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Uranyl ion coordination  

USGS Publications Warehouse

A review of the known crystal structures containing the uranyl ion shows that plane-pentagon coordination is equally as prevalent as plane-square or plane-hexagon. It is suggested that puckered-hexagon configurations of OH - or H2O about the uranyl group will tend to revert to plane-pentagon coordination. The concept of pentagonal coordination is invoked for possible explanations of the complex crystallography of the natural uranyl hydroxides and the unusual behavior of polynuclear ions in hydrolyzed uranyl solutions.

Evans, H.T., Jr.



Variable Denticity in Carboxylate Binding to the Uranyl Coordination Complexes  

SciTech Connect

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.

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



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


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

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



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

SciTech Connect

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.

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



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

SciTech Connect

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)].

Ni, Chengbao; Shuh, David; Raymond, Kenneth



Uranyl monocarboxylates of aromatic acids: a density functional model study of uranyl humate complexation.  


Using a scalar relativistic all-electron density functional method, we studied uranium(VI) complexation with benzoic acid and its derivatives in aqueous solution as models of uranyl humates. We explored monodentate, bidentate, and chelate coordination of various isomers of methyl and hydroxyl substituted benzoic acid ligands. Monodentate complexes were determined to be energetically preferred as long as entropy effects were neglected. However, bidentate structures were favored at the Gibbs free energy level. Coordination of aromatic carboxylic acids tends to be weaker than that of aliphatic ones, while structural characteristics were determined to be quite similar. Optimized geometries yield uranyl bonds and U-C distances in agreement with EXAFS results for monocarboxylate of benzoate and p-hydroxy benzoate. Average uranyl-oxygen distances to equatorial ligands, U-O(eq), are shorter than in experiment, which is tentatively rationalized by variations in the coordination numbers. As for aliphatic monocarboxylate complexes studied earlier, U-O(eq) values of benzoic acid derivatives do not discriminate mono- and bidentate coordinated species. Structures and energies determined support the interpretation of uranyl humate complexes as bidentate carboxylate species with fivefold coordination of uranyl. PMID:19381422

Ray, Rupashree Shyama; Krüger, Sven; Rösch, Notker



Dimeric uranyl complexes with bridging perrhenates.  


The reaction between [UO2(ReO4)2.H(2)O] and two equivalents of either tri-n-butyl phosphine oxide (TBPO) or tri-iso-butyl phosphate (TiBP) results in the formation of [UO2(mu2-ReO4)(ReO4)(TBPO)2]2 (1) and [UO2(mu2-ReO4)(ReO4)(TiBP)2]2 (2) respectively. Both complexes crystallise as two structurally similar centrosymmetric dimers, the cores containing two uranyl moieties linked by bridging perrhenates. Two P=O donor ligands and one monodenatate perrhenate complete the pentagonal bipyramidal coordination sphere at each metal centre. Both complexes have also been characterised in the solid state by vibrational and absorption spectroscopy. Solution spectroscopic characterisation indicates that both perrhenate and phosphine oxide (1) or phosphate (2) remain coordinated, although it is not possible to state conclusively that the dimeric species remain intact. A low resolution structural study of a minor product from the reaction that yielded revealed a monomeric complex with only monodentate perrhenate coordination, [UO2(ReO4)2(H2O)(TiBP)2] (2'). These results represent the first structural evidence for the bridging coordination mode of perrhenate on coordination to an actinide and yields further insight into the possible solvent phase pertechnetate complexes that may exist in PUREX process phosphate rich solvent. PMID:17426862

John, Gordon H; May, Iain; Sarsfield, Mark J; Collison, David; Helliwell, Madeleine



Uranyl-oxo coordination directed by non-covalent interactions.  


Directed coordination of weakly Lewis acidic K(+) ions to weakly Lewis basic uranyl oxo ligands is accomplished through non-covalent cation-? and cation-F interactions for the first time. Comparison of a family of structurally related diarylamide ligands highlights the role that the cation-? and cation-F interactions play in guiding coordination. Cation binding to uranyl is demonstrated in the solid state and in solution, providing the shortest reported crystallographic uranyl-oxo to potassium distance. UV-Vis, TD-DFT calculations, and electrochemical measurements show that cation coordination directly impacts the electronics at the uranium(vi) cation. PMID:24894554

Lewis, Andrew J; Yin, Haolin; Carroll, Patrick J; Schelter, Eric J



Uranyl coordination environment in hydrophobic ionic liquids: an in situ investigation.  


Different inner-sphere coordination environments are observed for the uranyl nitrate complexes formed with octyl-phenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and tributyl phosphate in dodecane and in the hydrophobic ionic liquids (ILs) [C(4)mim][PF(6)] and [C(8)mim][N(SO(2)CF(3))(2)]. Qualitative differences in the coordination environment of the extracted uranyl species are implied by changes in peak intensity patterns and locations for uranyl UV-visible spectral bands when the solvent is changed. EXAFS data for uranyl complexes in dodecane solutions is consistent with hexagonal bipyramidal coordination and the existence of UO(2)(NO(3))(2)(CMPO)(2). In contrast, the complexes formed when uranyl is transferred from aqueous nitric acid solutions into the ILs exhibit an average equatorial coordination number of approximately 4.5. Liquid/liquid extraction results for uranyl in both ILs indicate a net stoichiometry of UO(2)(NO(3))(CMPO)(+). The concentration of the IL cation in the aqueous phase increases in proportion to the amount of UO(2)(NO(3))(CMPO)(+) in the IL phase, supporting a predominantly cation exchange mechanism for partitioning in the IL systems. PMID:12665350

Visser, Ann E; Jensen, Mark P; Laszak, Ivan; Nash, Kenneth L; Choppin, Gregory R; Rogers, Robin D



First principles NEXAFS simulations of N-donor Uranyl complexes  

NASA Astrophysics Data System (ADS)

The synthesis and study of soft-donor uranyl complexes can provide new insights into the coordination chemistry of non-aqueous [UO]2^+ Recently, the tunable N-donor ligand 2,6-Bis(2-benzimidazyl)pyridine (BBP) was employed to produce novel uranyl complexes in which the [UO]2^+ cation is ligated by anionic and covalent groups with discrete chemical differences. In this work we investigate the electronic structure of the three such uranyl-BBP complexes via near-edge X-ray absorption fine structure (NEXAFS) experiments and simulations using the eXcited electron and Core-Hole (XCH) approach [1]. The evolution of the structural as well as electronic properties across the three complexes is studied systematically. Computed N K-edge and O K-edge NEXAFS spectra are compared with experiment and spectral features assigned to specific electronic transitions in these complexes. Studying the variations in spectral features arising from N K-edge absorption provides a clear picture of ligand-uranyl bonding in these systems. References: [1] D. Prendergast and G. Galli, X-ray absorption spectra of water from first-principles calculations, Phys. Rev. Lett., 215502 (2006).

Pemmaraju, C. D.; Duan, R.; Copping, R.; Jeon, B.; Teat, S. J.; Janousch, M.; Tyliszczak, T.; Canning, A.; Grønbech-Jensen, N.; Shuh, D. K.; Prendergast, D.



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

SciTech Connect

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.

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



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

SciTech Connect

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.

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



EXAFS Study of Uranyl Complexation at Pseudomonas fluorescens Cell Surfaces  

NASA Astrophysics Data System (ADS)

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.

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



Bonding and Charge Transfer in Nitrogen-Donor Uranyl Complexes: Insights from NEXAFS Spectra.  


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

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



Surface complexation model of uranyl sorption on Georgia kaolinite  

USGS Publications Warehouse

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.

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



Stereognostic coordination chemistry. 1. The design and synthesis of chelators for the uranyl ion  

SciTech Connect

A new approach to the molecular recognition of metal oxo cations is introduced based on a ligand design strategy that provides at least one hydrogen bond donor for interaction with oxo group(s) as well as conventional electron pair donor ligands for coordination to the metal center. This concept of stereognostic coordination of oxo metal ions is exemplified in the design of four tripodal ligands-tris[2-(2-carboxyphenoxy)ethyl]amine[NEB],tris[3-(2-carboxyphenoxy)propyl]amine[NPB], tris[3-(2-carboxynaphthyl-3-oxy)propyl]amine [NPN], and tris[3-(2-carboxy=4octadecylphenoxy)propyl]amine[NPodB] - for sequestration of the uranyl ion. The ligands NEB, NPB, and NPN form 1:1 complexes with UO{sub 2}{sup 2+}. The bidentate coordination of carboxyl groups of these compounds is indicated by the infrared spectra, which offer some support for the presence of a hydrogen bond to the uranyl group. Mass spectral data corroborate CPK model predictions that more than five intervening atoms between the tertiary nitrogen atom and the carboxylate groups are required for metal ion incorporation and monomeric complex formation. Solvent extractions of aqueous UO{sub 2}{sup 2+} into chloroform solutions of the ligands have shown them to be powerful extractants. In the case of the very hydrophobic ligand NPodB the stoichiometry of the complexation reaction is shown to be 1:1 UO{sub 2}/ligand complex formed by the release of 3 protons. The extraction is quantitative at pH 2.5, and an effective extraction coefficient of about 10{sup 11} is estimated for neutral aqueous solutions of UO{sub 2}{sup 2+}. 81 refs., 13 figs., 2 tabs.

Franczyk, T.S.; Czerwinski, K.R.; Raymond, K.N. [Univ. of Caifornia, Berkeley, CA (United States)



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

SciTech Connect

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).

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



Cation-cation complexes of pentavalent uranyl: from disproportionation intermediates to stable clusters.  


Three new cation-cation complexes of pentavalent uranyl, stable with respect to the disproportionation reaction, have been prepared from the reaction of the precursor [(UO(2)py(5))(KI(2)py(2))](n) (1) with the Schiff base ligands salen(2-), acacen(2-), and salophen(2-) (H(2)salen = N,N'-ethylene-bis(salicylideneimine), H(2)acacen = N,N'-ethylenebis(acetylacetoneimine), H(2)salophen = N,N'-phenylene-bis(salicylideneimine)). The preparation of stable complexes requires a careful choice of counter ions and reaction conditions. Notably the reaction of 1 with salophen(2-) in pyridine leads to immediate disproportionation, but in the presence of [18]crown-6 ([18]C-6) a stable complex forms. The solid-state structure of the four tetranuclear complexes, {[UO(2)(acacen)](4)[?(8)-](2)[K([18]C-6)(py)](2)} (3) and {[UO(2)(acacen)](4)[?(8)-]}?2?[K([222])(py)] (4), {[UO(2)(salophen)](4)[?(8)-K](2)[?(5)-KI](2)[(K([18]C-6)]}?2?[K([18]C-6)(thf)(2)]?2?I (5), and {[UO(2)(salen)(4)][?(8)-Rb](2)[Rb([18]C-6)](2)} (9) ([222] = [222]cryptand, py = pyridine), presenting a T-shaped cation-cation interaction has been determined by X-ray crystallographic studies. NMR spectroscopic and UV/Vis studies show that the tetranuclear structure is maintained in pyridine solution for the salen and acacen complexes. Stable mononuclear complexes of pentavalent uranyl are also obtained by reduction of the hexavalent uranyl Schiff base complexes with cobaltocene in pyridine in the absence of coordinating cations. The reactivity of the complex [U(V)O(2)(salen)(py)][Cp*(2)Co] with different alkali ions demonstrates the crucial effect of coordinating cations on the stability of cation-cation complexes. The nature of the cation plays a key role in the preparation of stable cation-cation complexes. Stable tetranuclear complexes form in the presence of K(+) and Rb(+), whereas Li(+) leads to disproportionation. A new uranyl-oxo cluster was isolated from this reaction. The reaction of [U(V)O(2)(salen)(py)][Cp*(2)Co] (Cp* = pentamethylcyclopentadienyl) with its U(VI) analogue yields the oxo-functionalized dimer [UO(2)(salen)(py)](2)[Cp*(2)Co] (8). The reaction of the {[UO(2)(salen)(4)][?(8)-K](2)[K([18]C-6)](2)} tetramer with protons leads to disproportionation to U(IV) and U(VI) species and H(2)O confirming the crucial role of the proton in the U(V) disproportionation. PMID:21053213

Mougel, Victor; Horeglad, Pawel; Nocton, Grégory; Pécaut, Jacques; Mazzanti, Marinella



Experimental and theoretical approaches to redox innocence of ligands in uranyl complexes: what is formal oxidation state of uranium in reductant of uranyl(VI)?  


Redox behavior of [UO2(gha)DMSO](-)/UO2(gha)DMSO couple (gha = glyoxal bis(2-hydroxanil)ate, DMSO = dimethyl sulfoxide) in DMSO solution was investigated by cyclic voltammetry and UV-vis-NIR spectroelectrochemical technique, as well as density functional theory (DFT) calculations. [UO2(gha)DMSO](-) was found to be formed via one-electron reduction of UO2(gha)DMSO without any successive reactions. The observed absorption spectrum of [UO2(gha)DMSO](-), however, has clearly different characteristics from those of uranyl(V) complexes reported so far. Detailed analysis of molecular orbitals and spin density of the redox couple showed that the gha(2-) ligand in UO2(gha)DMSO is reduced to gha(•3-) to give [UO2(gha)DMSO](-) and the formal oxidation state of U remains unchanged from +6. In contrast, the additional DFT calculations confirmed that the redox reaction certainly occurs at the U center in other uranyl(V/VI) redox couples we found previously. The noninnocence of the Schiff base ligand in the [UO2(gha)DMSO](-)/UO2(gha)DMSO redox couple is due to the lower energy level of LUMO in this ligand relative to those of U 5f orbitals. This is the first example of the noninnocent ligand system in the coordination chemistry of uranyl(VI). PMID:24848497

Takao, Koichiro; Tsushima, Satoru; Ogura, Toshinari; Tsubomura, Taro; Ikeda, Yasuhisa



Complex formation between uranyl and various thiosemicarbazide derivatives  

SciTech Connect

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.

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




Microsoft Academic Search

Modification of polymers, such as polyacrolein, which possess complexing ; groups makes it possible to prepare compounds able to react selectively with ; inorganic salts. Experiments carried out under static conditions on the ; formation of coordination complexes with uranyl nitrate showed that the amount of ; U extracted with pH values ranging from 3 to 4 varies greatly: the

I. V. Andreeva; P. F. Andreev; E. M. Rogozina



Complexation of the Carbonate, Nitrate, and Acetate Anions with the Uranyl Dication: Density Functional Studies with Relativistic Effective Core Potentials  

SciTech Connect

The structures and vibrational frequencies of uranyl carbonates, [UO?(CO?)n](?- ??) and [(UO?)?(CO?)?]??, uranyl nitrates, [UO? (NO?)n](?-?), and uranyl acetates, [UO?(CH?COO)n](?-?) (n = 1,2,3) have been calculated by using local density functional theory (LDFT). Only bidentate ligand coordination modes to the uranyl dication have been modeled. The calculated structures and frequencies are compared to available experimental data, including IR, Raman, X-ray diffraction, and EXAFS solution and crystal structure data. The energetics of ligand binding have been calculated using the B3LYP hybrid functional. In general, the structural and vibrational results at the LDFT level are in good agreement with experimental results and provide realistic pictures of solution phase and solid state behavior. For the [UO? (CO?)?]?? anion, calculations suggest that complexity in the CO??? stretching signature upon complexation is due to the formation of C=O and C-O domains, the latter of which can split by as much as 300 cm??. Assessment of the binding energies indicate that the [UO? (CO?)?]?? anion is more stable than the [UO?(CO?)?]?? anion due to the accumulation of excess charge, whereas the tri-ligand species are the most stable in the nitrate and acetate anions.

De Jong, Wibe A.; Apra, Edoardo; Windus, Theresa L.; Nichols, Jeffrey A.; Harrison, Robert J.; Gutowski, Keith E.; Dixon, David A.



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

SciTech Connect

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.

Park, Sang-Won; Leckie, J.O. [Stanford Univ., CA (United States)] [Stanford Univ., CA (United States); Siegel, M.D. [Sandia National Labs., Albuquerque, NM (United States)] [Sandia National Labs., Albuquerque, NM (United States)



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

SciTech Connect

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.

Szigethy, Geza; Raymond, Kenneth



Investigation of Uranyl Nitrate Ion Pairs Complexed with Amide Ligands using Electrospray Ionization Ion Trap Mass Spectrometry and Density Functional Theory  

SciTech Connect

Ion populations formed from electrospray of uranyl nitrate solutions containing different amides vary depending on ligand nucleophilicity and steric crowding at the metal center. The most abundant species were ion pair complexes having the general formula [UO2(NO3)(amide)n=2,3]+, and complexes containing the amide conjugate base, reduced uranyl UO2+, and a 2+ charge were also formed. The formamide experiment produced the greatest diversity of species that stems from weaker amide binding leading to dissociation and subsequent solvent coordination or metal reduction. Experiments using methyl formamide, dimethyl formamide, acetamide, and methyl acetamide produced ion pair and doubly charged complexes that were more abundant, and less abundant complexes containing solvent or reduced uranyl. This pattern is reversed in the dimethylacetamide experiment, which displayed reduced doubly charged complexes and augmented reduced uranyl complexes. DFT investigations of the tris-amide ion pair complexes showed that inter-ligand repulsion distorts the amide ligands out of the uranyl equatorial plane, and that complex stabilities do not increase with increasing amide nucleophilicity. Elimination of an amide ligand largely relieves the interligand repulsion, and the remaining amide ligands become closely aligned with the equatorial plane in the structures of the bis-amide ligands. The studies show that the phenomenological distribution of coordination complexes in a metal-ligand electrospray experiment is a function of both ligand nucleophilicity and interligand repulsion, and that the latter factor begins exerting influence even in the case of relatively small ligands like the substituted methyl-formamide and –acetamide ligands.

Gary S. Groenewold; Adriana Dinescu; Michael T. Benson; Garold L. Gresham; Michael J. van Stipdonk



Synthesis, structure, and bonding of stable complexes of pentavalent uranyl.  


Stable complexes of pentavalent uranyl [UO(2)(salan-(t)Bu(2))(py)K](n) (3), [UO(2)(salan-(t)Bu(2))(py)K(18C6)] (4), and [UO(2)(salophen-(t)Bu(2))(thf)]K(thf)(2)}(n) (8) have been synthesized from the reaction of the complex {[UO(2)py(5)][KI(2)py(2)]}(n) (1) with the bulky amine-phenolate ligand potassium salt K(2)(salan-(t)Bu(2)) or the Schiff base ligand potassium salt K(2)(salophen-(t)Bu(2)) in pyridine. They were characterized by NMR, IR, elemental analysis, single crystal X-ray diffraction, UV-vis spectroscopy, cyclic voltammetry, low-temperature EPR, and variable-temperature magnetic susceptibility. X-ray diffraction shows that 3 and 8 are polymeric and 4 is monomeric. Crystals of the monomeric complex [U(V)O(2)(salan-(t)Bu(2))(py)][Cp*(2)Co], 6, were also isolated from the reduction of [U(VI)O(2)(salan-(t)Bu(2))(py)], 5, with Cp*(2)Co. Addition of crown ether to 1 afforded the highly soluble pyridine stable species [UO(2)py(5)] (2). The measured redox potentials E(1/2) (U(VI)/U(V)) are significantly different for 2 (-0.91 and -0.46 V) in comparison with 3, 4, 5, 7 and 9 (in the range -1.65 to -1.82 V). Temperature-dependent magnetic susceptibility data are reported for 4 and 7 and give mu(eff) of 2.20 and 2.23 mu(B) at 300 K respectively, which is compared with a mu(eff) of 2.6(1) mu(B) (300 K) for 2. Complexes 1 and 2 are EPR silent (4 K) while a rhombic EPR signal (g(x) = 1.98; g(y) = 1.25; g(z) = 0.74 (at 4 K) was measured for 4. The magnetic and the EPR data can be qualitatively analyzed with a simple crystal field model where the f electron has a nonbonding character. However, the temperature dependence of the magnetic susceptibility data suggests that one or more excited states are relatively low-lying. DFT studies show unambiguously the presence of a significant covalent contribution to the metal-ligand interaction in these complexes leading to a significant lowering of the pi(u)*. The presence of a back-bonding interaction is likely to play a role in the observed solution stability of the [UO(2)(salan-(t)Bu(2))(py)K] and [UO(2)(salophen-(t)Bu(2))(py)K] complexes with respect to disproportionation and hydrolysis. PMID:20000767

Nocton, Grégory; Horeglad, Pawel; Vetere, Valentina; Pécaut, Jacques; Dubois, Lionel; Maldivi, Pascale; Edelstein, Norman M; Mazzanti, Marinella



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

SciTech Connect

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.

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



Density functional theory study of the complexation of the uranyl dication with anionic phosphate ligands with and without water molecules.  


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. PMID:23905705

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



Syntheses and crystal structures of two novel alkaline uranyl chromates A2(UO2)(CrO4)2 (A=Rb, Cs) with bidentate coordination mode of uranyl ions by chromate anions  

NASA Astrophysics Data System (ADS)

Single crystals of Cs2(UO2)(CrO4)2 and Rb2(UO2)(CrO4)2 were prepared by solid state reactions. The structures are based upon the [(UO2)(CrO4)2]2- chains. Within the chains, UrO5 pentagonal bipyramids (Ur=uranyl) form Ur2O8 dimers, which are linked via CrO4 tetrahedra into one-dimensional chains. The CrO4 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+ and Rb+ cations.

Siidra, Oleg I.; Nazarchuk, Evgeny V.; Krivovichev, Sergey V.



