. Synthesis and crystal structures of two coordination polymers and a binuclear cadmium(II) complex containing 3- and 4-aminobenzoate ligands.

    PubMed

    Zhou, Dong-Mei; Zhao, Xiao-Lan; Liu, Feng-Yi; Kou, Jun-Feng

    2015-08-01

    Due to their wide range of coordination modes and versatile conformations when binding to metal atoms, multicarboxylate ligands are of interest in the design of metal-organic frameworks (MOFs). Three Cd(II) complexes, namely catena-poly[diammonium [[chloridocadmium(II)]-di-μ-chlorido-[chloridocadmium(II)]-bis(μ-3-aminobenzoato)-κ(3)N:O,O';κ(3)O,O':N

  2. Structure and dynamics of aqueous solution of uranyl ions

    SciTech Connect

    Chopra, Manish; Choudhury, Niharendu

    2014-04-24

    The present work describes a molecular dynamics simulation study of structure and dynamics of aqueous solution of uranyl ions in water. Structural properties of the system in terms of radial distribution functions and dynamical characteristics as obtained through velocity autocorrelation function and mean square displacements have been analyzed. The results for radial distribution functions show the oxygen of water to form the first solvation shell at 2.4 Å around the uranium atom, whereas the hydrogen atoms of water are distributed around the uranium atom with the major peak at around 3.0 Å. Analyses of transport behaviors of ions and water through MSD indicates that the diffusion of the uranyl ion is much less as compared to that of the water molecules. It is also observed that the dynamical behavior of water molecules gets modified due to the presence of uranyl ion. The effect of increase in concentration of uranyl ions on the structure and dynamics of water molecules is also studied.

  3. Colorimetric peroxidase mimetic assay for uranyl detection in sea water.

    PubMed

    Zhang, Dingyuan; Chen, Zhuo; Omar, Haneen; Deng, Lin; Khashab, Niveen M

    2015-03-01

    Uranyl (UO2(2+)) is a form of uranium in aqueous solution that represents the greatest risk to human health because of its bioavailability. Different sensing techniques have been used with very sensitive detection limits especially the recently reported uranyl-specific DNAzymes systems. However, to the best of our knowledge, few efficient detection methods have been reported for uranyl sensing in seawater. Herein, gold nanoclusters (AuNCs) are employed in an efficient spectroscopic method to detect uranyl ion (UO2(2+)) with a detection limit of 1.86 μM. In the absence of UO2(2+), the BSA-stabilized AuNCs (BSA-AuNCs) showed an intrinsic peroxidase-like activity. In the presence of UO2(2+), this activity can be efficiently restrained. The preliminary quenching mechanism and selectivity of UO2(2+) was also investigated and compared with other ions. This design strategy could be useful in understanding the binding affinity of protein-stabilized AuNCs to UO2(2+) and consequently prompt the recycling of UO2(2+) from seawater. PMID:25658750

  4. Analysis of High Enriched Uranyl Nitrate Solution Containing Cadmium

    SciTech Connect

    S. S. Kim

    2006-09-01

    A benchmark evaluation has been performed for a set of twenty-one critical experiments involving high enriched uranyl nitrate solution with and without cadmium nitrate as a soluble neutron absorber. The critical experiments analyzed include two types of cylindrical vessels with 24.18 and 29.16 cm in diameters. The vessels were reflected with water and in some cases with water containing dissolved cadmium nitrate. The uranium concentration ranged from 482 to 529 g/l, and cadmium concentration in the uranyl nitrate solution ranged from 0.0 to 11.31 g/l. The cadmium concentration in the reflector solution ranged from 0.0 to 15.16 g/l. Using MCNP and KENO-V.a, complete three-dimensional models were created for the two vessels filled with the uranyl nitrate solution and reflector solution. A series of criticality calculations were performed with KENO-V.a, MCNP4b, and MCNP5. In general, good agreement between KENO-V.a and MCNP4b was observed. However, MCNP5 results show consistently lower values compared with MCNP4b results with the maximum difference of 1.2 %. This ICSBEP supported evaluation provides valuable data for the effect of soluble neutron absorber (cadmium nitrate) on the criticality safety of high-enriched uranyl nitrate solution. These data can also be used in determining critical controls and for validation of the calculation methods.