Electronic structure of complex compounds of uranyl with consideration of the inner orbitals of the uranium atom  

SciTech Connect

The electronic structure and spectra of halo, nitrato, and acetato complexes of uranyl have been calculated by a semiempirical MO method. The valence basis was expanded by taking into account the inner 6p orbitals of the U atom. An analysis of the populations on the atoms was carried out. According to the calculated data, the structure of the uranyl grouping in all the complexes considered remains practically the same, accounting for the similarity in the structure of the electronic absorption and fluorescence spectra of uranyl compounds.

Borkovskii, N.B.; Kovrikov, A.B.; Umreiko, D.S.



Trace level uranyl complexation with phenylphosphonic acid in aqueous solution: direct speciation by high resolution mass spectrometry.  


The complexation of U(VI) by organic P-containing ligands in humic substances (HS) is an important issue of uranyl mobility in soil. We have investigated the complexation of uranyl by a model ligand for aromatic phosphorus functionalities in HS, phenylphosphonic acid, by using ultrahigh resolution electrospray ionization-mass spectrometry (ESI-MS). The high sensitivity permitted to investigate the complexation of trace level uranyl and to explore directly in the native aqueous solutions the nature of the uranyl-phenylphosphonate complexes. Positive identification of the complexes coexisting in solutions with low pH and varying ligand-to-metal ratio was achieved thanks to the high resolving power, high mass accuracy, and reliability of ion abundance of the technique. The positively charged and neutral uranyl species were detected simultaneously on negative ion mass spectra, evidencing formation of three types of U(VI)-phenylphosphonate complexes. Two complexes with a metal-to-ligand stoichiometry of 1:1 (in the monoprotonated and nonprotonated forms) existed in solutions at pH 3-5, and a 1:2 complex was additionally formed at relatively high ligand-to-metal ratio. A strategy based on the use of uranyl-phosphate solution complexes as internal standards was developed to determine from the ESI(-)MS results the stability constants of the complexes, which were calculated to be log K111 = 3.4 ± 0.2 for UO2(HPhPO3)(+), log K101 = 7.1 ± 0.1 for UO2PhPO3, and log K112 = 7.2 ± 0.2 for UO2(HPhPO3)2. The speciation model presented here suggests that organic P existing at low concentration in HS is involved significantly in binding by humic and fulvic acids of trace level uranyl in soil. PMID:23527599

Galindo, Catherine; Del Nero, Mirella



Coordination Complexes of Cobalt.  

ERIC Educational Resources Information Center

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…

Williams, Gregory M.; And Others



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

SciTech Connect

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.

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



Composition for detecting uranyl  


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.

Baylor, Lewis C. (North Augusta, SC); Stephens, Susan M. (Athens, GA)



The Synthesis, Characterization, Spectroscopic Studies and Catalyst Properties of Some New Dinuclear Uranyl (VI) Metal Complexes Bearing Different vic?Dioxime Groups  

Microsoft Academic Search

The synthesis, characterization and spectroscopic studies of some new dinuclear uranyl (VI) metal complexes prepared from different vic?dioximes ligands and the uranyl acetate metal salt. The structure of these uranyl (VI) metal complexes have been determined as according to elemental analysis, H?NMR spectra, FT?IR spectra, UV?Vis spectra, magnetic susceptibility measurements, melting point and molar conductivity measurements. The metal to ligand

A. Kilic; E. Tas



D.C. electrical conductivity and conduction mechanism of some azo sulfonyl quinoline ligands and uranyl complexes.  


Supramolecular coordination of dioxouranium(VI) heterochelates 5-sulphono-7-(4'-X phenylazo)-8-hydroxyquinoline HL(n) (n=1, X=CH(3); n=2, X=H; n=3, X=Cl; n=4, X=NO(2)) have been prepared and characterized with various physico-chemical techniques. The infrared spectral studies showed a monobasic bidentate behavior with the oxygen and azonitrogen donor system. The temperature dependence of the D.C. electrical conductivity of HL(n) ligands and their uranyl complexes has been studied in the temperature range 305-415 K. The thermal activation energies E(a) for HL(n) compounds were found to be in the range 0.44-0.9 eV depending on the nature of the substituent X. The complexation process decreased E(a) values to the range 0.043-045 eV. The electrical conduction mechanism has been investigated for all samples under investigation. It was found to obey the variable range hopping mechanism (VRH). PMID:21906992

El-Ghamaz, N A; Diab, M A; El-Sonbati, A Z; Salem, O L



Uranium(VI) sulfilimine complexes: a new class of nitrogen analogues of the uranyl ion.  


The compound tetraphenylphosphonium tetrachlorooxo-S,S-diphenylsulfiliminatouranium, [Ph4P][UOCl4(NSPh2)], has been prepared in high yield from [Ph4P][UOCl5] and [Ph2S=NSiMe3]. An X-ray structure of this compound shows that the uranium atom has a pseudooctahedral geometry with oxygen and nitrogen atoms in trans positions. The structure of the analogous phosphoriminato complex [Ph4P][UOCl4(NPPh3)] has been determined for comparison. Derivatization of the sulfide group shows that only a limited range of functionalization confers stability toward reduction. The emission spectrum of the first electronic excited state reveals a greatly reduced energy compared with that of the uranyl ion. This red shift in the transition is consistent with the weakening of the U-N bond relative to the U-O bond. PMID:11197007

Williams, V C; Müller, M; Leech, M A; Denning, R G; Green, M L



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


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

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



Scale-dependent rates of uranyl surface complexation reaction in sediments  

NASA Astrophysics Data System (ADS)

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 show that the grain-scale rate constant of U(VI) surface complexation was over 3-10 orders of magnitude smaller than the rate constant calculated using the molecular simulations. 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 that the rate of coupled diffusion and molecular surface complexation reaction in the intragranular porous domains was slower than either individual process alone. The results provide important implications for developing models to scale geochemical/biogeochemical reactions.

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



Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models  

USGS Publications Warehouse

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ???7-8 (I = 0.1 M NaNO3 solution, suspension density = 0.4 g/L [U(VI)]i = 0.01-30 ??M, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and ?? charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in controlling U(VI) mobility in low-temperature geochemical environments over a wide pH range (???5-9), even at the partial pressure of carbon dioxide of ambient air (pCO2 = 10-3.45 atm). ?? 2006 Elsevier Inc. All rights reserved.

Arai, Y.; McBeath, M.; Bargar, J. R.; Joye, J.; Davis, J. A.



Scale-Dependent Rates of Uranyl Surface Complexation Reaction in Sediments  

SciTech Connect

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.

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



Critical Parameters of Complex Geometry Intersecting Cylinders Containing Uranyl Nitrate Solution  

SciTech Connect

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.

Rothe, Robert Emil; Briggs, Joseph Blair



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

SciTech Connect

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.

J. B. Briggs (INEEL POC); R. E. Rothe



Structural/electronic properties and reaction energies of a series of mono- and bis-uranyl dihalides equatorially coordinated by N/O ligands.  


Monometallic (UO2)(X)2(L)3 (L?=?pyridine (py), X?=?F (1), Cl (2), Br (3) and I (4); L?=?tetrahydrofuran (thf), X?=?Cl (5); L?=?pyrrole (pl), X?=?Cl (6)) as well as bimetallic [(UO2)(?2-X)(X)(L)2]2 (L?=?py, X?=?F (7), Cl (8), Br (9) and I (10); L?=?thf, X?=?Cl (11); L?=?pl, X?=?Cl (12); ? 2?=?doubly bridged) were examined using relativistic density functional theory. With changing from F, Cl, Br to I irregardless of in mono- or bis-uranyl complexes, bond lengths of U?=?O were calculated to be decreasing, resulting from strengthening of axial U?=?O bonds while weakening equatorial X???U coordination. This is further evidenced by calculated bond orders of U?=?O and stretching vibrational frequencies. A similar situation was is found in 2, 5 and 6 as well as in 8, 11 and 12, where N/O ligands are varied but the chlorine atoms are retained. The present study reveals that all these complexes have U(f)-character low-lying unoccupied orbitals, and their ?*(U?=?O) antibonds are located on higher-energy orbitals. Complex 1 was calculated to show ?(U?=?O) bonding character for HOMO, and pyridine-character for other occupied orbitals; the fluorine ligand occurs in a relatively low-energy region. In contrast, the ?(p) characters of heavier halogen atoms significantly contribute to most frontier molecular orbitals of 2, 3 and 4. Unlike this electronic feature of 2, complexes 5 and 6 exhibit mainly thf and pyrrole characters, respectively, for their high-lying occupied orbitals. Electronic structures of bisuranyl complexes 7-12, albeit a little more complicated, are revealed to be similar to those of the corresponding monouranyl complexes. Finally, energies of formation reactions of the above complexes were calculated and compared with available experimental results. PMID:24869781

Yao, Jun; Wang, Yong-Ming; Pan, Qing-Jiang; Guo, Yuan-Ru; Zhang, Hong-Xing



Uncertainty Analysis and Extrapolation of Additive Uranyl Surface Complexation Kinetic Models  

NASA Astrophysics Data System (ADS)

Tremendous progress has been made in the last few years in using Multi-rate Skinetic surface Complex complexation Reactionreaction (SCR) models for the analysis and predicting prediction of uranyl (U(VI) )adsorption/desorption in sediments. However, such analysis and prediction s with the model are often deterministic, and as such they focusing only on the most probable forecastscenario, without considering various model uncertaintiesan explicit estimate of the associated uncertainty. In this presentationstudy, thewe will describe a generalized likelihood uncertainty estimation method framework was adopted in the Differential Evolution Markov Chain Monte Caro framework to explore the explicit consider model structure and parameter uncertaintiesy in the U(VI) SCR models and their effects on the model extrapolation. Both sStirred-flow cell and column experiments were conducted carried out to investigate derive experimental data of U(VI) sorption/desorption for model application and uncertainty analysis.uranium release from different size fractions of sediments from US DOE Hanford site. The U(VI)-contaminated sediment used in the experiments was collected from US DOE Hanford site, and was air-dried and dry-sieved to four size fractions (<75 ?m, 75-500?m, 500-2000 ?m and 2000-8000?m) to investigate desorption kinetics. The experimental results were used to parameterize SCR kinetic models and to determine model structure and parameter uncertainties for individual size fractions. The individual size fraction models were then used to evaluate the predictivity of the size-additivity model and to analyze the extrapolation of both parameter and model structure uncertainties. The results demonstrated that model uncertainty, especially model structure uncertainty, is an important factor to be considered in model prediction and evalution of the applicability of the extrapolated models.

Zhang, X.; Liu, C.; Hu, Q.; Hu, X. B.



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

SciTech Connect

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.

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



Uranium complexation and uptake by a green alga in relation to chemical speciation: the importance of the free uranyl ion.  


The bioavailability and toxicity of dissolved metals are closely linked to the metals' chemical speciation in solution. Normally the complexation of a metal by a ligand would be expected to decrease its bioavailability. The aqueous speciation of uranium (U) undergoes tremendous changes in the presence of ligands commonly found in natural waters (carbonate, phosphate, hydroxide, and natural organic matter). In the present project, links between speciation, medium composition, and bioavailability of uranium toward Chlamydomonas reinhardtii, a unicellular green alga, were investigated. Short-term metal uptake rates were determined in simple inorganic media at constant low pH (5.0) and hardness with particular emphasis on the differentiation between adsorbed and intracellular metal. While intracellular uptake was fairly linear over 1 h, partly reversible adsorption reached steady-state within minutes. Both adsorption and absorption were saturable processes (with a half-saturation constant Km of 0.51 microM). Addition of phosphate, citrate, or ethylenediaminetetraacetic acid (EDTA) as ligands decreased uranium bioavailability. No evidence indicating the transport of intact uranyl complexes was found (i.e., facilitated diffusion of metal bound to an assimilable ligand such as uranium-phosphate complexes). Within these experimental conditions, uranium uptake was correlated with the free uranyl ion concentration as predicted by the free-ion activity model (FIAM) and biotic ligand model (BLM). PMID:15095894

Fortin, Claude; Dutel, Laurent; Garnier-Laplace, Jacqueline



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


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

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



Complexation of the uranyl ion with the aminomethylenediphosphonates MAMDP and AMDP  

Microsoft Academic Search

The use of uranium as a nuclear energy source has made it a valuable mineral resource over the past forty years. Processing uranium generally involves leaching the metal as the uranyl ion (UOâ){sup 2+} from ore, followed by solvent extraction, precipitation or batch adsorption onto ion exchange-type resins. Uranium reserves exist also in the form of UOâ(COâ)â⁴⁻ dissolved in seawater,

James E. Bollinger; D. Max Roundhill



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

SciTech Connect

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.

Wang, L.; Yang, Z.; Gao, J.; Xu, K.; Gu, H.; Xu, B. [Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong (China); Zhang, B.; Zhang, X. [Department of Physics, Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong (China)



Coordination Chemistry Reviews 250 (2006) 30683080 Anion recognition using dimetallic coordination complexes  

E-print Network

Coordination Chemistry Reviews 250 (2006) 3068­3080 Review Anion recognition using dimetallic coordination complexes Edward J. O'Neil, Bradley D. Smith Department of Chemistry and Biochemistry, University . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3068 2. Dimetallic coordination complexes

Smith, Bradley D.



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...


Relativistic theoretical studies on hydrogen bonds and the electronic structure of aqueous solvated bis(uranyl) complex: an insight into explicit and/or implicit solvent effects.  


To understand the chemical behavior of uranyl complexes in water, a bis-uranyl [(phen)(UO2)(?2-F)(F)]2 (A; phen?=?phenanthroline, ?2?=?doubly bridged) and its hydrated form A·(H2O)n (n?=?2, 4 and 6) were examined using scalar relativistic density functional theory. The addition of water caused the phen ligands to deviate slightly from the U2(?2-F)2 plane, and red-shifts the U-F-terminal and U?=?O stretching vibrations. Four types of hydrogen bonds are present in the optimized hydrated A·(H2O)n complexes; their energies were calculated to fall within the range 4.37-6.77 kcal mol(-1), comparable to the typical values of 5.0 kcal mol(-1) reported for hydrogen bonds. An aqueous environment simulated by explicit and/or implicit models lowers and re-arranges the orbitals of the bis-uranyl complex. PMID:23666033

Guo, Yuan-Ru; Zhou, Xin; Pan, Qing-Jiang



Coordinating Tectons: Bipyridyl Terminated Allenylidene Complexes  

SciTech Connect

A series of complexes with {pi}-conjugated carbon chains terminated by bipyridyl moieties has been prepared. These allenylidene complexes were derived from 9-hydroxy-9-ethynyl-4,5-diazafluorene, the preparation of which is reported; the new allenylidene complexes are highly colored with the cumulated carbon chain terminating in a bipyridyl unit providing a site for further coordination. The synthesis, characterization, and X-ray structure determination of trans-[MCl(P{intersection}P){sub 2}{sub {double_bond}}C{sub {double_bond}}C{sub {double_bond}}(4,5-diazafluoren-9-yl)]PF{sub 6} (M = Ru, P{intersection}P = bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,2-bis(dimethylphosphino)ethane (dmpe); M = Os, P{intersection}P = dppm) are described. The effect of the variation in metal and ligand on electronic and electrochemical characteristics of these complexes has been investigated by using UV-vis, solution electrochemistry, and a combination of these techniques in spectroelectrochemical experiments. DFT calculations have been performed on trans-[RuCl(P{intersection}P){sub 2}{sub {double_bond}}C{sub {double_bond}}C{sub {double_bond}}(4,5-diazafluoren-9-yl)]{sup q} (P{intersection}P = dppm, bis(dimethylphosphino)methane (dmpm); q = -1, 0, +1, +2) and subsequently solvent-corrected calculations with use of COSMO were also undertaken to examine the nature of electronic transitions in various oxidation states.

Cifuentes, Marie P.; Humphrey, Mark G.; Koutsantonis, George A.; Lengkeek, Nigel A.; Petrie, Simon; Sanford, Vanessa; Schauer, Phil A.; Skelton, Brian W.; Stranger, Robert; White, Allan H. (UWA); (ANU)



2-Electron 3-Atom Bond in Side-on (n2) Uranyl (V) Superoxo Complexes  

SciTech Connect

Theoretical calculations suggest a novel two-electron three-atom bonding scheme for complexation of O2 with U(V) compounds, leading to the stabilization of superoxo complexes in the side-on (?2) configuration. This binding motif is likely to play an important role in the oxidative processes involving trans-uranium compounds having valence 5ff electrons.

V. S. Bryantsev; W. A. de Jong; K. C. Cossel; M. S. Diallo; W. A. Goddard III; G. S. Groenewold; W. Chien; M. J. Stipdonk




SciTech Connect

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,

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



Development and Application of an Assay for Uranyl Complexation by Fungal Metabolites, Including Siderophores  

PubMed Central

An assay to detect UO22+ 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-Fe3+ dye and the other containing a CAS-UO22+ 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-UO22+ agar to the discoloration on the CAS-Fe3+ 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 UO22+ 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 UO22+ chelating ligands. We suggest that hydroxamate siderophores can be produced by mucoraceous fungi. PMID:12788768

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



Uranyl peroxide oxalate cage and core-shell clusters containing 50 and 120 uranyl ions.  


Cage clusters built from uranyl hexagonal bipyramids and oxalate ligands crystallize from slightly acidic aqueous solution under ambient conditions, facilitating structure analysis. Each cluster contains uranyl ions coordinated by peroxo ligands in a bidentate configuration. Uranyl ions are bridged by shared peroxo ligands, oxalate ligands, or through hydroxyl groups. U(50)Ox(20) contains 50 uranyl ions and 20 oxalate groups and is a topological derivative of the U(50) cage cluster that has a fullerene topology. U(120)Ox(90) contains 120 uranyl ions and 90 oxalate groups and is the largest and highest mass cluster containing uranyl ions that has been reported. It has a core-shell structure, in which the inner shell (core) consists of a cluster of 60 uranyl ions and 30 oxalate groups, identical to U(60)Ox(30), with a fullerene topology. The outer shell contains 12 identical units that each consist of five uranyl hexagonal bipyramids that are linked to form a ring (topological pentagon), with each uranyl ion also coordinated by a side-on nonbridging oxalate group. The five-membered rings of the inner and outer shells (the topological pentagons) are in correspondence and are linked through K cations. The inner shell topology has therefore templated the location of the outer shell rings, and the K counterions assume a structure-directing role. Small-angle X-ray scattering data demonstrated U(50)Ox(20) remains intact in aqueous solution upon dissolution. In the case of clusters of U(120)Ox(90), the scattering data for dissolved crystals indicates the U(60)Ox(30) core persists in solution, although the outer rings of uranyl bipyramids contained in the U(120)Ox(90) core-shell cluster appear to detach from the cluster when crystals are dissolved in water. PMID:22296269

Ling, Jie; Qiu, Jie; Burns, Peter C



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

SciTech Connect

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{sub 2}{sup 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{sub d} values decrease from 48 to 17 L kg{sup -1} for goethite, from 64 to 29 L kg{sup -1} for Hanford sediments, and from 95 to 51 L kg{sup -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 ({approx}5) and limited dissolved calcium are optimal for uranium adsorption.

Stewart, B.D. [Stanford University; Mayes, Melanie [ORNL; Fendorf, Scott [ORNL



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

PubMed Central

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

Odorico, Michael; Teulon, Jean-Marie; Bessou, Therese; Vidaud, Claude; Bellanger, Laurent; Chen, Shu-wen W.; Quemeneur, Eric; Parot, Pierre; Pellequer, Jean-Luc



Electronic Structure and Reactivity of Three-Coordinate Iron Complexes  

PubMed Central

Conspectus The identity and oxidation state of the metal in a coordination compound are typically thought to be the most important determinants of its reactivity. However, the coordination number (the number of bonds to the metal) can be equally influential. This Account describes iron complexes with a coordination number of only three, which differ greatly from iron complexes with octahedral (six-coordinate) geometries with respect to their magnetism, electronic structure, preference for ligands, and reactivity. Three-coordinate complexes with a trigonal-planar geometry are accessible using bulky, anionic, bidentate ligands (?-diketiminates) that steer a monodentate ligand into the plane of their two nitrogen donors. This strategy has led to a variety of three-coordinate iron complexes in which iron is in the +1, +2, and +3 oxidation states. Systematic studies on the electronic structures of these complexes have been useful in interpreting their properties. The iron ions are generally high spin, with singly occupied orbitals available for ? interactions with ligands. Trends in ?-bonding show that iron(II) complexes favor electronegative ligands (O, N donors) over electropositive ligands (hydride). The combination of electrostatic ?-bonding and the availability of ?-interactions stabilizes iron(II) fluoride and oxo complexes. The same factors destabilize iron(II) hydride complexes, which are reactive enough to add the hydrogen atom to unsaturated organic molecules and to take part in radical reactions. Iron(I) complexes use strong ?-backbonding to transfer charge from iron into coordinated alkynes and N2, whereas iron(III) accepts charge from a ?-donating imido ligand. Though the imidoiron(III) complex is stabilized by ?-bonding in the trigonal-planar geometry, addition of pyridine as a fourth donor weakens the ?-bonding, which enables abstraction of H atoms from hydrocarbons. The unusual bonding and reactivity patterns of three-coordinate iron compounds may lead to new catalysts for oxidation and reduction reactions, and may be used by nature in transient intermediates of nitrogenase enzymes. PMID:18646779

Holland, Patrick L.



Polythiophene coordination complexes as high performance lithium storage materials  

NASA Astrophysics Data System (ADS)

Polythiophene (PTh)-based coordination complexes, polythiophene-iron (PTh-Fe) and polythiophene-iron-oxygen (PTh-Fe-O) were synthesized by chemical method and proved to be novel high-performance organometallic lithium-storage materials. Extended X-ray absorption ?ne structural (EXAFS) spectroscopy and density functional theory (DFT) calculations indicate that these complexes have layered structures. It is believed that the strong and stable Fe-S coordination creates sites of lithium storage and ensures the high specific capacity and outstanding cycle performance of the PTh-based complexes.

Mao, Ya; Kong, Qingyu; Shen, Lian; Wang, Zhaoxiang; Chen, Liquan



Colloidal nanocrystals fluoresced by surface coordination complexes.  


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

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



Probing the electronic structure and chemical bonding in tricoordinate uranyl complexes UO2X3- (X = F, Cl, Br, I): competition between Coulomb repulsion and U-X bonding.  


While uranyl halide complexes [UO2(halogen)n](2-n) (n = 1, 2, 4) are ubiquitous, the tricoordinate species have been relatively unknown until very recently. Here photoelectron spectroscopy and relativistic quantum chemistry are used to investigate the bonding and stability of a series of gaseous tricoordinate uranyl complexes, UO2X3(-) (X = F, Cl, Br, I). Isolated UO2X3(-) ions are produced by electrospray ionization and observed to be highly stable with very large adiabatic electron detachment energies: 6.25, 6.64, 6.27, and 5.60 eV for X = F, Cl, Br, and I, respectively. Theoretical calculations reveal that the frontier molecular orbitals are mainly of uranyl U-O bonding character in UO2F3(-), but they are from the ligand valence np lone pairs in the heavier halogen complexes. Extensive bonding analyses are carried out for UO2X3(-) as well as for the doubly charged tetracoordinate complexes (UO2X4(2-)), showing that the U-X bonds are dominated by ionic interactions with weak covalency. The U-X bond strength decreases down the periodic table from F to I. Coulomb barriers and dissociation energies of UO2X4(2-) ? UO2X3(-) + X(-) are calculated, revealing that all gaseous dianions are in fact metastable. The dielectric constant of the environment is shown to be the key in controlling the thermodynamic and kinetic stabilities of the tetracoordinate uranyl complexes via modulation of the ligand-ligand Coulomb repulsions. PMID:23662677

Su, Jing; Dau, Phuong Diem; Qiu, Yi-Heng; Liu, Hong-Tao; Xu, Chao-Fei; Huang, Dao-Ling; Wang, Lai-Sheng; Li, Jun



Giant regular polyhedra from calixarene carboxylates and uranyl  

PubMed Central

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

Pasquale, Sara; Sattin, Sara; Escudero-Adan, Eduardo C.; Martinez-Belmonte, Marta; de Mendoza, Javier



Charge transfer vibronic transitions in uranyl tetrachloride compounds;  

SciTech Connect

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.

Liu, G. K.; Deifel, N. P.; Cahill, C. L. (Chemical Sciences and Engineering Division); (George Washington University)



Special Features of the Correlation between the Uranium–Oxygen Interatomic Distances and the Frequencies of the Valence Vibrations of the UO 2 2+ Group in Complex Compounds of Uranyl  

Microsoft Academic Search

We considered the factors due to which the dependences between the uranium–oxygen distances R0 and the frequencies of valence vibrations ?as for complex compounds of uranyl are described by two independent expressions generally represented by equations of the type R0 = a + b?as-2\\/3 (b > 0) with the coefficients a and b differing in the regions R0 R0 >

V. V. Syt'ko; E. N. Kabaeva



Chiral lanthanide complexes: coordination chemistry, spectroscopy, and catalysis.  


The coordination chemistry and catalytic applications of organometallic and related lanthanide complexes bearing chiral oxazoline ligands is an area that has been largely underdeveloped, in comparison to complexes based upon lanthanide triflates for use in Lewis acid catalysis. In this article we report on the coordination chemistry of the bis(oxazolinylphenyl)amide (BOPA) ligand with lanthanide alkyl and amide co-ligands (Ln = Y, La, Pr, Nd, Sm). Their structural and spectroscopic characterisation are reported, including an assessment of their photophysical properties using luminescence spectroscopy, and are supported by density functional calculations. The application of these complexes in the hydroamination/cyclisation of aminoalkenes, and in the ring-opening polymerisation of rac-lactide is reported. PMID:24577185

Bennett, Stacey D; Core, Bryony A; Blake, Matthew P; Pope, Simon J A; Mountford, Philip; Ward, Benjamin D



Coordinating complex problem-solving among distributed intelligent agents  

NASA Technical Reports Server (NTRS)

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.

Adler, Richard M.



Six-coordinate nitrito and nitrato complexes of manganese porphyrin.  


Reaction of small increments of NO2 gas with sublimed amorphous layers of Mn(II)(TPP) (TPP = meso-tetra-phenylporphyrinato dianion) in a vacuum cryostat leads to formation of the 5-coordinate monodentate nitrato complex Mn(III)(TPP)(?(1)-ONO2) (II). This transformation proceeds through the two distinct steps with initial formation of the five coordinate O-nitrito complex Mn(III)(TPP)(?(1)-ONO) (I) as demonstrated by the electronic absorption spectra and by FTIR spectra using differently labeled nitrogen dioxide. A plausible mechanism for the second stage of reaction is offered based on the spectral changes observed upon subsequent interaction of (15)NO2 and NO2 with the layered Mn(TPP). Low-temperature interaction of I and II with the vapors of various ligands L (L = O-, S-, and N-donors) leads to formation of the 6-coordinate O-nitrito Mn(III)(TPP)(L)(?(1)-ONO) and monodentate nitrato Mn(III)(TPP)(L)(?(1)-ONO2) complexes, respectively. Formation of the 6-coordinate O-nitrito complex is accompanied by the shifts of the ?(N?O) band to lower frequency and of the ?(N-O) band to higher frequency. The frequency difference between these bands ?? = ?(N?O) - ?(N-O) is a function of L and is smaller for the stronger bases. Reaction of excess NH3 with I leads to formation of Mn(TPP)(NH3)(?(1)-ONO) and of the cation [Mn(TPP)(NH3)2](+) plus ionic nitrite. The nitrito complexes are relatively unstable, but several of the nitrato species can be observed in the solid state at room temperature. For example, the tetrahydrofuran complex Mn(TPP)(THF)(?(1)-ONO2) is stable in the presence of THF vapors (?5 mm), but it loses this ligand upon high vacuum pumping at RT. When L = dimethylsulfide (DMS), the nitrato complex is stable only to ?-30 °C. Reactions of II with the N-donor ligands NH3, pyridine, or 1-methylimidazole are more complex. With these ligands, the nitrato complexes Mn(III)(TPP)(L)(?(1)-ONO2) and the cationic complexes [Mn(TPP)(L)2](+) coexist in the layer at room temperature, the latter formed as a result of NO3(-) displacement when L is in excess. PMID:25369232

Kurtikyan, T S; Hayrapetyan, V A; Mehrabyan, M M; Ford, P C



Energetic lanthanide complexes: coordination chemistry and explosives applications  

NASA Astrophysics Data System (ADS)

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.

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



Formic acid interaction with the uranyl(VI) ion: structural and photochemical characterization.  


Complex formation between the uranyl(VI) ion and formic acid was studied by infrared absorption (IR) and X-ray absorption (EXAFS) spectroscopy as well as density functional theory (DFT) calculations. In contrast to the acetate ion which forms exclusively a bidentate complex with uranyl(VI), the formate ion binds to uranyl(VI) in a unidentate fashion. The photochemistry of the uranyl(VI)-formic acid system was explored by DFT calculations and photoreduction of uranyl(VI) in the presence of formic acid was found to occur via an intermolecular process, that is, hydrogen abstraction from hydrogenformate by the photo-excited uranyl(VI). There is no photo-induced decarboxylation of uranyl(VI) formate via an intramolecular process, presumably due to lack of a C=C double bond. PMID:23900668

Lucks, Christian; Rossberg, André; Tsushima, Satoru; Foerstendorf, Harald; Fahmy, Karim; Bernhard, Gert



{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

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.

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



Isocyanide and Phosphine Oxide Coordination in Binuclear Chromium Pacman Complexes  

PubMed Central

The new binuclear chromium Pacman complex [Cr2(L)] of the Schiff base pyrrole macrocycle H4L has been synthesized and structurally characterized. Addition of isocyanide, C?NR (R = xylyl, tBu), or triphenylphosphine oxide donors to [Cr2(L)] gives contrasting chemistry with the formation of the new coordination compounds [Cr2(?-CNR)(L)], in which the isocyanides bridge the two Cr(II) centers, and [Cr2(OPPh3)2(L)], a Cr(II) phosphine oxide adduct with the ligands exogenous to the cleft. PMID:24489428



Nuclear magnetic resonance and calorimetric study of the structure, dynamics, and phase behavior of uranyl ion/dipalmitoylphosphatidylcholine complexes.  

PubMed Central

The interaction of UO2(2+) with dipalmitoylphosphatidylcholine (DPPC) has been studied as a function of temperature and composition using nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry (DSC), and monolayer studies. Computer simulations of the 31P-NMR powder spectra of DPPC dispersions in the presence of various concentrations of UO2(2+) are consistent with the binding stoichiometry of [UO2(2+)]/[DPPC] = 1:4 at [UO2(2+)]/[DPPC] less than 0.3. This complex undergoes a phase transition to the liquid crystalline phase at T'm = 50 +/- 3 degrees C with a breadth delta T'm = 7 +/- 3 degrees C. This broad transition gradually disappears at higher UO2(2+) concentrations, suggesting the presence of yet another UO2(2+)/DPPC complex (or complexes) whose NMR spectra are indistinguishable from those of the 1:4 UO2(2+)/DPPC species. The temperature-dependent 13C powder spectra of 2(1-13C) DPPC dispersions in the presence of 1.2 mol ratio of UO2(2+) show that this higher order complex (complexes) also undergoes a phase transition to the liquid crystalline state at T'm +/- = 58 +/- 3 degrees C with a breadth delta T"m = 15 +/- 5 degrees C. The NMR spectra indicate that exchange among these various UO2(2+)/DPPC complexes is slow. In addition, computer simulations of the 31P-, 13C-, and 2H-NMR powder spectra show that axial diffusion of the DPPC molecules about their long axes is quenched by addition of UO2(2+) and acyl chain isomerization is the dominant motional mode. The isomerization is best described as two-site hopping of the greater than C-D bond at a rate of approximately 10(6) s-1, a motional mode which is expected for a kink diffusion. PMID:3416028

Huang, T H; Blume, A; Das Gupta, S K; Griffin, R G



Investigation of the interaction between organic compounds and uranyl ions by raman spectroscopy  

NASA Astrophysics Data System (ADS)

Raman spectra of uranyl oxalate, salinate, salicylate, terephthalate and humate have been measured. The O=U=O symmetric stretching frequency of uranyl oxalate, malonate, terephthalate and humate had similar values, suggesting the same number of ligands co-ordinating to central uranium atom, i.e. one carboxyl group is co-ordinated to one uranium atom. The smaller frequency was observed in uranyl salicylate, suggesting the co-ordination of both carboxyl and phenyl groups, under the formation of a 6-membered chelate ring. Ab initio MO calculation supported this idea.

Tsushima, S.; Nagasaki, S.; Tanaka, S.; Suzuki, A.



Effect of the TBP and Water on the Complexation of Uranyl Nitrate and the Dissolution of Nitric Acid into Supercritical CO2. A Theoretical Study  

E-print Network

containing the acid and uranyl salts. The simulations show that a high TBP/nitric acid ratio is needed that are highly soluble in SC-CO2. Concentrated nitric acid contains a large amount of water (up to 30% for "pure Acid into Supercritical CO2. A Theoretical Study R. Schurhammer and G. Wipff* Institut de Chimie - 4

Boyer, Edmond


Similarities between GCS and human motor cortex: complex movement coordination  

NASA Astrophysics Data System (ADS)

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.

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



Three-coordinate, luminescent, water-soluble gold(I) phosphine complexes: structural characterization and photoluminescence  

E-print Network

Three-coordinate, luminescent, water-soluble gold(I) phosphine complexes: structural some beautiful work involving gold Abstract The trigonal planar Au(I) complex Cs8[Au(TPPTS)3]Ã?/5.25H2O The photoluminescent properties of several types of three-coordinate gold(I) complexes in organic solvents

Abdou, Hanan E.


Binuclear uranium(VI) complexes with a "pacman" expanded porphyrin: computational evidence for highly unusual bis-actinyl structures.  


On the basis of uranyl complexes reacting with a polypyrrolic ligand (H(4)L), we explored structures and reaction energies of a series of new binuclear uranium(VI) complexes using relativistic density functional theory. Full geometry optimizations on [(UO(2))(2)(L)], in which two uranyl groups were initially placed into the pacman ligand cavity, led to two minimum-energy structures. These complexes with cation-cation interactions (CCI) exhibit unusual coordination modes of uranyls: one is a T-shaped (T) skeleton formed by two linear uranyls {O(exo)=U(2)=O(endo)-->U(1)(=O(exo))(2)}, and another is a butterfly-like (B) unit with one linear uranyl coordinating side-by-side to a second cis-uranyl. The CCI in T was confirmed by the calculated longest distance and lowest stretching vibrational frequency of U(2)=O(endo) among the four U=O bonds. Isomer B is more stable than T, for which experimental tetrameric analogues are known. The formation of B and T complexes from the mononuclear [(UO(2))(H(2)L)(thf)] (M) was found to be endothermic. The further protonation and dehydration of B and T are thermodynamically favorable. As a possible product, we have found a trianglelike binuclear uranium(VI) complex having a O=U=O=U=O unit. PMID:20066688

Pan, Qing-Jiang; Shamov, Grigory A; Schreckenbach, Georg



Ionothermal synthesis of uranyl compounds that incorporate imidazole derivatives  

SciTech Connect

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. (C{sub 4}H{sub 7}N{sub 2})[(UO{sub 2})(PO{sub 3}F)(F)] (1) crystallizes in space group C2, a=17.952(1) A, b=6.9646(6) A, c=8.5062(7) A, {beta}=112.301(1) Degree-Sign , (C{sub 6}H{sub 11}N{sub 2}){sub 2}[(UO{sub 2})(SO{sub 4}){sub 2}] (2) crystallizes in space group C2/c, a=31.90(1) A, b=9.383(5) A, c=13.770(7) A, {beta}=93.999(7) Degree-Sign and (C{sub 6}H{sub 11}N{sub 2})[(UO{sub 2}){sub 2}(PO{sub 4})(HPO{sub 4}) (3) crystallizes in space group P2{sub 1}/n, a=9.307(2), b=18.067(4), c=9.765(2), {beta}=93.171(2). The U{sup 6+} cations are present as (UO{sub 2}){sup 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. - Graphical abstract: The synthesis of uranyl compounds by ionothermal treatment is explored, and provides three novel compounds and insights concerning the role of water in controlling the structural units. Highlights: Black-Right-Pointing-Pointer Ionothermal syntheses have produced three new uranyl compounds. Black-Right-Pointing-Pointer Imidazole derivatives are incorporated as charge-balancing agents. Black-Right-Pointing-Pointer X-ray and spectroscopic analyses reveal variability between imidazole derivatives. Black-Right-Pointing-Pointer This method offers synthetic insight in the absence of water at low temperatures.

Wylie, Ernest M.; Dustin, Megan K.; Smith, Jeremy S. [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN 46556 (United States); Burns, Peter C., E-mail: [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States)



Analyst, July 1996, Vol. 121 (905-908) 905 Uranyl Photophysics on Colloidal Silica: an  

E-print Network

-3 (0.2 ppb) being routinely measurable. The luminescence of uranyl on dried silica gel is found complexes, sulfates and fluo- rides.3.4.8--1" Although the useful ion-exchange properties of silica gel to the effect of silica gel15and colloidal silica'b on the spectroscopic properties of uranyl and its analytical

Strathclyde, University of


Highly distorted uranyl ion coordination and one/two-dimensional structural relationship in the Ba2[UO2(TO4)2] (T = P, As) system: an experimental and computational study.  


Uranium compounds ?-Ba2[UO2(PO4)2] (1), ?-Ba2[UO2(PO4)2] (2), and Ba2[UO2(AsO4)2] (3) were synthesized by H3BO3/B2O3 flux reactions, though boron is not incorporated into the structures. Phases 1 and 2 are topologically identical, but 1 is heavily distorted with respect to 2. An unusual UO7 pentagonal bipyramid occurs in 1, exhibiting a highly distorted equatorial configuration and significant bending of the uranyl group, due to edge-sharing with one neighboring PO4(3-) tetrahedron. Compound 2 contains more normal square bipyramids that share corners with four neighboring PO4(3-) tetrahedra, but the uranyl cation UO2(2+) is tilted relative to the equatorial plane. Experimental evidence as well as density functional theory (DFT) calculations suggest that 1 is more stable than 2. In theory, 1 and 2 can interconvert by forming/releasing the shared edge between the uranyl polyhedron and the phosphate tetrahedron. Similar fundamental building blocks in ?-Ba2[UO2(PO4)2] and Ba2[UO2(AsO4)2] indicate a possible evolution of uranyl-based structures from chain to layer type and formation of an accretional series. PMID:24991981

Wu, Shijun; Kowalski, Piotr M; Yu, Na; Malcherek, Thomas; Depmeier, Wulf; Bosbach, Dirk; Wang, Shuao; Suleimanov, Evgeny V; Albrecht-Schmitt, Thomas E; Alekseev, Evgeny V



Vibrational spectroscopy and structural analysis of complex uranium compounds (review)  

SciTech Connect

The paper reports on the combined application of experimental and theoretical methods of vibrational spectroscopy together with low-temperature luminescence data to determine the characteristic features of the formation and structure of complex systems, not only containing ligands directly coordinated to the CA uranium, but also associated with the extraspherical polyatomic electrically charged particles: organic cations. These include uranyl complexes and heterocyclical amines. Studied here were compounds of tetra-halouranylates with pyridine and its derivates, as well as dipyridyl, quinoline and phenanthroline. Structural schemes are also proposed for other uranyl complexes with protonated heterocyclical amines with a more complicated composition, which correctly reflect their spectroscopic properties.

Umreiko, D.S.; Nikanovich, M.V.




NSDL National Science Digital Library

This introduction to the labeling of points on a plane by their Cartesian coordinates can optionally be extended to coordinates in 3-dimensional space, to plane polar coordinates and to 3-dimensional polar coordinates. Students should learn to use Cartesian coordinates (x,y) for defining the position of a point in two dimensions and to use Cartesian coordinates (x,y,z) in 3-dimensional space and learn to appreciate the two ways of defining the z axis. Students should also become familiar with some of the tools and terms used by surveyors such as theodolite, azimuth, elevation, and zenith. Optional items for students familiar with trigonometry and with the theorem of Pythagoras are polar coordinates (r,f ) on the plane, Converting (r,f) to (x,y) and vice versa, at least for r, and Spherical polar coordinates (r,q, f) in 3-dimensional space.

Stern, David



NSDL National Science Digital Library

Coordination is an organized working together of muscles and groups of muscles aimed at bringing about a purposeful movement such as walking or standing. Coordination involves timing and concentration.

Olivia Worland (Purdue University;Biological Sciences)



Assessment of accidental intakes of uranyl acetylacetonate (UAA)  

Microsoft Academic Search

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

D. R. Fisher; J. K. Briant



Preparation of Linear ?-Conjugated Coordination Polymers Having Ruthenium(II) Complex in the Main Chain  

Microsoft Academic Search

Soluble p-conjugated coordination polymers having a ruthenium(II) complex in the main chain were prepared from a “soluble metal complex monomer” and a “bridging ligand” via coordination. Refluxing of an ethanol-water suspension containing (4,4'-dinonyl-2,2'-bipyridyl)Ru(III) with 2,3-bis(2'-pyridyl)pyrazine gave the coordination polymer. The resulting polymer was soluble in common organic solvents. The structure was confirmed by uv\\/vis spectra and gpc analysis.

Gen-ichi Konishi; Kensuke Naka; Yoshiki Chujo



Barium uranyl diphosphonates  

SciTech Connect

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 mineralizing agent and a ligand.

Nelson, Anna-Gay D., E-mail: [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States); Alekseev, Evgeny V. [Institute of Energy and Climate Research (IEK-6), Forschungszentrum Juelich Wilhelm-Johnen-Strasse, Juelich 52428 (Germany); Ewing, Rodney C. [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States); Albrecht-Schmitt, Thomas E. [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States)



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


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

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



Six-Coordinate Lanthanide Complexes: Slow Relaxation of Magnetization in the Dysprosium(III) Complex.  


A series of six-coordinate lanthanide complexes {(H3 O)[Ln(NA)2 ]?H2 O}n (H2 NA=5-hydroxynicotinic acid; Ln=Gd(III) (1?Gd); Tb(III) (2?Tb); Dy(III) (3?Dy); Ho(III) (4?Ho)) have been synthesized from aqueous solution and fully characterized. Slow relaxation of the magnetization was observed in 3?Dy. To suppress the quantum tunneling of the magnetization, 3?Dy diluted by diamagnetic Y(III) ions was also synthesized and magnetically studied. Interesting butterfly-like hysteresis loops and an enhanced energy barrier for the slow relaxation of magnetization were observed in diluted 3?Dy. The energy barrier (?? ) and pre-exponential factor (?0 ) of the diluted 3?Dy are 75?K and 4.21×10(-5) ?s, respectively. This work illustrates a successful way to obtain low-coordination-number lanthanide complexes by a framework approach to show single-ion-magnet-like behavior. PMID:25297951

Na, Bo; Zhang, Xue-Jing; Shi, Wei; Zhang, Yi-Quan; Wang, Bing-Wu; Gao, Chen; Gao, Song; Cheng, Peng



How can the principles of complexity science be applied to improve the coordination of care for complex pediatric patients?  