  5. Novel Ni(II) and Zn(II) complexes coordinated by 2-arylaminomethyl-1H-benzimidazole: Molecular structures, spectral, DFT studies and evaluation of biological activity

    NASA Astrophysics Data System (ADS)

    Abdel-Ghani, Nour T.; Abo El-Ghar, Maha F.; Mansour, Ahmed M.

    2013-03-01

    [NiL1,2Cl2(OH2)3]·zH2O and [ZnL1,2(CH3CO2)2] (L1 = (1H-benzimidazol-2-ylmethyl)-N-phenyl amine, z = 0 and L2 = 2-[(1H-Benzimidazol-2-ylmethyl)-amino]-benzoic acid methyl ester, z = 1) complexes have been synthesized and characterized by a variety of physico-chemical techniques. The central Ni(II) ion is coordinated by only the pyridine-type nitrogen (Npy) of benzimidazole ring, three water molecules and two chlorido ligands forming a distorted octahedral geometry. Five coordinated zinc complexes were obtained, where the coordination sphere of zinc ion is made up of secondary amino group (NHsec), Npy and two acetate groups, one acts as a unidentate and the other as a bidentate. A theoretical DFT/UB3LYP method combined with LANL2DZ basis set shows that all the metal-ligand bonds are of the L → M type. Electronic structures have been calculated using TD-DFT method. The antibacterial activity of NiL2 complexes decreases by the introduction of COOCH3 group in the ortho-position of the aniline moiety.

  6. A structure-based analysis of the vibrational spectra of nitrosyl ligands in transition-metal coordination complexes and clusters

    NASA Astrophysics Data System (ADS)

    De La Cruz, Carlos; Sheppard, Norman

    2011-01-01

    The vibrational spectra of nitrogen monoxide or nitric oxide (NO) bonded to one or to several transition-metal (M) atom(s) in coordination and cluster compounds are analyzed in relation to the various types of such structures identified by diffraction methods. These structures are classified in: (a) terminal (linear and bent) nitrosyls, [M(σ-NO)] or [M(NO)]; (b) twofold nitrosyl bridges, [M 2(μ 2-NO)]; (c) threefold nitrosyl bridges, [M 3(μ 3-NO)]; (d) σ/π-dihaptonitrosyls or " side-on" nitrosyls; and (e) isonitrosyls (oxygen-bonded nitrosyls). Typical ranges for the values of internuclear N-O and M-N bond-distances and M-N-O bond-angles for linear nitrosyls are: 1.14-1.20 Å/1.60-1.90 Å/180-160° and for bent nitrosyls are 1.16-1.22 Å/1.80-2.00 Å/140-110°. The [M 2(μ 2-NO)] bridges have been divided into those that contain one or several metal-metal bonds and those without a formal metal/metal bond (M⋯M). Typical ranges for the M-M, N-O, M-N bond distances and M-N-M bond angles for the normal twofold NO bridges are: 2.30-3.00 Å/1.18-1.22 Å/1.80-2.00 Å/90-70°, whereas for the analogous ranges of the long twofold NO bridges these are 3.10-3.40 Å/1.20-1.24 Å/1.90-2.10 Å/130-110°. In both situations the N-O vector is approximately at right angle to the M-M (or M⋯M) vector within the experimental error; i.e. the NO group is symmetrical bonded to the two metal atoms. In contrast the threefold NO bridges can be symmetrically or unsymmetrically bonded to an M 3-plane of a cluster compound. Characteristic values for the N-O and M-N bond-distances of these NO bridges are: 1.24-1.28 Å/1.80-1.90 Å, respectively. As few dihaptonitrosyl and isonitrosyl complexes are known, the structural features of these are discussed on an individual basis. The very extensive vibrational spectroscopy literature considered gives emphasis to the data from linearly bonded NO ligands in stable closed-shell metal complexes; i.e. those which are consistent with the

  7. A structure-based analysis of the vibrational spectra of nitrosyl ligands in transition-metal coordination complexes and clusters.