Clinical and technological advances in medicine have resulted in more patients requiring multidisciplinary care and coordination of services. This is particularly challenging in pediatrics, given the dependency of children. Coordination of care is a key ingredient of quality care; when suboptimal, clinical outcomes and satisfaction can suffer. In this article we view coordination of care through the lens of complexity science in an effort to find new solutions to this healthcare challenge. PMID:16585105

Matlow, A G; Wright, J G; Zimmerman, B; Thomson, K; Valente, M



Bidentate and tridentate metal-ion coordination states within ternary complexes of RB69 DNA polymerase  

SciTech Connect

Two divalent metal ions are required for primer-extension catalyzed by DNA polymerases. One metal ion brings the 3'-hydroxyl of the primer terminus and the {alpha}-phosphorus atom of incoming dNTP together for bond formation so that the catalytically relevant conformation of the triphosphate tail of the dNTP is in an {alpha},{beta},{gamma}-tridentate coordination complex with the second metal ion required for proper substrate alignment. A probable base selectivity mechanism derived from structural studies on Dpo4 suggests that the inability of mispaired dNTPs to form a substrate-aligned, tridentate coordination complex could effectively cause the mispaired dNTPs to be rejected before catalysis. Nevertheless, we found that mispaired dNTPs can actually form a properly aligned tridentate coordination complex. However, complementary dNTPs occasionally form misaligned complexes with mutant RB69 DNA polymerases (RB69pols) that are not in a tridentate coordination state. Here, we report finding a {beta},{gamma}-bidentate coordination complex that contained the complementary dUpNpp opposite dA in the structure of a ternary complex formed by the wild type RB69pol at 1.88 {angstrom} resolution. Our observations suggest that several distinct metal-ion coordination states can exist at the ground state in the polymerase active site and that base selectivity is unlikely to be based on metal-ion coordination alone.

Xia, Shuangluo; Eom, Soo Hyun; Konigsberg, William H.; Wang, Jimin (Yale); (Gwangju)



Novel zwitterionic complexes arising from the coordination of an ambiphilic phosphorus-aluminum ligand to gold.  


Coordination of Mes2PC([double bond, length as m-dash]CHPh)AltBu2 to metal chlorides has been studied. Bridging P?M-Cl?Al coordinations were observed with Rh and Pd fragments, while chloride abstraction systematically occurred with gold. The resulting zwitterionic complexes have been fully characterized and analyzed by DFT calculations. PMID:25319140

Devillard, Marc; Nicolas, Emmanuel; Appelt, Christian; Backs, Jana; Mallet-Ladeira, Sonia; Bouhadir, Ghenwa; Slootweg, J Chris; Uhl, Werner; Bourissou, Didier



Coordinating complex decision support activities across distributed applications  

NASA Technical Reports Server (NTRS)

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.

Adler, Richard M.



Distributed detection of communities in complex networks using synthetic coordinates  

NASA Astrophysics Data System (ADS)

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.

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



Barium uranyl diphosphonates  

NASA Astrophysics Data System (ADS)

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.

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



cyanides using a rhodiumtrispyrazolylborate complex Coordination Chemistry of Saturated Molecules Special Feature: The activation of alkyl  

E-print Network

cyanides using a rhodiumtrispyrazolylborate complex Coordination Chemistry of Saturated To order reprints, see: Notes: #12;The activation of alkyl cyanides using a rhodiumtrispyrazolylborate

Jones, William D.


A Bridge to Coordination Isomer Selection in Lanthanide(III) DOTA-tetraamide Complexes  

PubMed Central

Interest in macrocyclic lanthanide complexes such as DOTA is driven largely through interest in their use as contrast agents for MRI. The lanthanide tetraamide derivatives of DOTA have shown considerable promise as PARACEST agents, taking advantage of the slow water exchange kinetics of this class of complex. We postulated that water exchange in these tetraamide complexes could be slowed even further by introducing a group to sterically encumber the space above the water coordination site, thereby hindering the departure and approach of water molecules to the complex. The ligand 8O2-bridged-DOTAM was synthesized in a 34% yield from cyclen. It was found that the lanthanide complexes of this ligand did not possess a water molecule in the inner coordination sphere of the bound lanthanide. The crystal structure of the ytterbium complex revealed that distortions to the coordination sphere were induced by the steric constraints imposed on the complex by the bridging unit. The extent of the distortion was found to increase with increasing ionic radius of the lanthanide ion, eventually resulting in a complete loss of symmetry in the complex. Because this ligand system is bicyclic, the conformation of each ring in the system is constrained by that of the other, in consequence inclusion of the bridging unit in the complexes means only a twisted square antiprismatic coordination geometry is observed for complexes of 8O2-bridged-DOTAM. PMID:17295475

Vipond, Jeff; Woods, Mark; Zhao, Piyu; Tircso, Gyula; Ren, Jimin; Bott, Simon G.; Ogrin, Doug; Kiefer, Garry E.; Kovacs, Zoltan; Sherry, A.Dean



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

NASA Astrophysics Data System (ADS)

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.

Kühn, Eva; Mordinyi, Richard; Schreiber, Christian


Coordination mode and reactivity of copper(II) complexes with kasugamycin.  


Protonation and Cu(II) coordination of kasugamycin were studied by potentiometry, UV-vis, CD, EPR, 13C NMR, and 1H NMR. Mononuclear complexes with stoichiometries ranging from CuHL to CuH(-1)L were found. The aminoamidine moiety provides the coordination site in the CuHL species. The additional axial coordination of the amino nitrogen of the aminosugar ring is present in CuL. Finally, the CuH(-1)L complex is formed as a result of a deprotonation and coordination of the hydroxyl group of the inositol ring. The non-planar arrangement of the chelate rings results in the relative stabilization of a Cu(I) species. As a consequence, Cu(I) and superoxide radicals are involved in the redox mechanism of H(2)O(2) activation by the Cu(II) complex of kasugamycin. PMID:11410229

Jezowska-Bojczuk, M; Le?niak, W



First synthesis of uranyl aluminate nanoparticles.  


This paper describes, for the first time, a simple method for the synthesis of uranyl aluminate (URAL) nanoparticles. URAL was prepared by U(VI) hydrolytic precipitation with ammonia at pH = 11 in the presence of mesoporous alumina MSU-X under 20 kHz of sonication followed by annealing of the obtained solids at 800 degrees C. TEM, XAFS, powder XRD, and (27)Al MAS NMR studies revealed that the speciation of uranium in this system strongly depends on uranium concentration. The sample with 5 wt % of uranium yields air-stable nanoparticles ( approximately 5 nm) of URAL. Presumably, UO(2)(2+) cations in this compound are coordinated with bidentate AlO(2)(-) groups. The increase of uranium concentration to 30 wt % causes mostly formation of U(3)O(8) fine particles ( approximately 50 nm) and small amounts of URAL. PMID:20552992

Chave, Tony; Nikitenko, Sergey I; Scheinost, Andreas C; Berthon, Claude; Arab-Chapelet, Bénédicte; Moisy, Philippe



Spectroscopic properties and design of highly luminescent lanthanide coordination complexes  

Microsoft Academic Search

In this paper recent advances in the development of efficient light conversion molecular devices (LCMD) based on lanthanide complexes are reviewed, with emphasis on the work of our group. We have adopted a strategy based upon both theoretical and experimental (synthesis and methodological) investigations. The theoretical aspects are described in terms of the well known theory of 4f–4f transitions and

G. F de Sá; O. L Malta; C de Mello Donegá; A. M Simas; R. L Longo; P. A Santa-Cruz; E. F da Silva



The coordination and atom transfer chemistry of titanium porphyrin complexes  

SciTech Connect

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.

Hays, J.A.



Alkane Coordination Selectivity in Hydrocarbon Activation by [TpRh(CNneopentyl)]: The Role of Alkane Complexes  

E-print Network

Alkane Coordination Selectivity in Hydrocarbon Activation by [TpRh(CNneopentyl)]: The Role of Alkane Complexes Andrew J. Vetter, Christine Flaschenriem, and William D. Jones* Contribution from in many cases that activation of alkanes occurs through a two-step process: formation of a -alkane complex

Jones, William D.


Supramolecular coordination and antimicrobial activities of constructed mixed ligand complexes  

NASA Astrophysics Data System (ADS)

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]Cl2?2H2O. 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.

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



Ligand Dependence of Binding to Three-Coordinate Fe(II) Complexes  

PubMed Central

A series of three- and four-coordinate iron(II) complexes with nitrogen, chlorine, oxygen, and sulfur ligands is presented. The electronic variation is explored by measuring the association constant of the neutral ligands, and the reduction potential of the iron(II) complexes. Varying the neutral ligand gives large changes in Keq, which decrease in the order CNtBu > pyridine > 2-picoline > DMF > MeCN > THF > PPh3. These differences can be attributed to a mixture of steric effects and electronic effects (both ? and ?). The binding constants and the reduction potentials are surprisingly insensitive to changes in an anionic spectator ligand. This suggests that three-coordinate iron(II) complexes may have similar binding trends as proposed three-coordinate iron(II) intermediates in the FeMoco of nitrogenase, even though the anionic spectator ligands in the synthetic complexes differ from the sulfides in the FeMoco. PMID:19438179

Chiang, Karen P.; Barrett, Pamela M.; Ding, Feizhi; Smith, Jeremy M.; Kingsley, Savariraj; Brennessel, William W.; Clark, Meghan M.; Lachicotte, Rene J.; Holland, Patrick L.



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

SciTech Connect

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.

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



Role of the coordination center in photocurrent behavior of a tetrathiafulvalene and metal complex dyad.  


Small organic molecule-based compounds are considered to be promising materials in photoelectronics and high-performance optoelectronic devices. However, photoelectron conversion research based on functional organic molecule and metal complex dyads is very scarce. We design and prepare a series of compounds containing a tetrathiafulvalene (TTF) moiety substituted with pyridylmethylamide groups of formulas [Ni(acac)2L]·2CH3OH (1), [Cu2I2L2]·THF·2CH3CN (2), and [MnCl2L2]n·2nCH3CH2OH (3) (L = 4,5-bis(3-pyridylmethylamide)-4',5'-bimethylthio-tetrathiafulvalene, acac = acetylacetone) to study the role of the coordination center in photocurrent behavior. Complex 1 is a mononuclear species, and complex 2 is a dimeric species. Complex 3 is a two-dimensional (2-D) coordination polymer. Spectroscopic and electrochemical properties of these complexes indicate that they are electrochemically active materials. The tetrathiafulvalene ligand L is a photoelectron donor in the presence of electron acceptor methylviologen. The effect of metal coordination centers on photocurrent response behavior is examined. The redox-active metal coordination centers should play an important role in improvement of the photocurrent response property. The different morphologies of the electrode films reflect the dimensions in molecular structures of the coordination compounds. PMID:24592888

Sun, Yong-Gang; Ji, Shu-Fang; Huo, Peng; Yin, Jing-Xue; Huang, Yu-De; Zhu, Qin-Yu; Dai, Jie



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

PubMed Central

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

Li, Xiang; Liu, Ming



From manufacturing scheduling to supply chain coordination: The control of complexity and uncertainty  

Microsoft Academic Search

With time-based competition and rapid technology advancements, effective manufacturing scheduling and supply chain coordination\\u000a are critical to quickly respond to changing market conditions. These problems, however, are difficult in view of inherent\\u000a complexity and various uncertainties involved. Based on a series of results by the authors, decomposition and coordination\\u000a by using Lagrangian relaxation is identified in this paper as an

Peter B. Luh; Weidong Feng



Siderophilin metal coordination. 1. Complexation of thorium by transferrin: structure-function implications  

Microsoft Academic Search

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

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



ESEEM analysis of multi-histidine Cu(II)-coordination in model complexes, peptides, and amyloid-?.  


We validate the use of ESEEM to predict the number of (14)N 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-? (A?). A? 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 (15)N-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

Silva, K Ishara; Michael, Brian C; Geib, Steven J; Saxena, Sunil



Coordination and redox isomerization in the reduction of a uranium(III) monoarene complex.  


Synthetic studies on the redox chemistry of trivalent uranium monoarene complexes were undertaken with a complex derived from the chelating tris(aryloxide)arene ligand ((Ad,Me) ArO)3 mes(3-) . Cyclic voltammetry of [{((Ad,Me) ArO)3 mes}U(III) ] (1) revealed a nearly reversible and chemically accessible reduction at -2.495?V vs. Fc/Fc(+) -the first electrochemical evidence for a formally divalent uranium complex. Chemical reduction of 1 indicates that reduction induces coordination and redox isomerization to form a uranium(IV) hydride, and addition of a crown ether results in hydride insertion into the coordinated arene to afford uranium(IV) complexes. This stoichiometric reaction sequence provides structural insight into the mechanism of arene functionalization at diuranium inverted sandwich complexes. PMID:24889470

La Pierre, Henry S; Kameo, Hajime; Halter, Dominik P; Heinemann, Frank W; Meyer, Karsten



Progress towards a fiber-optic uranium sensor (detection of uranyl at PPB levels via fluorescence quenching followed by uranyl photooxidation)  

SciTech Connect

Much emphasis has been placed on the determination of nuclear waste products in recent years. We have developed a simple, sensitive and selective method for the determination of uranium as uranyl ion in solution. At low pH uranyl ion will quench the fluorescence of a fluorescein type dye, Fluorexon (Calcein). We attribute this quenching to complex formation between the dye and attribute uranyl ion. In buffered medium, this quenching follows the Stern-Volmer relation with a limit of detection of less than 10 ppb but with a limited linear range. In order to improve selectivity, a second experiment is performed after quenching. Excitation of the sample at a uranyl absorption band (420-450nm) forms the highly oxidative UO{sub 2}{sup 2+} species. This excited state species has an oxidation potential of 2.6V, a photooxidation quantum efficiency of 0.573 and the potential to be regenerated in the reaction cycle. The excited state uranyl presumably photooxidizes the dye causing an increase in fluorescence of the sample solution over time. The degree of fluorescence regeneration and recovery time are proportional to the uranyl ion concentration. Few interfering metal species have been found that exhibit similar behavior. We are attempting to use this system to develop a second-order fiberoptic sensor. The sensor uses a cation-exchange membrane (Nafion) to immobilize the dye and minimize potential interference from dichromate anion.

Nivens, D.A.; Skvoretz, M.E.; Zhang, Yunke; Angel, S.M. [Univ. of South Carolina, Columbia, SC (United States)



Density functional theory and molecular dynamics study of the uranyl ion (UO?)²?.  


The detection of uranium is very important, especially in water and, more importantly, in the form of uranyl ion (UO?)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

Rodríguez-Jeangros, Nicolás; Seminario, Jorge M



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


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 [(?(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 [(?(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(?(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(?(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 [(?(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 rhodium complex showed catalytic activity in Suzuki-Miyaura type reaction. As a result of the excellent stability of the homogeneous catalyst [(quinone)Rh(COD)](-) in water, we also successfully demonstrated catalyst recycling in 1,2- and 1,4-addition reactions. The compound [(quinone)Ir(COD)](-) showed significantly poorer catalytic activity in 1,4-addition reactions. Following upon the excellent coordination ability of the quinonoid rhodium complexes to metal centers, we synthesized organometallic coordination polymer nanocatalysts and silica gel-supported quinonoid rhodium catalysts, the latter using a surface sol-gel technique. The resulting heterogeneous catalysts showed activity in the stereospecific polymerization of phenylacetylene. PMID:23745596

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



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


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

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



From Manufacturing Scheduling to Supply Chain Coordination: The Control of Complexity and Uncertainty  

Microsoft Academic Search

With time-based competition and rapid technology advancements, effective manufacturing scheduling and supply chain coordination are critical to quickly respond to changing market conditions. These problems, however, are difficult in view of inherent complexity and various uncertainties involved. A manufacturing scheduling problem is first formulated within the job shop context with order arrivals, processing times, due dates, and part priorities as

Peter B. Luh



Modeling the Reactivity of Superoxide Reducing Metalloenzymes with a Nitrogen and Sulfur Coordinated Iron Complex  

E-print Network

Modeling the Reactivity of Superoxide Reducing Metalloenzymes with a Nitrogen and Sulfur Coordinated Iron Complex Jason Shearer, Jennifer Nehring, Scott Lovell, Werner Kaminsky, and Julie A. KovacsVibrio desulfuricans).3,4 The active sites of both of these enzymes contain a cysteinate-ligated iron center

Kaminsky, Werner


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


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

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



Analysis of Perfectly Matched Double Negative Layers Via Complex Coordinate Transformations  

Microsoft Academic Search

Complex coordinate transformations are introduced for the analysis of time-harmonic electromagnetic wave propagation in perfectly matched double negative layers. The layer is perfectly matched to free space in the sense that any incident plane wave is transmitted through the free space-material interface without reflection, irrespective of the frequency and angle of incidence of the plane wave. The material constitutive parameters

Mustafa Kuzuoglu



Influence of topology in the evolution of coordination in complex networks under information diffusion constraints  

NASA Astrophysics Data System (ADS)

In this paper, we study the influence of the topological structure of social systems on the evolution of coordination in them. We simulate a coordination game ("Stag-hunt") on four well-known classes of complex networks commonly used to model social systems, namely scale-free, small-world, random and hierarchical-modular, as well as on the well-mixed model. Our particular focus is on understanding the impact of information diffusion on coordination, and how this impact varies according to the topology of the social system. We demonstrate that while time-lags and noise in the information about relative payoffs affect the emergence of coordination in all social systems, some topologies are markedly more resilient than others to these effects. We also show that, while non-coordination may be a better strategy in a society where people do not have information about the payoffs of others, coordination will quickly emerge as the better strategy when people get this information about others, even with noise and time lags. Societies with the so-called small-world structure are most conducive to the emergence of coordination, despite limitations in information propagation, while societies with scale-free topologies are most sensitive to noise and time-lags in information diffusion. Surprisingly, in all topologies, it is not the highest connected people (hubs), but the slightly less connected people (provincial hubs) who first adopt coordination. Our findings confirm that the evolution of coordination in social systems depends heavily on the underlying social network structure.

Kasthurirathna, Dharshana; Piraveenan, Mahendra; Harré, Michael



Uranyl carboxyphosphonates that incorporate Cd(II)  

SciTech Connect

The hydrothermal treatment of UO{sub 3}, Cd(CH{sub 3}CO{sub 2}){sub 2}.2H{sub 2}O, and triethyl phosphonoacetate results in the formation of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O (CdUPAA-1), [Cd{sub 3}(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 6}(H{sub 2}O){sub 13}].6H{sub 2}O (CdUPAA-2), and Cd(H{sub 2}O){sub 2}[(UO{sub 2})(PO{sub 3}CH{sub 2}CO{sub 2})(H{sub 2}O)]{sub 2} (CdUPAA-3). CdUPAA-1 adopts a cubic three-dimensional structure constructed from planar uranyl oxide clusters containing both UO{sub 7} pentagonal bipyramids and UO{sub 8} hexagonal bipyramids that are linked by Cd(II) cations and phosphonoacetate to yield large cavities approximately 16 A across that are filled with disordered water molecules. CdUPAA-2 forms a rhombohedral three-dimensional channel structure that is assembled from UO{sub 7} pentagonal bipyramids that are bridged by phosphonoacetate. CdUPAA-3 is layered with the hydrated Cd(II) cations incorporated directly into the layers linking one-dimensional uranyl phosphonate substructures together. In this structure, there are complex networks of hydrogen bonds that exist within the sheets, and also stitch the sheets together. -- Graphical abstract: A view of part of the cubic structure of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O. Display Omitted highlights: > High symmetry uranyl compounds. > Three-dimensional structures. > Porous materials. > Heterobimetallic compounds.

Alsobrook, Andrea N. [Department of Civil Engineering and Geological Sciences, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556 (United States); Alekseev, Evgeny V.; Depmeier, Wulf [Institut fuer Geowissenschaften, Universitaet zu Kiel, 24118 Kiel (Germany); Albrecht-Schmitt, Thomas E., E-mail: talbrec1@nd.ed [Department of Civil Engineering and Geological Sciences, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556 (United States); Department of Chemistry and Biochemistry, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556 (United States)



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

NASA Astrophysics Data System (ADS)

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.

Iyer, Swami; Killingback, Timothy



Coordination and structural properties of encumbering 6-mesityl-2-picolinate complexes.  


In an effort to enforce a sterically hindered environment in transition-metal and main-group 2-picolinate complexes, the synthesis of the encumbering derivative 6-mesityl-2-picolinate ((Mes)pic) is presented. The coordination and structural properties of (Mes)pic are demonstrated with a range of transition-metal and main-group fragments. The 6-position mesityl group of (Mes)pic is shown to alter both the primary and secondary coordination spheres of metal centers relative to the ubiquitous and unencumbered parent 2-picolinate anion. PMID:22549113

Smith, Patrick W; Moore, Curtis E; Rheingold, Arnold L; Figueroa, Joshua S



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

PubMed Central

Reaction of 1-adamantyl azide with iron(I) diketiminate precursors gives metastable but isolable imidoiron(III) complexes LFe=NAd (L = bulky ?-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

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



Optical apparatus and method for sensing uranyl  


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.

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



Zinc(II)-Coordination Complexes as Membrane Active Fluorescent Probes and Antibiotics  

PubMed Central

Molecular probes with zinc(II)-(2,2’-dipicolylamine) coordination complexes associate with oxyanions in aqueous solution and target biomembranes that contain anionic phospholipids. This study examines a new series of coordination complexes with 2,6-bis(zinc(II)-dipicolylamine) phenoxide as the molecular recognition unit. Two lipophilic analogues are observed to partition into the membranes of zwitterionic and anionic vesicles and induce the transport of phospholipids and hydrophilic anions (carboxyfluorescein). These lipophilic zinc complexes are moderately toxic to mammalian cells. A more hydrophilic analogue does not exhibit mammalian cell toxicity (LD50 >50 µg/mL), but it is highly active against the Gram-positive bacteria Staphylococcus aureus (MIC of 1 µg/mL). Furthermore, it is active against clinically important S. aureus strains that are resistant to various antibiotics including vancomycin and oxacillin. The antibiotic action is attributed to its ability to depolarize the bacterial cell membrane. The intense bacterial staining exhibited by a fluorescent conjugate suggests that this family of zinc coordination complexes can be used as molecular probes for the detection and imaging of bacteria. PMID:18076009

DiVittorio, Kristy M.; Leevy, W. Matthew; O'Neil, Edward J.; Johnson, James R.; Vakulenko, Sergei; Morris, Joshua D.; Rosek, Kristine D.; Serazin, Nathan; Hilkert, Sarah; Hurley, Scott; Marquez, Manuel; Smith, Bradley D.



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

NASA Technical Reports Server (NTRS)

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.

Beck, M.



Coordination properties of hydralazine Schiff base. Synthesis and equilibrium studies of some metal ion complexes  

NASA Astrophysics Data System (ADS)

In the present study, a new ligand is prepared by condensation of hydralazine (1-Hydralazinophthalazine) with 2-butanon-3-oxime. The acid-base equilibria of the schiff-base and the complex formation equilibria with the metal ions as Cu(II), Ni(II), Co(II), Cd(II), Mn(II) and Zn(II) are investigated potentiometrically. The stability constants of the complexes are determined and the concentration distribution diagrams of the complexes are evaluated. The effect of metal ion properties as atomic number, ionic radius, electronegativity and ionization potential are investigated. The isolated solid complexes are characterized by conventional chemical and physical methods. The potential coordination sites are assigned using the i.r. and 1H NMR spectra. The structures of the isolated solid complexes are proposed on the basis of the spectral and magnetic studies.

Shoukry, Azza A.; Shoukry, Mohamed M.



Characterization of Two Different Five-Coordinate Soluble Guanylate Cyclase Ferrous–Nitrosyl Complexes †  

Microsoft Academic Search

ABSTRACT: Soluble guanylate cyclase (sGC), a hemoprotein, is the primary nitric oxide (NO) receptor in higher eukaryotes. The binding of NO to sGC leads to the formation of a five-coordinate ferrous-nitrosyl complex,and a several hundred-fold increase in cGMP synthesis. NO activation of sGC is influenced by GTP and the allosteric activators YC-1 and BAY 41-2272. Electron paramagnetic resonance (EPR) spectroscopy

Emily R. Derbyshire; Alexander Gunn; Mohammed Ibrahim; Thomas G. Spiro; R. David Britt; Michael A. Marletta



Formation of Au(III)DNA Coordinate Complex by Laser Ablation of Au Nanoparticles in Solution  

Microsoft Academic Search

We discovered that an Au(III)-DNA coordinate complex, Au(III)(DNA-base)2(amine)l, are formed by laser ablation of Au nanoparticles in an aqueous solution containing DNA molecules in the presence of amines and multi-valent cations, where l represents an unknown ligand (either amine or water). Optical absorption spectrum of the solution after laser ablation exhibited a 360 nm absorption peak assigned to ligand?Au(III) charge

Yoshihiro Takeda; Tamotsu Kondow; Fumitaka Mafuné



Coronin 1B coordinates Arp2/3 complex and Cofilin activities at the leading edge  

PubMed Central

Summary Actin filament nucleation and turnover are interdependent processes in migrating cells, but the mechanisms coordinating these events are unknown. Coronin 1B influences motility, lamellipodial dynamics and actin filament architecture at the leading edge of Rat2 cells in a manner consistent with a role in coordinating filament formation and turnover. Coronin 1B interacts simultaneously with both Arp2/3 complex and Slingshot (SSH1L) phosphatase, two regulators of actin filament formation and turnover, respectively. Coronin 1B inhibits filament nucleation by Arp2/3 complex and this inhibition is attenuated by phosphorylation of Coronin 1B on Serine 2, a site targeted by SSH1L. Coronin 1B directs SSH1L to lamellipodia where it likely regulates Cofilin. Accordingly, depleting Coronin 1B increases phospho-Cofilin levels and expressing activated Cofilin partially suppresses the effects on lamellipodia dynamics of Coronin 1B depletion. Thus, Coronin 1B coordinates filament nucleation via Arp2/3 complex and turnover by Cofilin at the leading edge of migrating cells. PMID:17350576

Cai, Liang; Marshall, Thomas W.; Uetrecht, Andrea C.; Schafer, Dorothy A.; Bear, James E.



Anion-regulated assemblies of diverse CuII coordination complexes with a versatile tripyridyltriazole ligand  

NASA Astrophysics Data System (ADS)

In this work, a series of five CuII coordination complexes, {[Cu(L)(dca)(OAc)]?1.5H2O}n (1), [Cu(L)(dca)Br]2 (2), [Cu(L)(OAc)2]2 (3), [Cu(L)Cl2]2 (4), and [Cu(L)2(ClO4)2] (5), have been prepared with a novel tripyridyltriazole ligand 3,4-bis(2-pyridyl)-5-(3-pyridyl)-1,2,4-triazole (L) and different CuII sources. Single-crystal X-ray diffraction analysis reveals that these complexes show diverse 1-D (for 1), dimeric (for 2-4) and monomeric (for 5) coordination motifs, in which the L ligands exhibit different coordination fashions. These results obviously demonstrate that the structural assembly of complexes 1-5 can be exclusively dominated by the counter anions of metal salts and the auxiliary dicyanamide (dca) anion. Their thermal stabilities have also been investigated and discussed.

Wang, Fei-Fei; Guo, Wei; Jiang, Cheng-Hui; Guo, Ya-Mei




SciTech Connect

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 rapidly. At pH 6 and a Th(IV)/transferrin ratio of 2, only ~0.3 Th(IV) are bound per protein ([Th] = 10{sup -5}M). The N-terminal site is more rapidly affected by lowering the pH, so that coordination is entirely at the C-terminal site at low pH. Above pH 9, the conformation at the C-terminal site (two tyrosines) changes such that only one tyrosine is bound, the same that pertains at the N-terminal site at neutral pH. In addition to the three protons released by the coordinating tyrosine residues, the complexation of two Th(IV) ions releases two more protons at pH 8.6, which are ascribed to hydrolysis, so that the metal is bound as a monohydroxo species. It is suggested that diferric transferrin undergoes a similar reaction, and the other implications of these results for the structure and function of the native ferric transferrin are discussed.

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



Uranium(VI) organoimido complexes  

SciTech Connect

Complexes containing multiply bonded alkylidene, alkylidyne, imido, nitrido, and oxo ligands, and selected combinations thereof, are part of the tapestry of tungsten(VI) chemistry. Aside from uranyl complexes, the only reported molecular coordination compounds of U(VI) are UF{sub 6}, UCl{sub 6}, and the binary alkoxides, U(OR){sub 6}. Uranium(VI) compounds containing the other functional groups listed above have never been reported. Here the authors describe the synthesis and structural characterization of the first uranium(VI) systems containing a multiple bond to nitrogen.

Burns, C.J.; Smith, W.H.; Sattelberger, A.P. (Los Alamos National Lab., NM (USA)); Huffman, J.C. (Indiana Univ., Bloomington (USA))



Complexation of U(VI) with dipicolinic acid: thermodynamics and coordination modes.  


Complexation of UO2(2+) with dipicolinic acid (DPA) has been investigated in 0.1 M NaClO4. The stability constants (log ?1 and log ?2) for two successive complexes, UO2L and UO2L2(2-) where L(2-) stands for the deprotonated dipicolinate anion, were determined to be 10.7 ± 0.1 and 16.3 ± 0.1 by spectrophotometry. The enthalpies of complexation (?H1 and ?H2) were measured to be -(6.9 ± 0.2) and -(28.9 ± 0.5) kJ·mol(-1) by microcalorimetry. The entropies of complexation (?S1 and ?S2) were calculated accordingly to be (181 ± 3) and (215 ± 4) J·K(-1)·mol(-1). The strong complexation of UO2(2+) with DPA is driven by positive entropies as well as exothermic enthalpies. The crystal structure of Na2UO2L2(H2O)8(s) shows that, in the 1:2 UO2(2+)/DPA complex, the U atom sits at a center of inversion and the two DPA ligands symmetrically coordinate to UO2(2+) via its equatorial plane in a tridentate mode. The structural information suggests that, due to the conjugated planar structure of DPA with the donor atoms (the pyridine nitrogen and two carboxylate oxygen atoms) arranged at optimal positions to coordinate with UO2(2+), little energy is required for the preorganization of the ligand, resulting in strong UO2(2+)/DPA complexation. PMID:23421621

Xu, Chao; Tian, Guoxin; Teat, Simon J; Rao, Linfeng



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

NASA Astrophysics Data System (ADS)

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.

Ikotun, Oluwatayo (Tayo) F.


Synthesis and reactivity of coordinatively unsaturated halocarbonyl molybdenum PNP pincer complexes.  


In the present study a series of six-coordinate neutral 16e halocarbonyl Mo(ii) complexes of the type [Mo(PNP(Me)-iPr)(CO)X2] (X = I, Br, Cl), featuring the PNP pincer ligand N,N'-bis(diisopropylphosphino)-N,N'-dimethyl-2,6-diaminopyridine (PNP(Me)-iPr), were prepared and fully characterized. The synthesis of these complexes was accomplished by different methodologies depending on the halide ligands. For X = I and Br, [Mo(PNP(Me)-iPr)(CO)I2] and [Mo(PNP(Me)-iPr)(CO)Br2] were obtained by reacting [Mo(PNP(Me)-iPr)(CO)3] with stoichiometric amounts of I2 and Br2, respectively. In the case of X = Cl, [Mo(PNP(Me)-iPr)(CO)Cl2] was afforded by the reaction of [Mo(CO)4(?-Cl)Cl]2 with 1 equiv. of PNP(Me)-iPr. The equivalent procedure also worked for X = Br. The modification of the 2,6-diaminopyridine scaffold by introducing NMe instead of NH spacers between the aromatic pyridine ring and the phosphine moieties changed the steric properties of the PNP-iPr ligand significantly. While in the present case exclusively neutral six-coordinate complexes of the type [Mo(PNP(Me)-iPr)(CO)X2] were obtained, with the parent PNP-iPr ligand, i.e. featuring NH spacers, cationic seven-coordinate complexes of the type [Mo(PNP-iPr)(CO)3X]X were afforded. Upon treatment of [Mo(PNP(Me)-iPr)(CO)X2] (X = Br, Cl) with Ag(+) in CH3CN, the cationic complexes [Mo(PNP(Me)-iPr)(CO)(CH3CN)X](+) were formed. Halide abstraction from [Mo(PNP(Me)-iPr)(CO)Cl2] in THF-CH2Cl2 afforded [Mo(PNP(Me)-iPr)(CO)(THF)Cl](+). In keeping with the facile synthesis of monocationic complexes preliminary ESI-MS and DFT/B3LYP studies revealed that one halide ligand in complexes [Mo(PNP(Me)-iPr)(CO)X2] is labile forming cationic fragments [Mo(PNP(Me)-iPr)(CO)X](+) which react with molecular oxygen in parallel pathways to yield mono and dioxo Mo(iv) and Mo(vi) species. Structures of representative complexes were determined by X-ray single crystal analyses. PMID:25142749

de Aguiar, Sara R M M; Oztopcu, Ozgür; Stöger, Berthold; Mereiter, Kurt; Veiros, Luis F; Pittenauer, Ernst; Allmaier, Günter; Kirchner, Karl



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

PubMed Central

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

Miettinen, Sari; Ashorn, Ulla; Lehto, Juhani



Extremely Facile Template Synthesis of Gold(III) Complexes of a Saturated Azamacrocycle and Crystal Structure of a Six-Coordinate Gold(III) Complex  

E-print Network

Extremely Facile Template Synthesis of Gold(III) Complexes of a Saturated Azamacrocycle and Crystal Structure of a Six-Coordinate Gold(III) Complex Myunghyun Paik Suh,* Il Soon Kim, Boo Yong Shim, Daewon Hong University, Seoul 151-742, Republic of Korea ReceiVed February 2, 1996X Two gold(III) complexes

Paik Suh, Myunghyun


U(VI)-kaolinite surface complexation in absence and presence of humic acid studied by TRLFS.  


Time-resolved laser-induced fluorescence spectroscopy (TRLFS) was applied to study the U(VI) surface complexes on kaolinite in the presence and absence of humic acid (HA). Two uranyl surface species with fluorescence lifetimes of 5.9 +/- 1.4 and 42.5 +/- 3.4 micros and 4.4 +/- 1.2 and 30.9 +/- 7.2 micros were identified in the binary (U(VI)-kaolinite) and ternary system (U(VI)-HA-kaolinite), respectively. The fluorescence spectra of adsorbed uranyl surface species are described with six and five fluorescence emission bands in the binary and ternary system, respectively. The positions of peak maxima are shifted significantly to higher wavelengths compared to the free uranyl ion in perchlorate medium. HA has no influence on positions of the fluorescence emission bands. In the binary system, both surface species can be attributed to adsorbed bidentate mononuclear surface complexes, which differ in the number of water molecules in their coordination environment. In the ternary system, U(VI) prefers direct binding on kaolinite rather than via HA, but it is sorbed as a uranyl-humate complex. Consequently, the hydration shell of the U(VI) surface complexes is displaced with complexed HA, which is simultaneously distributed between kaolinite particles. Aluminol binding sites are assumed to control the sorption of U(VI) onto kaolinite. PMID:17937294

Krepelova, Adela; Brendler, Vinzenz; Sachs, Susanne; Baumann, Nils; Bernhard, Gert



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

PubMed Central

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

Sadasivam, Subhashini; DeCaprio, James A.



Mononuclear Three-Coordinate Magnesium Complexes of a Highly Sterically Encumbered ?-Diketiminate Ligand.  


The highly sterically encumbered chelating ?-diketiminate ligand, [HC{C(Me)N(2,6-CHPh2-4-MeC6H2)}2](-), (Ar)L(-), has been used to prepare a series of heteroleptic three-coordinate magnesium complexes. Both the bis(imine) and imine-enamine tautomers of the ligand precursor, (Ar)LH, as well as the diethyl ether adduct of the bromide complex [(Ar)LMgBr(OEt2)], the monomeric methyl complex [(Ar)LMgMe], the THF-solvated and unsolvated n-butylmagnesium complexes [(Ar)LMg(n)Bu(THF)] and [(Ar)LMg(n)Bu], and the 1-hexynyl analogue [(Ar)LMgC?C(n)Bu] have been crystallographically characterized. Both n-butylmagnesium complexes showed remarkable stability in air, both in the solid state and in solution. Single crystals of the highly sensitive magnesium hydride, [(Ar)LMgH], underwent partial hydrolysis by solid-state water diffusion to the isostructural hydroxide compound [(Ar)LMgOH]. PMID:25203490

Arrowsmith, Merle; Maitland, Brant; Kociok-Köhn, Gabriele; Stasch, Andreas; Jones, Cameron; Hill, Michael S



Small molecule regulation of self-association and catalytic activity in a supramolecular coordination complex.  


Herein, we report the synthesis and characterization of the first weak-link approach (WLA) supramolecular construct that employs the small molecule regulation of intermolecular hydrogen bonding interactions for the in situ control of catalytic activity. A biaryl urea group, prone to self-aggregation, was functionalized with a phosphinoalkyl thioether (P,S) hemilabile moiety and incorporated into a homoligated Pt(II) tweezer WLA complex. This urea-containing construct, which has been characterized by a single crystal X-ray diffraction study, can be switched in situ from a rigid fully closed state to a flexible semiopen state via Cl(-) induced changes in the coordination mode at the Pt(II) structural node. FT-IR and (1)H NMR spectroscopy studies were used to demonstrate that while extensive urea self-association persists in the flexible semiopen complex, these interactions are deterred in the rigid, fully closed complex because of geometric and steric restraints. Consequently, the urea moieties in the fully closed complex are able to catalyze a Diels-Alder reaction between cyclopentadiene and methyl vinyl ketone to generate 2-acetyl-5-norbornene. The free urea ligand and the semiopen complex show no such activity. The successful incorporation and regulation of a hydrogen bond donating catalyst in a WLA construct open the doors to a vast and rapidly growing catalogue of allosteric catalysts for applications in the detection and amplification of organic analytes. PMID:24628075

McGuirk, C Michael; Stern, Charlotte L; Mirkin, Chad A



Intramolecular nucleophilic substitution on coordinated borabenzenes: A new entry into boratabenzene complexes  

SciTech Connect

Electrophilic complexes containing boratabenzene ligands are finding applications in olefin polymerization and oligomerization reactions. Most significant is the ability to control the reactivity of boratabenzene catalysts by adjusting the degree of orbital overlap between boron and its exocyclic substituent. Boratabenzene catalysts have appeared with reactivities that complement those observed with standard group 4 metallocenes. Furthermore, while both cyclopentadienyl (Cp) and boratabenzene are formally monoanionic 6{pi} electron donors, boratabenzene is a weaker donor. Isostructural complexes containing boratabenzene instead of Cp therefore have a greater tendency for lower oxidation states and offer altered mechanistic pathways for elementary reactions. One of the main difficulties in advancing a broader use of boratabenzene complexes in industry and in noncatalytic reactions useful for organic chemistry is the multistep synthesis of the boratabenzene complexes in industry and in noncatalytic reactions useful for organic chemistry is the multistep synthesis of the boratabenzene framework. Methods for coordination typically make direct analogy to Cp chemistry, namely, salt metathesis by addition of ligand salts to metal halides. In this paper the authors report a new type of reaction that gives transition metal-boratabenzene complexes directly from neutral borabenzene-base adducts.

Putzer, M.; Rogers, J.S.; Bazan, G.C.



Dynamics of complex molecular systems with numerical kinetic energy operators in generalized coordinates  

NASA Astrophysics Data System (ADS)

Dynamics of complex molecular systems in generalized coordinates ( q, p) using numerical kinetic energy operators is investigated. The kinematical tools necessary for quantum, classical or semiclassical dynamics with or without constraints mainly come from the covariant and contravariant components of the metric tensor and their derivatives up to the second ones. These quantities are computed numerically but without any other approximation than the numerical precision by the code TNUM. This code generates kinetic energy operators in the internal coordinates of the Z-matrix describing the molecular frame geometry in the ab initio quantum chemistry step or in symmetry adapted coordinates [D. Lauvergnat, A. Nauts, J. Chem. Phys. 116 (2002) 8560]. Various reduced dimensionality models can be used in the upgraded code. The interface with an ab initio code is calibrated on a 22-atom system for which a two-dimensional quantum treatment with a constrained Hamiltonian has been carried out previously. The test application concerns the spreading properties of a wave packet in an unstable flat region around a valley ridge inflexion point between two transition states in the Endo-dimerization of cyclopentadiene. We perform here on-the-fly classical or semiclassical dynamics in full or reduced dimensionality.

Lauvergnat, David; Baloïtcha, Ezinvi; Dive, Georges; Desouter-Lecomte, Michèle



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

NASA Astrophysics Data System (ADS)

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, ?=72.974(2), ?=74.261(2), ?=79.498(2); and UInP crystallizes in P-1, a=7.9856(5), b=9.159(1), c=9.2398(6) Å ?=101.289(1), ?=114.642(1), ?=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.

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



Flexible coordination of diphosphine ligands leading to cis and trans Pd(0), Pd(II), and Rh(I) complexes.  


A series of diphosphine ligands (i)Pr2P-C6H4-X-C6H4-P(i)Pr2 (for ligand L(1), X = CH2; for ligand L(2), X = CH2CH2) was investigated to determine the preference for cis/trans coordination to palladium(0), palladium(II), and rhodium(I). Increasing the length of the bridging alkyl backbone from one to two carbons changes the geometry of the resulting palladium(II) complexes, with L(1) coordinating preferentially cis, while L(2) coordinates in a trans fashion. Coordination to Pd(0) leads to L(1)Pd(dba) and L(2)Pd(dba), in which both ligands accommodate a P-M-P angle close to 120°. L(2) was found to coordinate cis in a rhodium(I) complex ([L(2)Rh(nbd)][BF4], where nbd = norbornadiene). PMID:25102103

Comanescu, Cezar C; Iluc, Vlad M



Synthesis and structure of six-coordinate iron borohydride complexes supported by PNP ligands.  