    PubMed

    De La Cruz, Carlos; Sheppard, Norman

    2011-01-01

    The vibrational spectra of nitrogen monoxide or nitric oxide (NO) bonded to one or to several transition-metal (M) atom(s) in coordination and cluster compounds are analyzed in relation to the various types of such structures identified by diffraction methods. These structures are classified in: (a) terminal (linear and bent) nitrosyls, [M(σ-NO)] or [M(NO)]; (b) twofold nitrosyl bridges, [M2(μ2-NO)]; (c) threefold nitrosyl bridges, [M3(μ3-NO)]; (d) σ/π-dihaptonitrosyls or "side-on" nitrosyls; and (e) isonitrosyls (oxygen-bonded nitrosyls). Typical ranges for the values of internuclear N-O and M-N bond-distances and M-N-O bond-angles for linear nitrosyls are: 1.14-1.20 Å/1.60-1.90 Å/180-160° and for bent nitrosyls are 1.16-1.22 Å/1.80-2.00 Å/140-110°. The [M2(μ2-NO)] bridges have been divided into those that contain one or several metal-metal bonds and those without a formal metal/metal bond (M⋯M). Typical ranges for the M-M, N-O, M-N bond distances and M-N-M bond angles for the normal twofold NO bridges are: 2.30-3.00 Å/1.18-1.22 Å/1.80-2.00 Å/90-70°, whereas for the analogous ranges of the long twofold NO bridges these are 3.10-3.40 Å/1.20-1.24 Å/1.90-2.10 Å/130-110°. In both situations the N-O vector is approximately at right angle to the M-M (or M⋯M) vector within the experimental error; i.e. the NO group is symmetrical bonded to the two metal atoms. In contrast the threefold NO bridges can be symmetrically or unsymmetrically bonded to an M3-plane of a cluster compound. Characteristic values for the N-O and M-N bond-distances of these NO bridges are: 1.24-1.28 Å/1.80-1.90 Å, respectively. As few dihaptonitrosyl and isonitrosyl complexes are known, the structural features of these are discussed on an individual basis. The very extensive vibrational spectroscopy literature considered gives emphasis to the data from linearly bonded NO ligands in stable closed-shell metal complexes; i.e. those which are consistent with the

  8. The metal complexes of amino acids and their N-substituted derivatives—VII. The i.r. spectra and normal coordinate analyses of bivalent metal complexes with N-methylglycine and N-phenylglycine

    NASA Astrophysics Data System (ADS)

    Inomata, Yoshie; Shibata, Akio; Yukawa, Yasuhiko; Takeuchi, Toshio; Moriwaki, Takao

    Twelve complexes of bivalent metals with N-methylglycine (sarcosine) and N-phenylglycine have been prepared over wide pH ranges and characterized by means of i.r. powder diffuse reflection, electronic spectra and magnetic susceptibility. These complexes are classified into two types, either with or without chloride ions, from elemental analyses: the former type (A) consists of ML 2· nH 2O (M = Co, Ni, Cu, Zn for L = sarcosinate anion; M = Co, Ni, Cu, Zn, Cd for L = N-phenylglycinate anion), which appear to be octahedral complexes. The metal is coordinated through a nitrogen atom, a carboxyl oxygen atom and water molecules or the carboxyl oxygen atoms of neighboring molecules. The latter type (B) consists of CoCl 2 (HL) 2·2H 2O, ZnCl 2 (HL) 2 and CdCl 2 (HL) (HL = sarcosine), in which the ligand has a zwitterion structure and has metal ions coordinated through only a carboxyl oxygen atom, but does not chelate through a nitrogen atom. In the cadmium (II) complex, a chloride ion seems to bridge to two cadmium (II) ions. In order to assign the observed frequencies of i.r. spectra in detail, normal coordinate analyses have been carried out for the complexes of the A type. The frequency separation of COO - antisymmetric and symmetric vibrations of A type complexes with sarcosine increases in the order: Co (II) < Ni (II) < Zn (II) < Cu (II). These separations of A type complexes with sarcosine and N-phenylglycine are larger than those of the corresponding complexes with glycine, alanine and other α-amino acids. The frequencies of metal-nitrogen and metal-oxygen stretching vibrations increase in the order: Co (II) < Zn (II) < Ni (II) < Cu (II) for sarcosine A type complexes.