The preparation of a number of iron complexes supported by ligands of the type HN{CH2CH2(PR2)}2 [R = isopropyl (((i)Pr)PNP) or cyclohexyl ((Cy)PNP)] is reported. This is the first time this important bifunctional ligand has been coordinated to iron. The iron(II) complexes (((i)Pr)PNP)FeCl2(CO) (1a) and ((Cy)PNP)FeCl2(CO) (1b) were synthesized through the reaction of the appropriate free ligand and FeCl2 in the presence of CO. The iron(0) complex (((i)Pr)PNP)Fe(CO)2 (2a) was prepared through the reaction of Fe(CO)5 with ((i)Pr)PNP, while irradiating with UV light. Compound 2a is unstable in CH2Cl2 and is oxidized to 1a via the intermediate iron(II) complex [(((i)Pr)PNP)FeCl(CO)2]Cl (3a). The reaction of 2a with HCl generated the related complex [(((i)Pr)PNP)FeH(CO)2]Cl (4a), while the neutral iron hydrides (((i)Pr)PNP)FeHCl(CO) (5a) and ((Cy)PNP)FeHCl(CO) (5b) were synthesized through the reaction of 1a or 1b with 1 equiv of (n)Bu4NBH4. The related reaction between 1a and excess NaBH4 generated the unusual ?(1)-HBH3 complex (((i)Pr)PNP)FeH(?(1)-HBH3)(CO) (6a). This complex features a bifurcated intramolecular dihydrogen bond between two of the hydrogen atoms associated with the ?(1)-HBH3 ligand and the N-H proton of the pincer ligand, as well as intermolecular dihydrogen bonding. The protonation of 6a with 2,6-lutidinium tetraphenylborate resulted in the formation of the dimeric complex [{(((i)Pr)PNP)FeH(CO)}2(?2,?(1):?(1)-H2BH2)][BPh4] (7a), which features a rare example of a ?2,?(1):?(1)-H2BH2 ligand. Unlike all previous examples of complexes with a ?2,?(1):?(1)-H2BH2 ligand, there is no metal-metal bond and additional bridging ligand supporting the borohydride ligand in 7a; however, it is proposed that two dihydrogen-bonding interactions stabilize the complex. Complexes 1a, 2a, 3a, 4a, 5a, 6a, and 7a were characterized by X-ray crystallography. PMID:24499462

Koehne, Ingo; Schmeier, Timothy J; Bielinski, Elizabeth A; Pan, Cassie J; Lagaditis, Paraskevi O; Bernskoetter, Wesley H; Takase, Michael K; Würtele, Christian; Hazari, Nilay; Schneider, Sven



Coordination of uranium(VI) with N,N'-diethyl-N,N'-ditolyldipicolinamide  

Microsoft Academic Search

Structural analyses of uranyl complexes with isomers of N,N'-diethyl-N,N'-ditolyl-dipicolinamide were carried out using IR spectroscopy and single crystal x-ray diffraction. From these analyses it was determined that complexation takes place through coordination with the carbonyl and pyridine nitrogen moieties. The uranium-oxygen and uranium-nitrogen bond distances for Et(p)TDPA are U(1)-O(1): 2.394(3), U(1)-O(2): 2.460(3), U(1)-N(1): 2.661(3) and for Et(o)TDPA U(1)-O(1): 2.415(5), U(1)-O(2):

J. L. Lapka; A. Paulenova; L. N. Zakharov; M. Yu Alyapyshev; V. A. Babain



Coordination polymers  

Microsoft Academic Search

This paper is a review of the metal complex forming coordination polymers. A polymer–metal complex is composed of synthetic polymer and metal ions bound to the polymer ligand by a coordinate bond. A polymer ligand contains anchoring sites like nitrogen, oxygen or sulphur obtained either by the polymerization of monomer possessing the coordinating site or by a chemical reaction between

T. Kaliyappan; P. Kannan



ORNL/TM-2008/048 Uranyl Nitrate Flow Loop  

E-print Network

ORNL/TM-2008/048 Uranyl Nitrate Flow Loop October 2008 Jennifer L. Ladd-Lively #12;DOCUMENT Government or any agency thereof. #12;ORNL/TM-2008/048 Nuclear Science and Technology Division URANYL NITRATE

Pennycook, Steve


Seven-coordinate lanthanide sandwich-type complexes with a tetrathiafulvalene-fused Schiff base ligand.  


Three seven-coordinate lanthanide(III) sandwich-type mononuclear complexes with ?-conjugated TTF-Schiff base ligand H2L (L(2-) = 2,2'-((2-(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)-1,3-benzodithiole-5,6-diyl)bis(nitrilomethylidyne)bis(4-chlorophenolate)) and the tripodal ligand L(OEt)(-) (L(OEt)(-) = [(?(5)-C5H5)Co(P(?O)(OEt)2)3](-)), [(L(OEt))Ln(L)]·0.25H2O (Ln(3+) = Dy(3+), 1; Tb(3+), 2; Ho(3+), 3), have been synthesized and structurally characterized. All of the complexes are also characterized by absorption spectra and electrochemical, spectroelectrochemical, and magnetic studies. The Dy complex exhibits the field-induced slow relaxation of magnetization with an energy barrier of 41.6 K, indicating it shows single lanthanide-based SMM behavior. Introduction of the redox-active TTF unit into the sandwich-type lanthanide(III) complexes with interesting magnetic properties renders them promising for elaboration of new hybrid inorganic-organic materials. PMID:24063409

Gao, Feng; Cui, Long; Liu, Wei; Hu, Liang; Zhong, Yu-Wu; Li, Yi-Zhi; Zuo, Jing-Lin



Integrated complex care coordination for children with medical complexity: A mixed-methods evaluation of tertiary care-community collaboration  

PubMed Central

Background Primary care medical homes may improve health outcomes for children with special healthcare needs (CSHCN), by improving care coordination. However, community-based primary care practices may be challenged to deliver comprehensive care coordination to complex subsets of CSHCN such as children with medical complexity (CMC). Linking a tertiary care center with the community may achieve cost effective and high quality care for CMC. The objective of this study was to evaluate the outcomes of community-based complex care clinics integrated with a tertiary care center. Methods A before- and after-intervention study design with mixed (quantitative/qualitative) methods was utilized. Clinics at two community hospitals distant from tertiary care were staffed by local community pediatricians with the tertiary care center nurse practitioner and linked with primary care providers. Eighty-one children with underlying chronic conditions, fragility, requirement for high intensity care and/or technology assistance, and involvement of multiple providers participated. Main outcome measures included health care utilization and expenditures, parent reports of parent- and child-quality of life [QOL (SF-36®, CPCHILD©, PedsQL™)], and family-centered care (MPOC-20®). Comparisons were made in equal (up to 1 year) pre- and post-periods supplemented by qualitative perspectives of families and pediatricians. Results Total health care system costs decreased from median (IQR) $244 (981) per patient per month (PPPM) pre-enrolment to $131 (355) PPPM post-enrolment (p=.007), driven primarily by fewer inpatient days in the tertiary care center (p=.006). Parents reported decreased out of pocket expenses (p<.0001). Parental QOL did not significantly change over the course of the study. Child QOL improved between baseline and 6 months in two PedsQL™ domains [Social (p=.01); Emotional (p=.003)], and between baseline and 1 year in two CPCHILD© domains [Health Standardization Section (p=.04); Comfort and Emotions (p=.03)], while total CPCHILD© score decreased between baseline and 1 year (p=.003). Parents and providers reported the ability to receive care close to home as a key benefit. Conclusions Complex care can be provided in community-based settings with less direct tertiary care involvement through an integrated clinic. Improvements in health care utilization and family-centeredness of care can be achieved despite minimal changes in parental perceptions of child health. PMID:23088792



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

SciTech Connect

Single crystals of Zn{sub 4}(OH){sub 2}[(UO{sub 2})(PO{sub 4}){sub 2}(OH){sub 2}(H{sub 2}O)] (UZnP), Cs[(UO{sub 2})(HPO{sub 4})NO{sub 3}] (UCsP), and In{sub 3}[(UO{sub 2}){sub 2}(PO{sub 4}){sub 4}OH(H{sub 2}O){sub 6}].2H{sub 2}O (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) A; UCsP crystallizes in P-1, a=7.015(2), b=7.441(1), c=9.393(2) A, {alpha}=72.974(2), {beta}=74.261(2), {gamma}=79.498(2); and UInP crystallizes in P-1, a=7.9856(5), b=9.159(1), c=9.2398(6) A {alpha}=101.289(1), {beta}=114.642(1), {gamma}=99.203(2). The U{sup 6+} cations are present as (UO{sub 2}){sup 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. - Graphical abstract: Three new uranyl phosphates with unique structural units are reported. Black-Small-Square Highlights: Black-Right-Pointing-Pointer Three new uranyl phosphates have been synthesized hydrothermally. Black-Right-Pointing-Pointer Single crystal analyses reveal unique structural units. Black-Right-Pointing-Pointer The dimensionality of these compounds deviate from typical U{sup 6+} layered structures.

Wylie, Ernest M.; Dawes, Colleen M. [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN 46556 (United States)] [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN 46556 (United States); Burns, Peter C., E-mail: [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States)



Three new silver uranyl diphosphonates: structures and properties.  


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

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



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

SciTech Connect

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.

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



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

ERIC Educational Resources Information Center

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…

Coe, Benjamin J.



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)

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.

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



Change in the fluorescence of uranyl ions during the hydrolytic reduction of xenon difluoride  

SciTech Connect

The hydrolytic reduction of xenon difluoride in solutions containing uranyl ions has been studied using iodometric titration and recording of the photoluminescence of UO/sub 2//sup 2 +/. It was found that uranyl ions increase the XeF/sub 2/ hydrolysis rate. A theoretical relationship was found between the uranyl ion photolumuinescence intensity and the F- concentration. It was assumed first that under slow ligand exchange conditions, when the radiative deactivation rate exceeds the ligand substitution rate, the complexes (UO/sub 2//sup 2 +/)aq, UO/sub 2/F/sup +/, and UO/sub 2/F/sub 2/ can be considered as independent emitters, and second that instead of the relative luminescence quantum yields the lifetime of the uranyl complexes in the electronically excited state can be used. This relationship is in good agreement with the experimental increase in the photoluminescence intensity of UO/sub 2//sup 2 +/ during the hydrolysis of XeF/sub 2/. There was not detectable spectroscopic evidence for the formation of the complex (UO/sub 2//sup 2 +/ x XeF/sub 2/). The responses of a fluorine-selective electrode were found to give incorrect results when XeF/sub 2/ was present in solution.

Kazakov, B.P.; Afonichev, D.D.; Khamidullina, L.A.; Kuleshov, S.P.



Multiple proton-transfer reactions in DNA base pairs by coordination of pt complex.  


The possibility of multiple proton-transfer reactions in DNA base pairs because of coordination of cisplatin is theoretically elucidated by density functional theory (DFT) and by quantum mechanics/molecular mechanics (QM/MM) methods with an ONIOM method. From the energetics of two base pairs with the cisplatin, it is theoretically confirmed that the Pt complex is likely to bind in the order cis-(CG)-Pt-(GC), cis-(CG)-Pt-(AT), cis-(TA)-Pt-(AT), where G, C, A, and T are guanine, cytosine, adenine, and thymine, respectively, and the Pt atom bonds to the N7 site of G and A. This result supports the experimental evidence, where the structure cis-A-Pt-A is seldom observed at room temperature. The single proton-transfer reaction occurs in one of the two GC pairs. No simultaneous single proton-transfer reaction can occur in both base pairs. Two different single proton-transferred structures (cis-(CG*)(d)-Pt-(GC)(p) and cis-(CG)(d)-Pt-(G*C)(p), where the asterisk means a proton donor of G) are as stable as the original structures (CG)(d)-Pt-(GC)(p). The same tendency was observed with cis-(CG*)-Pt-(AT). In contrast to cisplatin, multiple single proton-transfer reactions occur in the system consisting of two base pairs with transplatin. The optimized structure agrees with the experimental data for Pt-G coordination except for the hydrogen-bonding length. PMID:17266272

Matsui, Toru; Shigeta, Yasuteru; Hirao, Kimihiko



New class of scorpionate: tris(tetrazolyl)-iron complex and its different coordination modes for alkali metal ions.  


We report formation of a new metallascorpionate ligand, [FeL3](3-) (IPtz), containing a Fe core and three 5-(2-hydroxyphenyl)-1H-tetrazole (LH2) ligands. It features two different binding sites, oxygen and nitrogen triangles, which consist of three oxygen or nitrogen donors from tetrazole. The binding affinities of the complex for three alkali metal ions were studied using UV spectrophotometry titrations. All three alkali metal ions show high affinities and binding constants (>3 × 10(6) M(-1)), based on the 1:1 binding isotherms to IPtz. The coordination modes of the alkali metals and IPtz in the solid were studied using X-ray crystallography; two different electron-donor sites show different coordination numbers for Li(+), Na(+), and K(+) ions. The oxygen triangles have the ?(2) coordination mode with Li(+) and ?(3) coordination mode with Na(+) and K(+) ions, whereas the nitrogen triangles show ?(3) coordination with K(+) only. The different binding affinities of IPtz in the solid were manipulated using multiple metal precursors. A Fe-K-Zn trimetallic complex was constructed by assembly of an IPtz ligand, K, and Zn precursors and characterized using X-ray crystallography. Oxygen donors are coordinated with the K ion via the ?(3) coordination mode, and nitrogen donors are coordinated with Zn metal by ?(3) coordination. The solid-state structure was confirmed to be a honeycomb coordination polymer with a one-dimensional infinite metallic array, i.e., -(K-K-Fe-Zn-Fe-K)n-. PMID:25075636

Park, Ka Hyun; Lee, Kang Mun; Go, Min Jeong; Choi, Sung Ho; Park, Hyoung-Ryun; Kim, Youngjo; Lee, Junseong



An integrated X-ray and molecular dynamics study of uranyl-salen structures and properties.  


Uranium complexes of bis(p-tert-butyl-salicylidene)-1,2-diphenylethylenediamine (1) and bis(salicylidene)-1,2-diphenylethylenediamine (2) have been synthesized and investigated by X-ray single crystal diffraction and MD calculations in Periodic Boundary Conditions. Both compounds form crystals which are densely packed and do not provide voids accessible to solvent molecules. The configurations adopted by 1 and 2 are determined by well defined T-shaped and ?-stacking non covalent interactions between phenyl groups of adjacent molecules as well as by a network of hydrogen bonds. These interactions and the relative arrangements of the molecules, explain the packing in the crystal structures. Each uranyl moiety shows a penta-coordination in the equatorial plane perpendicular to the trans oxygens giving rise, in both compounds, to a bypiramidal geometry. As usual for this class of compounds, the 5th position is characterized by the presence of the coordinated solvent. The in silico simulations confirm this hypothesis in very fine details. Moreover, in 1, even the partial occupancy of the solvent molecule determined from the crystal structure refinement, was shown to be due to a constrained freedom of motion of the solvent molecule that can be reproduced by molecular dynamics. This suggests that the reported disorder is not due to a poor quality of the harvested crystals but to a structural feature. In further agreement with the above mentioned results, DFT calculations demonstrated that the molecular orbital configuration and energies suit the described properties of complexes 1 and 2 suggesting a potential enantioselective activity as already shown by molecules belonging to this class of compounds. PMID:22183509

Lombardo, Giuseppe M; Thompson, Amber L; Ballistreri, Francesco P; Pappalardo, Andrea; Sfrazzetto, Giuseppe Trusso; Tomaselli, Gaetano A; Toscano, Rosa M; Punzo, Francesco



Effects of solvent systems on two silver coordination complexes: From discrete structure to 2D sheet  

NASA Astrophysics Data System (ADS)

Two mixed-ligand silver(I) coordination complexes (CCs), [Ag4(mpyz)(npt)2·(H2O)2]n (1) and [Ag4(mpyz) (npt)2]n (2) were synthesized with reactions of methyl-pyrazine(mpyz) and 3-nitro-1,2-benzenedicarboxylic acid (H2npt) with silver nitrate in different solvent systems and were structurally characterized by single-crystal X-ray crystallography. Structural differences of CCs are due to the effects of solvent systems and the intricacy of the self-assembly process for these systems. For 1, the Ag4 unit which is like Y letter which stand upside and down and repeat to form a 1D-63-silver-ring which shares Ag1 and Ag2 only with npt ligands. The eight Ag ions of complex 2 are in a shape like the branches of a tree which repeat to form a 1D silver chain. Effects of solvents on the structures, as well as the intricacy of the self-assembly process were discussed. The photoluminescence, infrared spectroscopy (IR) and thermogravimetric analyses (TGA) behaviors of the compounds were also discussed.

Wang, Dan-Feng; Wang, Zhan-Hui; Lu, Bo-Wei; Chen, Shu-Fen; Zhang, Ting; Huang, Rong-Bin; Zheng, Lan-Sun



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

SciTech Connect

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?

Burns, R.M.; Hubbard, J.L.; McCullough, E.A. Jr. [Pacific Northwest Lab., Richland, WA (United States)] [and others



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


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

López-Torres, Elena; Dilworth, Jonathan R



Metal-metal bonding in low-coordinate dicobalt complexes supported by phosphinoamide ligands.  


Homobimetallic dicobalt complexes featuring metal centers in different coordination environments have been synthesized, and their multielectron redox chemistry has been investigated. Treatment of CoX(2) with MesNKP(i)Pr(2) leads to self-assembly of [(THF)Co(MesNP(i)Pr(2))(2)(?-X)CoX] [X = Cl (1), I (2)], with one Co center bound to two amide donors and the other bound to two phosphine donors. Upon two-electron reduction, a ligand rearrangement occurs to generate the symmetric species (PMe(3))Co(MesNP(i)Pr(2))(2)Co(PMe(3)) (3), where each Co has an identical mixed P/N donor set. One-electron oxidation of 3 to generate a mixed valence species promotes a ligand reararrangement back to an asymmetric configuration in [(THF)Co(MesNP(i)Pr(2))(2)Co(PMe(3))][PF(6)] (4). Complexes 1-4 have been structurally characterized, and their metal-metal interactions are discussed in the context of computational results. PMID:23298415

Mathialagan, Ramyaa; Kuppuswamy, Subramaniam; De Denko, Alexandra T; Bezpalko, Mark W; Foxman, Bruce M; Thomas, Christine M



Efficient water oxidation catalysts based on readily available iron coordination complexes  

NASA Astrophysics Data System (ADS)

Water oxidation catalysis constitutes the bottleneck for the development of energy-conversion schemes based on sunlight. To date, state-of-the-art homogeneous water oxidation catalysis is performed efficiently with expensive, toxic and earth-scarce transition metals, but 3d metal-based catalysts are much less established. Here we show that readily available, environmentally benign iron coordination complexes catalyse homogeneous water oxidation to give O2, with high efficiency during a period of hours. Turnover numbers >350 and >1,000 were obtained using cerium ammonium nitrate at pH 1 and sodium periodate at pH 2, respectively. Spectroscopic monitoring of the catalytic reactions, in combination with kinetic studies, show that high valent oxo-iron species are responsible for the O-O forming event. A systematic study of iron complexes that contain a broad family of neutral tetradentate organic ligands identifies first-principle structural features to sustain water oxidation catalysis. Iron-based catalysts described herein open a novel strategy that could eventually enable sustainable artificial photosynthetic schemes.

Fillol, Julio Lloret; Codolà, Zoel; Garcia-Bosch, Isaac; Gómez, Laura; Pla, Juan José; Costas, Miquel



A spectrochemical walk: single-site perturbation within a series of six-coordinate ferrous complexes.  


A series of ferrous complexes with the pentadentate ligand 2,6-(bis-(bis-2-pyridyl)methoxymethane)pyridine (PY5) was prepared and examined. PY5 binds ferrous iron in a square-pyramidal geometry, leaving a single coordination site accessible for complexation of a wide range of monodentate exogenous ligands: [Fe(II)(PY5)(X)](n+), X = MeOH, H(2)O, MeCN, pyridine, Cl-, OBz-, N(3)-, MeO-, PhO-, and CN-. The spin-states of these ferrous complexes are extremely sensitive to the nature of the single exogenous ligand; the spectroscopic and structural properties correlate with their high-spin (hs) or low-spin (ls) electronic ground state. Systematic metrical trends within six crystallographic structures clearly indicate a preferred conformational binding mode of the PY5 ligand. The relative binding affinities of the exogenous ligands in MeOH indicate that exogenous ligand charge is the primary determinant of the binding affinity; the [Fe(II)(PY5)](2+) unit preferentially binds anionic ligands over neutral ligands. At parity of charge, strong-field ligands are preferentially bound over weak-field ligands. In MeOH, the pK(a) of the exogenously ligated MeOH in [Fe(PY5)(MeOH)](2+) (9.1) limits the scope of exogenous ligands, as strongly basic ligands preferentially deprotonate [Fe(PY5)(MeOH)](2+) to yield [Fe(PY5)(OMe)](1+) rather than ligate to the ferrous center. Exogenous ligation by a strongly basic ligand, however, can be achieved in polar aprotic solvents. PMID:12206687

Goldsmith, Christian R; Jonas, Robert T; Cole, Adam P; Stack, T Daniel P



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

SciTech Connect

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.

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



X-ray emission spectroscopy to study ligand valence orbitals in Mn coordination complexes  

PubMed Central

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 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. PMID:19663435

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



Characterization of Ce SUP 3+-tributyl phosphate coordination complexes produced by fused droplet electrospray ionization with a target capillary  

SciTech Connect

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.

Gary S. Groenewold; Jean-Jacques Gaumet



Electronic Transitions as a Probe of Tetrahedral versus Octahedral Coordination in Nickel(II) Complexes: An Undergraduate Inorganic Chemistry Experiment.  

ERIC Educational Resources Information Center

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)

Filgueiras, Carlos A. L.; Carazza, Fernando



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

NASA Astrophysics Data System (ADS)

The mixed-valence chromium uranyl compounds Li5[(UO2)4(Cr(V)O5)(Cr(VI)O4)4](H2O)17 (1), (Mg(H2O)6)5[(UO2)8(Cr(V)O5)2(Cr(VI)O4)8] (2) and (NH4)5[(UO2)4(Cr(V)O5)(Cr(VI)O4)2]H2O11 (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 H2O groups reside between the sheets of uranyl and chromate polyhedra, where they provide linkages between adjacent sheets.

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



Coordination of tRNA transcription with export at nuclear pore complexes in budding yeast.  


tRNAs are encoded by RNA polymerase III-transcribed genes that reside at seemingly random intervals along the chromosomes of budding yeast. Existing evidence suggests that the genes congregate together at the nucleolus and/or centromeres. In this study, we re-examined spatial and temporal aspects of tRNA gene (tDNA) expression. We show that tDNA transcription fluctuates during cell cycle progression. In M phase, when tRNA synthesis peaks, tDNAs localize at nuclear pore complexes (NPCs). Docking of a tDNA requires the DNA sequence of the contacted gene, nucleoporins Nup60 and Nup2, and cohesin. Characterization of mutants that block NPC localization revealed that docking is a consequence of elevated tDNA transcription. NPC-tDNA contact falters in the absence of the principal exportin of nascent tRNA, Los1, and genetic assays indicate that gating of tDNAs at NPCs favors cytoplasmic accumulation of functional tRNA. Collectively, the data suggest that tDNAs associate with NPCs to coordinate RNA polymerase III transcription with the nuclear export of pre-tRNA. The M-phase specificity of NPC contact reflects a regulatory mechanism that may have evolved, in part, to avoid collisions between DNA replication forks and transcribing RNA polymerase III machinery at NPCs. PMID:24788517

Chen, Miao; Gartenberg, Marc R



Coordination of tRNA transcription with export at nuclear pore complexes in budding yeast  

PubMed Central

tRNAs are encoded by RNA polymerase III-transcribed genes that reside at seemingly random intervals along the chromosomes of budding yeast. Existing evidence suggests that the genes congregate together at the nucleolus and/or centromeres. In this study, we re-examined spatial and temporal aspects of tRNA gene (tDNA) expression. We show that tDNA transcription fluctuates during cell cycle progression. In M phase, when tRNA synthesis peaks, tDNAs localize at nuclear pore complexes (NPCs). Docking of a tDNA requires the DNA sequence of the contacted gene, nucleoporins Nup60 and Nup2, and cohesin. Characterization of mutants that block NPC localization revealed that docking is a consequence of elevated tDNA transcription. NPC–tDNA contact falters in the absence of the principal exportin of nascent tRNA, Los1, and genetic assays indicate that gating of tDNAs at NPCs favors cytoplasmic accumulation of functional tRNA. Collectively, the data suggest that tDNAs associate with NPCs to coordinate RNA polymerase III transcription with the nuclear export of pre-tRNA. The M-phase specificity of NPC contact reflects a regulatory mechanism that may have evolved, in part, to avoid collisions between DNA replication forks and transcribing RNA polymerase III machinery at NPCs. PMID:24788517

Chen, Miao; Gartenberg, Marc R.



Implementation of the external complex scaling method in spheroidal coordinates: Impact ionization of molecular hydrogen  

SciTech Connect

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.

Serov, Vladislav V.; Joulakian, Boghos B. [Department of Theoretical and Nuclear Physics, Saratov State University, 83 Astrakhanskaya, Saratov 410012 (Russian Federation); Laboratoire de Physique Moleculaire et des Collisions, Institut Jean Barriol FR CNRS no 2843, Universite Paul Verlaine-Metz, 1 Rue Arago, 57078 Metz Cedex 3 (France)



Two Zn(II) coordination complexes assembled by trithiocyanuric acid and two different N-donor auxiliary ligands.  


The dipyridyl-type building blocks 4-amino-3,5-bis(pyridin-3-yl)-1,2,4-triazole (3-bpt) and 4,4'-bipyridine (bpy) have been used to assemble with Zn(II) in the presence of trithiocyanuric acid (ttcH3) to afford two coordination compounds, namely bis[4-amino-3,5-bis(pyridin-3-yl)-1,2,4-triazole-?N(3)]bis(trithiocyanurato-?(2)N,S)zinc(II), [Zn(C3H2N3S3)2(C12H10N6)2]·2H2O, (1), and catena-poly[[[bis(trithiocyanurato-?(2)N,S)zinc(II)]-?-4,4'-bipyridine-?(2)N:N'] 4,4'-bipyridine monosolvate], {[Zn2(C3H2N3S3)4(C10H8N2)3]·C10H8N2}n, (2). Single-crystal X-ray analysis indicates that complex (1) is a mononuclear structure, while complex (2) presents a one-dimensional chain coordination motif. In both complexes, the central Zn(II) cation adopts an octahedral geometry, coordinated by four N- and two S-donor atoms. Notably, trithiocyanurate (ttcH2(-)) adopts the same bidentate chelating coordination mode in each complex and exists in the thione tautomeric form. The 3-bpt co-ligand in (1) adopts a monodentate coordination mode and serves as a terminal pendant ligand, whereas the 4,4'-bipyridine (bpy) ligand in (2) adopts a bidentate-bridging coordination mode. The different coordination characters of the different N-donor auxiliary ligands lead to structural diversity for complexes (1) and (2). Further analysis indicates that the resultant three-dimensional supramolecular networks for (1) and (2) arise through intermolecular N-H...S and N-H...N hydrogen bonds. Both complexes have been further characterized by FT-IR spectroscopy and elemental analyses. PMID:25093355

He, Xiao Xiao; Guo, Ya Mei



Two coordination modes around the Cu(II) cations in complexes with benzo[b]furancarboxylic acids  

NASA Astrophysics Data System (ADS)

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.

Drzewiecka, Aleksandra; Koziol, Anna E.; Klepka, Marcin T.; Wolska, Anna; Jimenez-Pulido, Sonia B.; Lis, Tadeusz; Ostrowska, Kinga; Struga, Marta



Interactions of platinum and ruthenium coordination complexes with pancreatic phospholipase A(2) and phospholipids investigated by MALDI TOF mass spectrometry.  


Phospholipase A2 is involved in propagation of inflammatory processes and carcinogenesis through its role in phospholipid metabolism, and release of arachidonic acid and lysophospholipids. Recent findings on correlation between elevated PLA2 activity and metastatic cancer render this enzyme an attractive target for cancer therapy. On the other hand, due to a broad range of oxidation states under physiological conditions and a high affinity for protein binding, platinum and ruthenium coordination complexes are promising candidates for PLA2 inhibitors. In this article, we discuss the interactions of Pt and Ru coordination complexes with PLA2 and phospholipids, as well as the application of MALDI-TOF mass spectrometry for screening PLA2 inhibitors. Owing to the ability of this technique to simultaneously detect and monitor changes in substrate and product concentrations, the inhibitor mechanisms of both Pt and Ru complexes with various ligands were determined. PMID:24243606

Kam?eva, Tina; Radisavljevi?, Maja; Vuki?evi?, Iva; Arnhold, Jürgen; Petkovi?, Marijana



Cyanex based uranyl sensitive polymeric membrane electrodes.  


Novel uranyl selective polymeric membrane electrodes were prepared using three different low-cost and commercially available Cyanex extractants namely, bis(2,4,4-trimethylpentyl) phosphinic acid [L1], bis(2,4,4-trimethylpentyl) monothiophosphinic acid [L2] and bis(2,4,4-trimethylpentyl) dithiophosphinic acid [L3]. Optimization and performance characteristics of the developed Cyanex based polymer membrane electrodes were determined. The influence of membrane composition (e.g., amount and type of ionic sites, as well as type of plasticizer) on potentiometric responses of the prepared membrane electrodes was studied. Optimized Cyanex-based membrane electrodes exhibited Nernstian responses for UO?(2+) ion over wide concentration ranges with fast response times. The optimized membrane electrodes based on L1, L2 and L3 exhibited Nernstian responses towards uranyl ion with slopes of 29.4, 28.0 and 29.3 mV decade(-1), respectively. The optimized membrane electrodes based on L1-L3 showed detection limits of 8.3 × 10(-5), 3.0 × 10(-5) and 3.3 × 10(-6) mol L(-1), respectively. The selectivity studies showed that the optimized membrane electrodes exhibited high selectivity towards UO?(2+) ion over large number of other cations. Membrane electrodes based on L3 exhibited superior potentiometric response characteristics compared to those based on L1 and L2 (e.g., widest linear range and lowest detection limit). The analytical utility of uranyl membrane electrodes formulated with Cyanex extractant L3 was demonstrated by the analysis of uranyl ion in different real samples for nuclear safeguards verification purposes. The results obtained using direct potentiometry and flow-injection methods were compared with those measured using the standard UV-visible and inductively coupled plasma spectroscopic methods. PMID:24274282

Badr, Ibrahim H A; Zidan, W I; Akl, Z F




E-print Network

Department of Physical Chemistry, Sciences II, University of Geneva 30, Quai Ernest Ansermet, 1211 Geneva 4 (Switzerland) Laura Gagliardi University of Minnesota, Department of Chemistry, 207 Pleasant St. SE Minneapolis leads to complexes with coordination numbers higher than 12. Although 14-coordinate actinide complexes

Girolami, Gregory S.


New class of phosphine oxide donor-based supramolecular coordination complexes from an in situ phosphine oxidation reaction or phosphine oxide ligands.  


A one-pot, multicomponent, coordination-driven self-assembly approach was used to synthesize the first examples of neutral bridging phosphine oxide donor-based supramolecular coordination complexes. The complexes were self-assembled from a fac-Re(CO)3 acceptor, an anionic bridging O donor, and a neutral soft phosphine or hard phosphine oxide donor. PMID:23984852

Shankar, Bhaskaran; Elumalai, Palani; Shanmugam, Ramasamy; Singh, Virender; Masram, Dhanraj T; Sathiyendiran, Malaichamy



Role of apoptosis in uranyl acetate-induced acute renal failure and acquired resistance to uranyl acetate  

Microsoft Academic Search

Role of apoptosis in uranyl acetate-induced acute renal failure and acquired resistance to uranyl acetate.BackgroundWe have previously reported that animals recovering from uranyl acetate (UA)-induced acute renal failure (ARF) were resistant to subsequent insult. Recent evidence suggests that apoptosis participates in tubular damage. We investigated the role of apoptosis in UA-induced ARF and attenuation of ARF in acquired resistance to

Koji Sano; Yoshihide Fujigaki; Takehiko Miyaji; Naoki Ikegaya; Kazuhisa Ohishi; Katsuhiko Yonemura; Akira Hishida



Structural Insights into Complete Metal Ion Coordination from Ternary Complexes of B Family RB69 DNA Polymerase  

SciTech Connect

We have captured a preinsertion ternary complex of RB69 DNA polymerase (RB69pol) containing the 3' hydroxyl group at the terminus of an extendable primer (ptO3') and a nonhydrolyzable 2'-deoxyuridine 5'-{alpha},{beta}-substituted triphosphate, dUpXpp, where X is either NH or CH{sub 2}, opposite a complementary templating dA nucleotide residue. Here we report four structures of these complexes formed by three different RB69pol variants with catalytically inert Ca{sup 2+} and four other structures with catalytically competent Mn{sup 2+} or Mg{sup 2+}. These structures provide new insights into why the complete divalent metal-ion coordination complexes at the A and B sites are required for nucleotidyl transfer. They show that the metal ion in the A site brings ptO3' close to the {alpha}-phosphorus atom (P{alpha}) of the incoming dNTP to enable phosphodiester bond formation through simultaneous coordination of both ptO3' and the nonbridging Sp oxygen of the dNTP's {alpha}-phosphate. The coordination bond length of metal ion A as well as its ionic radius determines how close ptO3' can approach P{alpha}. These variables are expected to affect the rate of bond formation. The metal ion in the B site brings the pyrophosphate product close enough to P{alpha} to enable pyrophosphorolysis and assist in the departure of the pyrophosphate. In these dUpXpp-containing complexes, ptO3' occupies the vertex of a distorted metal ion A coordination octahedron. When ptO3' is placed at the vertex of an undistorted, idealized metal ion A octahedron, it is within bond formation distance to P{alpha}. This geometric relationship appears to be conserved among DNA polymerases of known structure.

Xia, Shuangluo; Wang, Mina; Blaha, Gregor; Konigsberg, William H.; Wang, Jimin (Yale)



Mdm10 as a dynamic constituent of the TOB/SAM complex directs coordinated assembly of Tom40.  


The mitochondrial outer membrane contains two protein translocators: the TOM40 and TOB/SAM complexes. Mdm10 is distributed in the TOB complex for beta-barrel protein assembly and in the MMM1 complex for tethering of the endoplasmic reticulum and mitochondria. Here, we establish a system in which the Mdm10 level in the TOB complex--but not in the MMM1 complex--is altered to analyse its part in beta-barrel protein assembly. A decrease in the Mdm10 level results in accumulation of in vitro imported Tom40, which is a beta-barrel protein, at the level of the TOB complex. An increase in the Mdm10 level inhibits association not only of Tom40 but also of other beta-barrel proteins with the TOB complex. These results show that Mdm10 regulates the timing of release of unassembled Tom40 from the TOB complex, to facilitate its coordinated assembly into the TOM40 complex. PMID:20111053

Yamano, Koji; Tanaka-Yamano, Sachiko; Endo, Toshiya



Mononuclear complexes of amide-based ligands containing appended functional groups: role of secondary coordination spheres on catalysis.  


Amide-based ligands H2L(1), H2L(2) and H2L(3) containing thiazole, thiazoline and benzothiazole appended groups have been used to synthesize Zn(2+) ( and ), Cd(2+) complexes ( and ), and a Mn(2+) complex (). In all cases, potentially multidentate ligands create a meridional N3 coordination environment around the M(ii) ion whereas additional sites are occupied by labile nitrate ions in and MeOH in . Interestingly, metal complexation caused the migration of protons from amidic N-H sites to the appended heterocyclic rings in complexes . Structural studies show that the protonated heterocyclic rings in these complexes create a hydrogen bond based cavity adjacent to the metal ion. Importantly, binding studies confirm that the substrates are bound within the complex cavity closer to the Lewis acidic metal in all complexes including the oxidation-sensitive Mn ion in complex . All complexes have been utilized as the reusable and heterogeneous catalysts for ring-opening reactions of assorted epoxides, cyanation reactions of various aldehydes, and epoxidation reactions of several olefins. PMID:25166631

Bansal, Deepak; Kumar, Gulshan; Hundal, Geeta; Gupta, Rajeev



Preparation, structure and coordination properties of (? 6- p-cymene)ruthenium(II) sandwich complexes of catechol and 5-hydroxyindole derivatives  

Microsoft Academic Search

Bis(?6-arene)ruthenium(II) complexes of the type [(?6-cymene)Ru(?6-L)](CF3SO3)n (2–7), n=2–3, containing catechol and 5-hydroxyindole derivatives L may be prepared by treatment of [(?6-cymene)Ru(acetone)3](CF3SO3)2 with the appropriate compound in CF3COOH. For the l-Dopa and H-dopamine complexes 2 (n=2) and 3 (n=3), ?6-coordination leads to a dramatic reduction of more than 6 units in pKa to values of, respectively 3.67(3) and 3.98(7) for the

Anke Schlüter; Kirsten Bieber; William S Sheldrick



Three-coordinate gold(I) N-heterocyclic carbene complexes: a new class of strongly luminescent derivatives.  


A selected group of cationic three-coordinate Au(I)-NHC complexes of the form [Au(NHC)(dppbz)]OTf have been prepared from a commercially available bidentate phosphine. All complexes have been fully characterised by NMR and mass spectroscopy. The [Au(NHC)](+) fragment shows a pronounced tendency to form linear complexes which is confirmed by the molecular structure of [Au(IPr)(dppbz)]OTf in the solid state. The complexes are brightly luminescent and present very high quantum yield values in the solid state. The assignments of the electronic transitions involved in the emissions are of a phosphorescent nature and it is proposed that the origin of the emissions is derived from the ligand (dppbz) to metal-ligand (Au-NHC) charge-transfer (LML'CT) transition. PMID:24105255

Visbal, Renso; López-de-Luzuriaga, José M; Laguna, Antonio; Gimeno, M Concepción



Bis-tetradentate complexes of Cd(ii) and Hg(ii) with N8 coordination: structural and NMR comparisons.  


Tripodal N4 ligands tris[(1-methylimidazol-2-yl)methyl]amine (), bis[(1-methylimidazol-2-yl)methyl][(2-pyridyl)methyl]amine () and [(1-methylimidazol-2-yl)methyl]-bis-[(2-pyridyl)methyl]amine () were used to prepare five new [ML2](ClO4)2 (M = Cd(ii), Hg(ii)) complexes. All complexes had N8 metal coordination and a trans-bicapped octahedral structure as determined by X-ray crystallography. Metal-nitrogen bond distances generally decreased in the order M-Namine > M-Npyridyl > M-Nimidazoyl, and the perchlorates were well separated from the metal ions. Variable temperature solution state (1)H NMR spectroscopy revealed conditions for slow intramolecular reorganization were more readily accessible for the Cd(ii) complexes than for the Hg(ii) complexes. Both protons of imidazoyl ring ligand components had large, comparable J((199)Hg(1)H) despite sizable differences in nuclear separation. PMID:25250538

Bowers, Edith V; Murphy, Geoffrey S; Till, Stephanie N; VandenBussche, Christopher J; Yaroschak, Melissa M; Pike, Robert D; Butcher, Raymond J; Bebout, Deborah C



Carbene Rearrangements in Three-Coordinate N-Heterocyclic Carbene Complexes of Cobalt(II) Bis(trimethylsilyl)amide.  


The synthesis and molecular structures of the cobalt(II) N-heterocyclic carbene (NHC) complexes [(NHC)Co{N(SiMe3)2}2], where NHC = 1,3-bis(diisopropylphenyl)imidazolylidene (IPr) (6), 1,3-bis(mesityl)imidazolylidene (IMes) (7), and 1,3-bis(tert-butyl)imidazol-2-ylidene (I(t)Bu) (8), are reported. Complexes 6-8 are rare examples of three-coordinate cobalt NHC complexes. The steric congestion within the coordination environments of the cobalt(II) centers in 6 and 7 results in the longest Co-C(NHC) distances currently known. Investigating the thermal stability of 6-8, we have found that the steric congestion in 6 is such that heating the complex to reflux in toluene prompts a rearrangement from the normal, C2-bonding mode of the IPr ligand to the corresponding "abnormal" or mesoionic bonding mode. The rearrangement results in formation of [(aIPr)Co{N(SiMe3)2}2] (9), which is the first cobalt complex of an abnormal NHC ligand. The Co-C bond in 9 is 0.06 Å shorter than the analogous bond in 6, suggesting that, although the rearrangement occurs due to the spatial demands of the IPr ligand, there is also a thermodynamic driving force in terms of the Co-C bond. In contrast to the case for 6, complex 7 is stable with respect to the normal-to-abnormal rearrangement. Refluxing complex 8 in toluene results in activation of a tert-butyl substituent, which is eliminated as isobutene, followed by formation of the 1-tert-butylimidazole complex [((t)BuIm)Co{N(SiMe3)2}2] (10). PMID:25203858

Day, Benjamin M; Pal, Kuntal; Pugh, Thomas; Tuck, Jessica; Layfield, Richard A



Synthesis and crystal structure of a four-coordinate aryloxo samarium complex [Sm(OAr) 3(THF)](THF) (OAr = 2.6-ditertbutyl-4-methylphenoxo)  

Microsoft Academic Search

The aryloxo samarium complex [Sm(ArO)3(THF)](THF) has been prepared by the reaction of SmCl3 with 3 equiv. of NaOAr in THF. An X-ray crystallographic analysis shows the complex to be a four-coordinate aryloxide complex. Three oxygen atoms of aryloxo and one oxygen atom of THF coordinate to the samarium to form a distorted tetrahedron. The average Sm?O(Ar) distance is 2.151(7) Å.

Qi Shen



Uranyl and Arsenate Cosorption on Aluminum Oxide Surface  

SciTech Connect

In this study, we examined the effects of simultaneous adsorption of aqueous arsenate and uranyl onto aluminum oxide over a range of pH and concentration conditions. Arsenate was used as a chemical analog for phosphate, and offers advantages for characterization via X-ray absorption spectroscopy. By combining batch experiments, speciation calculations, X-ray absorption spectroscopy, and X-ray diffraction, we investigated the uptake behavior of uranyl, as well as the local and long-range structure of the final sorption products. In the presence of arsenate, uranyl sorption was greatly enhanced in the acidic pH range, and the amount of enhancement is positively correlated to the initial arsenate and uranyl concentrations. At pH 4-6, U L{sub III-} and As K-edge EXAFS results suggest the formation of surface-sorbed uranyl and arsenate species as well as uranyl arsenate surface precipitate(s) that have a structure similar to tr{umlt o}gerite. Uranyl polymeric species or oxyhydroxide precipitate(s) become more important with increasing pH values. Our results provide the basis for predictive models of the uptake of uranyl by aluminum oxide in the presence of arsenate and (by analogy) phosphate, which can be especially important for understanding phosphate-based uranium remediation systems.

Tang, Y.; Reeder, R



Pro-oxidative, genotoxic and cytotoxic properties of uranyl ions.  


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

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



Removal and recovery of uranyl ion using various microorganisms.  