  9. Synthesis and characterization of templated ion exchange resins for the selective complexation of actinide ions. 1998 annual progress report

    SciTech Connect

    Murray, G.M.; Uy, O.M.

    1998-06-01

    'The purpose of this research is to develop polymeric extractants for the selective complexation of uranyl ions (and subsequently other actinyl and actinide ions) from aqueous solutions (lakes, streams, waste tanks and body fluids). Selectivity for a specific actinide ion is obtained by providing polymers with cavities lined with complexing ligands so arranged as to match the charge, coordination number, coordination geometry, and size of the actinide metal ion. These cavity-containing polymers will be produced using a specific actinide ion (or surrogate) as a template around which monomeric complexing ligands will be polymerized. The polymers will provide useful sequestering agents for removing actinide ions from wastes and will form the basis for a variety of analytical techniques for actinide determinations.'

  10. P,C-Chelation versus P,P-coordination of unsymmetrical phosphorus ylides in palladacyclopropa[60]fullerene complexes; synthetic, spectroscopic, and theoretical studies.

    PubMed

    Sabounchei, Seyyed Javad; Hosseinzadeh, Marjan; Hashemi, Ali; Salehzadeh, Sadegh; Maleki, Farahnaz

    2016-09-21

    The new palladacyclopropa[60]fullerene complexes incorporating α-keto stabilized phosphorus ylides were synthesized in a three-component reaction of the unsymmetrical phosphorus ylides [Ph2P(CH2)nPPh2[double bond, length as m-dash]C(H)C(O)C6H4-m-R] (n = 1, R = Br, NO2, (Y(1), Y(2)); n = 2, R = Br, NO2, (Y(3), Y(4))), C60 and Pd(dba)2 (dba = dibenzylideneacetone). The obtained novel P,C-chelated [(η(2)-C60)Pd(κ(2)-Y(1))] (1) and [(η(2)-C60)Pd(κ(2)-Y(2))] (2) complexes and P,P-coordinated [(η(2)-C60)Pd(Y(3))2] (3) and [(η(2)-C60)Pd(Y(4))2] (4) complexes were characterized successfully by IR, UV-Vis, ESI-MS and NMR ((1)H, (13)C and (31)P) spectroscopic methods. Complexes 1-4 are rare examples of palladacyclopropa[60]fullerene complexes with phosphorus ylide ligands. Spectroscopic results revealed that none of possible side products including P,P-coordinated [(η(2)-C60)Pd(Y(1))2] and [(η(2)-C60)Pd(Y(2))2] complexes and also P,C-chelated [(η(2)-C60)Pd(κ(2)-Y(3))] and [(η(2)-C60)Pd(κ(2)-Y(4))] complexes are formed. The EDA analysis indicated that in all the above complexes the metal-ligand bonds are mostly electrostatic in nature. PMID:27524503

  11. Five-coordinate complexes [FeX(depe)(2)]BPh(4), X = Cl, Br: electronic structure and spin-forbidden reaction with N(2).

    PubMed

    Franke, Oliver; Wiesler, Beatrix E; Lehnert, Nicolai; Näther, Christian; Ksenofontov, Vadim; Neuhausen, Jörg; Tuczek, Felix

    2002-07-01

    The bonding of N(2) to the five-coordinate complexes [FeX(depe)(2)](+), X = Cl (1a) and Br (1b), has been investigated with th