The adsorption of uranyl ion by microorganisms was examined. Among the 76 strains of 69 species tested (23 bacteria, 20 actinomycetes, 18 fungi, and 15 yeasts), high uranyl ion adsorption ability was exhibited by strains of the bacteria, Arthrobacter nicotianae, Bacillus subtilis, and Micrococcus luteus. A. nicotianae cells, which showed the best performance, could adsorb about 698 mg uranyl ion (2.58 mmol) per gram dry wt. of microbial cells. The adsorption of uranyl ion was rapid, selective, and mostly dependent on physico-chemical binding to the cell components. As well as uranyl ion, A. nicotianae could adsorb thorium ion with high efficiency. Cells immobilized with polyacrylamide gel could be used during repeated adsorption-desorption cycles. PMID:16233264

Tsuruta, Takehiko



Behavior of the potential antitumor V(IV)O complexes formed by flavonoid ligands. 1. Coordination modes and geometry in solution and at the physiological pH.  


The coordination modes and geometry assumed in solution by the potent antitumor oxidovanadium(IV) complexes formed by different flavonoids were studied by spectroscopic (Electron Paramagnetic Resonance, EPR) and computational (Density Functional Theory, DFT) methods. A series of bidentate flavonoid ligands (L) with increasing structural complexity was examined, which can involve (CO, O(-)) donors and formation of five- and six-membered chelate rings, or (O(-), O(-)) donors and five-membered chelate rings. The geometry corresponding to these coordination modes can be penta-coordinated, [VOL2], or cis-octahedral, cis-[VOL2(H2O)]. The results show that, at physiological pH, ligands provided with (CO, O(-)) donor set yield cis-octahedral species with "maltol-like" coordination when five-membered chelate rings are formed (as with 3-hydroxyflavone), while penta-coordinated structures with "acetylacetone-like" coordination are preferred when the chelate rings are six-membered (as with chrysin). When both the binding modes are possible, as with morin, the "acetylacetone-like" coordination is observed. For the ligands containing a catecholic donor set, such as 7,8-dihydroxyflavone, baicalein, fisetin, quercetin and rutin, the formation of square pyramidal complexes with (O(-), O(-)) "catechol-like" coordination and five-membered chelate rings is preferred at physiological pH. The determination of the different coordination modes and geometry is important to define the biotransformation in the blood and the interaction of these complexes with the biological membranes. PMID:25127230

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



Pillared and open-framework uranyl diphosphonates  

SciTech Connect

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 a three-dimensional network of pillared structures of uranyl diphosphonates that fluoresce. > The fluorination of the phenyl ring under hydrothermal condition. > The large voids in this structure are suggestive of potential applications in sorption, separation of gases and in catalytic processes.

Adelani, Pius O. [Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Chemistry and Biochemistry, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, IN 46556 (United States); Albrecht-Schmitt, Thomas E., E-mail: [Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Chemistry and Biochemistry, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, IN 46556 (United States)



Merging of Healthy Motor Modules Predicts Reduced Locomotor Performance and Muscle Coordination Complexity Post-Stroke  

E-print Network

if such an organization applies to coordination of human walking, nor how nervous system injury may alter the organization, 2009; doi:10.1152/jn.00825.2009. Evidence suggests that the nervous system controls motor tasks using systems. I N T R O D U C T I O N Human movements exhibit considerable variability from trial to trial


Making Oxidation Potentials Predictable: Coordination of Additives Applied to the Electronic Fine Tuning of an Iron(II) Complex.  


This work examines the impact of axially coordinating additives on the electronic structure of a bioinspired octahedral low-spin iron(II) N-heterocyclic carbene (Fe-NHC) complex. Bearing two labile trans-acetonitrile ligands, the Fe-NHC complex, which is also an excellent oxidation catalyst, is prone to axial ligand exchange. Phosphine- and pyridine-based additives are used for substitution of the acetonitrile ligands. On the basis of the resulting defined complexes, predictability of the oxidation potentials is demonstrated, based on a correlation between cyclic voltammetry experiments and density functional theory calculated molecular orbital energies. Fundamental insights into changes of the electronic properties upon axial ligand exchange and the impact on related attributes will finally lead to target-oriented manipulation of the electronic properties and consequently to the effective tuning of the reactivity of bioinspired systems. PMID:25333790

Haslinger, Stefan; Kück, Jens W; Hahn, Eva M; Cokoja, Mirza; Pöthig, Alexander; Basset, Jean-Marie; Kühn, Fritz E



Coordination Polymer: Synthesis, Spectral Characterization and Thermal Behaviour of Starch-Urea Based Biodegradable Polymer and Its Polymer Metal Complexes  

PubMed Central

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

Malik, Ashraf; Parveen, Shadma; Ahamad, Tansir; Alshehri, Saad M.; Singh, Prabal Kumar; Nishat, Nahid



Using Coordinated Atomic Actions to Design Complex Safety-Critical Systems: The Production Cell Case Study  

Microsoft Academic Search

: Coordinated Atomic actions (CA actions) provide a scheme for coordinatingcomplex concurrent activities and supporting error recovery betweenmultiple interacting objects in a distributed object-oriented system. In this paperwe show how CA actions can be applied to two different areas: safety-criticalsystems and fault-tolerant parallel systems. We have used a Production Cellcase study to show how we can use CA actions to

A. f. Zorzo; A. Romanovsky; J. Xu; B. Randell; R. j. Stroud



Identification of Coordinating Ligand Atoms in Cu(calcimycin) 2 Complex from EPR Linewidths in Chloroform Solutions  

NASA Astrophysics Data System (ADS)

The X-band EPR spectra of Cu(cal) 2 complex in CHCl 3 solutions (cal = calcimycin) do not show resolved 14N hyperfine structure (J. S. Puskin and T. E. Gunter, Biochemistry14, 187, 1975) even though they are expected from the nitrogen coordination to divalent metal ions inferred by NMR acid by model building (C. M. Deber and D. R. Pfeiffer, Biochemistry15, 132, 1976). In the present work, unresolved hyperfine structure from two equivalent 14N has been inferred in the EPR spectra of Cu(cal) 2 from an analysis of linewidths and lineshapes of mI = {3}/{2} and {1}/{2} transitions at 298 K and mI = {3}/{2} transition at 253 K, in CHCl 3 solutions ( mI = nuclear magnetic quantum number associated with the Cu hyperfine transition); g(parallel to); g|| - g?(=0.24), | A|| - A?| (=131 G), and 14N hyperfine constant AN (˜11.3 G) determined from liquid solution linewidth studies in this work favor a solution structure of the complex in which two nitrogens and two oxygens are involved in the square-planar coordination at the metal ion similar to that suggested on the basis of the model for Ca(cal) 2 complex.

Prabhananda, B. S.; Kombrabail, M. H.


Liquid-liquid extraction of uranyl by an amide ligand: interfacial features studied by MD and PMF simulations.  


We report a molecular dynamics study of biphasic systems involved in the liquid-liquid extraction of uranyl nitrate by a monoamide ligand (L = N,N-di(2-ethylhexyl)isobutyramide, DEHiBA) to hexane, from pH neutral or acidic (3 M nitric acid) aqueous solutions. We first describe the neat interfaces simulated with three electrostatic models, one of which including atomic polarizabilities. The free energy profiles for crossing the water/hexane interface by L or its UO2(NO3)2L2 complex are then investigated by PMF (potential of mean force) calculations. They indicate that the free ligand and its complex are surface active. With the polarizable force field, however, the complexes have a lower affinity for the interface than without polarization. When DEHiBA gets more concentrated and in acidic conditions, their surface activity diminishes. Surface activity of UO2(NO3)2L2 complexes is further demonstrated by demixing simulations of randomly mixed DEHiBA, hexane, and neutral or acidic water. Furthermore, demixing of randomly mixed solvents, L molecules, UO2(NO3)2 salts, and nitric acid shows in some cases complexation of L to form UO2(NO3)2L2 and UO2(NO3)2L complexes that adsorb at the aqueous interfaces. These features suggest that uranyl complexation by amide ligands occurs "right at the interface", displaying marked analogies with the liquid-liquid extraction of uranyl by TBP (tri-n-butyl phosphate). Regarding the positive effect of nitric acid on extraction, the simulations point to several facets involving enhanced ion pairing of uranyl nitrate, decreased affinity of the complex for the interface, and finally, stabilization of the complex in the organic phase. PMID:23746355

Benay, G; Wipff, G



Dance choreography is coordinated with song repertoire in a complex avian display.  


All human cultures have music and dance, and the two activities are so closely integrated that many languages use just one word to describe both. Recent research points to a deep cognitive connection between music and dance-like movements in humans, fueling speculation that music and dance have coevolved and prompting the need for studies of audiovisual displays in other animals. However, little is known about how nonhuman animals integrate acoustic and movement display components. One striking property of human displays is that performers coordinate dance with music by matching types of dance movements with types of music, as when dancers waltz to waltz music. Here, we show that a bird also temporally coordinates a repertoire of song types with a repertoire of dance-like movements. During displays, male superb lyrebirds (Menura novaehollandiae) sing four different song types, matching each with a unique set of movements and delivering song and dance types in a predictable sequence. Crucially, display movements are both unnecessary for the production of sound and voluntary, because males sometimes sing without dancing. Thus, the coordination of independently produced repertoires of acoustic and movement signals is not a uniquely human trait. PMID:23746637

Dalziell, Anastasia H; Peters, Richard A; Cockburn, Andrew; Dorland, Alexandra D; Maisey, Alex C; Magrath, Robert D



Highly emissive, nine-coordinate enantiopure lanthanide complexes incorporating tetraazatriphenylenes as probes for DNA.  


The interaction of q = 0 delta- and lambda-Tb and Eu complexes with poly(dAdT), poly(dGdC) and calf-thymus DNA has been examined by absorption, emission and chiroptical spectroscopy and is sensitive to complex helicity, base-pair type and the nature of the lanthanide excited state. PMID:12123030

Bobba, Gabriella; Frias, Juan C; Parker, David



Coordinate Regulation of Complex T Cell Populations Responding to Bacterial Infection  

Microsoft Academic Search

Bacterial infections activate complex T cell populations that differ in size and antigen specificity. We used tetramerized MHC class I molecules complexed with Listeria monocytogenes–derived epitopes to characterize four distinct CD8+ T lymphocyte populations during bacterial infection. Surprisingly, T cell populations differing in antigen specificity expand, contract, and enter the T cell memory compartment synchronously. Because the four L. monocytogenes

Dirk H Busch; Ingrid M Pilip; Sujata Vijh; Eric G Pamer




Microsoft Academic Search

The preparation of cis- and trans-1,2-bis(2-pyridyl)-ethylene (BPE) is described and the different coordination behavior of the two isomers on the basis of their complexes with nickel(II) and zinc(II) are discussed. Fourteen new complexes have been prepared and characterized utilizing electronic spectra, vibrational spectra (conventional and far-infrared), magnetism, electrolytic conductance, and thermal analysis. Eleven further complexes could be detected by thermal

E. Bayer; E. G. Witte



Uranyl Incorporation in Organic-Bearing Soil Calcite  

NASA Astrophysics Data System (ADS)

Phosphor imaging and fission track maps reveal a close correlation between uranium and organic-rich calcite that lines roots in an ancient caliche soil. Concordant U-Pb ages show that this uranium has not been mobilized since the soil calcite formed 298 ñ 1 Ma ago. Luminescence spectroscopic analysis of the organic-rich calcite demonstrates that uranium is present in the oxidized state. More or less comparable luminescence spectra were collected using a CW lamp at room temperature and at liquid nitrogen (LN2) temperature. Spectra for inorganic U species are generally greatly enhanced at liquid nitrogen temperatures over room temperature and thus the similarity may suggest that the U is bound to organic matter. UV-excitation Raman spectroscopy of the calcite samples reveals a vibrational signature that is, in addition to the calcite peaks, essentially identical to that of sodium humate, acquired under similar conditions and consistent with those reported previously for humate substances. Since these spectra are dominated by the carbon backbone structure, the persistence of a carbon backbone structure is noted, but persistence of the ligating functional groups cannot be proven directly. We suggest that this sample records a snapshot of the process of uranium complexation with organic acids in natural systems. In our model organic acids with active functional groups that complex uranyl are sorbed onto the calcite surface and then incorporated as humate into the mineral with further calcite precipitation. Further, the uranyl complex is preserved through near-surface reducing conditions and temperatures to the conditions associated with 2700 meters burial depths. These combined observations suggest that the encapsulating calcite not only prevents reduction of uranium in the surface environment, but also inhibits the breakdown of the humate with burial. Due to the long time scale of immobilization of uranium, evidenced by the age of the calcite, this study has profound implications for understanding sampling for U-series and U-Pb dating of carbonates as well as for developing strategies for nuclear waste management. This study also has implications for any other deposits where uranium is associated with organic matter.

Rasbury, E.; Tait, C.; Donohoe, R. J.



A six-coordinate ytterbium complex exhibiting easy-plane anisotropy and field-induced single-ion magnet behavior.  


The field-induced blockage of magnetization behavior was first observed in an Yb(III)-based molecule with a trigonally distorted octahedral coordination environment. Ab initio calculations and micro-SQUID measurements were performed to demonstrate the exhibition of easy-plane anisotropy, suggesting the investigated complex is the first pure lanthanide field-induced single-ion magnet (field-induced SIM) of this type. Furthermore, we found the relaxation time obeys a power law instead of an exponential law, indicating that the relaxation process should be involved a direct process rather than an Orbach process. PMID:22799446

Liu, Jun-Liang; Yuan, Kang; Leng, Ji-Dong; Ungur, Liviu; Wernsdorfer, Wolfgang; Guo, Fu-Sheng; Chibotaru, Liviu F; Tong, Ming-Liang



A First-principles Study of Spin-polarized Transport Properties of a Co-coordination Complex  

NASA Astrophysics Data System (ADS)

Based on non-equilibrium Green's function formalism and density functional theory calculations, we investigate the spin-polarized transport properties of a Co-coordination complex between two gold electrodes, in which a Co ion is trapped between two 4-mercaptopyridine molecules. Our results demonstrate that the transmission spectra of the system show distinctive features in the spin-up and spin-down channels. Moreover, the current-voltage curves confirm that the system can exhibit robust spin-filtering effect at finite bias voltage, giving the system potential in molecular spintronics applications.

Wu, Qiu-Hua; Zhao, Peng; Liu, De-Sheng



Vinylimidazole copolymers: coordination chemistry, solubility, and cross-linking as function of Cu 2+ and Zn 2+ complexation  

Microsoft Academic Search

P(1-VIm-co-MMA) copolymers with 4 or 44 wt.% 1-VIm (abbreviated PVM-4 and PVM-44) where polymerized from 1-VIm (1-vinylimidazole)\\u000a and methylmethacrylate with azobisisobutyronitrile as initiator and reacted with either Cu2+ or Zn2+. The resulting coordinated polymer complexes were studied using ICP-AES, CP\\/MAS 13C NMR, conductivity measurements, vibrational spectroscopy (mid-FTIR and far-FTIR), DSC, and EPR. It was established by ICP-AES,\\u000a CP\\/MAS 13C NMR, conductivity,

Markus Andersson; Örjan Hansson; Lars Öhrström; Alexander Idström; Magnus Nydén


A DFT based assessment of coordination modes of the bis(1-methyl-2-imidazolyl)glyoxal ligand in mononuclear and dinuclear complexes  

Microsoft Academic Search

The ligand bis(1-methyl-2-imidazolyl)glyoxal (big) was studied by DFT with respect to energy minimum conformations in the neutral, cation and anion radical states. Coordination alternatives involving chelate rings of different size were calculated for the partly experimentally accessible mononuclear complexes of big with [AuCl2]+, [Rh(C5R5)Cl]+ and Re(CO)3Cl. Comparative DFT calculations of various coordination modes for mononuclear, homodinuclear and heterodinuclear complexes of

Orkan Sarper; Ece Bulak; Wolfgang Kaim; Tereza Varnali



Determination of uranyl incorporation into biogenic manganese oxides using X-ray absorption spectroscopy and scattering  

USGS Publications Warehouse

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.

Webb, S.M.; Fuller, C.C.; Tebo, B.M.; Bargar, J.R.



Structural changes within the alkaline earth uranyl phosphites.  


Three new alkaline earth (AE) uranyl phosphites and one barium uranium(IV) phosphate were synthesized under hydrothermal conditions. The carbonate salts of the AE's were employed both as cation sources and as pH regulators. Despite having very similar formulas and uranyl building units, the Ca(2+), Sr(2+) and Ba(2+) uranyl phosphites have three different extended networks. The calcium compound also contains a Ca(2+)/UO2(2+) mixed cation position. The four structure types will be presented herein with the AE cations generating distinct structural transformations. PMID:23677038

Villa, Eric M; Diwu, Juan; Alekseev, Evgeny V; Depmeier, Wulf; Albrecht-Schmitt, Thomas E



Dynamic Resectorization and Coordination Technology: An Evaluation of Air Traffic Control Complexity  

NASA Technical Reports Server (NTRS)

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.

Brinton, Christopher R.



The Drosophila Enhancer of split Gene Complex: Architecture and Coordinate Regulation by Notch, Cohesin, and Polycomb Group Proteins  

PubMed Central

The cohesin protein complex functionally interacts with Polycomb group (PcG) silencing proteins to control expression of several key developmental genes, such as the Drosophila Enhancer of split gene complex [E(spl)-C]. The E(spl)-C contains 12 genes that inhibit neural development. In a cell line derived from the central nervous system, cohesin and the PRC1 PcG protein complex bind and repress E (spl)-C transcription, but the repression mechanisms are unknown. The genes in the E(spl)-C are directly activated by the Notch receptor. Here we show that depletion of cohesin or PRC1 increases binding of the Notch intracellular fragment to genes in the E(spl)-C, correlating with increased transcription. The increased transcription likely reflects both direct effects of cohesin and PRC1 on RNA polymerase activity at the E(spl)-C, and increased expression of Notch ligands. By chromosome conformation capture we find that the E(spl)-C is organized into a self-interactive architectural domain that is co-extensive with the region that binds cohesin and PcG complexes. The self-interactive architecture is formed independently of cohesin or PcG proteins. We posit that the E(spl)-C architecture dictates where cohesin and PcG complexes bind and act when they are recruited by as yet unidentified factors, thereby controlling the E(spl)-C as a coordinated domain. PMID:23979932

Schaaf, Cheri A.; Misulovin, Ziva; Gause, Maria; Koenig, Amanda; Dorsett, Dale



New 2011 survey of patients with complex care needs in eleven countries finds that care is often poorly coordinated.  


Around the world, adults with serious illnesses or chronic conditions account for a disproportionate share of national health care spending. We surveyed patients with complex care needs in eleven countries (Australia, Canada, France, Germany, the Netherlands, New Zealand, Norway, Sweden, Switzerland, the United Kingdom, and the United States) and found that in all of them, care is often poorly coordinated. However, adults seen at primary practices with attributes of a patient-centered medical home--where clinicians are accessible, know patients' medical history, and help coordinate care--gave higher ratings to the care they received and were less likely to experience coordination gaps or report medical errors. Throughout the survey, patients in Switzerland and the United Kingdom reported significantly more positive experiences than did patients in the other countries surveyed. Reported improvements in the United Kingdom tracked with recent reforms there in health care delivery. Patients in the United States reported difficulty paying medical bills and forgoing care because of costs. Our study indicates a need for improvement in all countries through redesigning primary care, developing care teams accountable across sites of care, and managing transitions and medications well. The United States in particular has opportunities to learn from diverse payment innovations and care redesign efforts under way in the other study countries. PMID:22072063

Schoen, Cathy; Osborn, Robin; Squires, David; Doty, Michelle; Pierson, Roz; Applebaum, Sandra



Optical design of reflectionless complex media by finite embedded coordinate transformations.  


Transformation optics offers an unconventional approach to the control of electromagnetic fields. The transformation optical structures proposed to date, such as electromagnetic "invisibility" cloaks and concentrators, are inherently reflectionless and leave the transmitted wave undisturbed. Here, we expand the class of transformation optical structures by introducing finite, embedded coordinate transformations, which allow the electromagnetic waves to be steered or focused. We apply the method to the design of several devices, including a parallel beam shifter and a beam splitter, both of which are reflectionless and exhibit unusual electromagnetic behavior as confirmed by 2D full-wave simulations. PMID:18352474

Rahm, Marco; Cummer, Steven A; Schurig, David; Pendry, John B; Smith, David R



Complexation of Lanthanides with Nitrate at Variable Temperatures: Thermodynamics and Coordination Modes  

SciTech Connect

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.

Rao, Linfeng; Tian, Guoxin



Coordinate expression of the murine Hox-5 complex homoeobox-containing genes during limb pattern formation  

Microsoft Academic Search

The homoeobox-containing genes of the Hox-5 complex are expressed in different but overlapping domains in limbs during murine development. The more 5' the position of these genes in the complex, the later and more distal is their expression. Antero-posterior differences are also observed. A model is proposed that accounts for the establishment of these expression domains in relation to the

Pascal Dollé; Juan-Carlos Izpisúa-Belmonte; Hildegard Falkenstein; Armand Renucci; Denis Duboule



2-(N-Alkylcarboxamide)-6-iminopyridyl palladium and nickel complexes: coordination chemistry and catalysis.  


The 2-(N-alkylcarboxamide)-6-iminopyridine ligands (L1-L7) can bind as either mono-anionic tridentate N^N^N ligands on reaction with PdCl(2)(CH(3)CN)(2), to form complexes LPdCl (C1-C7), or as neutral tridentate N^N^O ligands with NiCl(2)·6H(2)O, to produce complexes LNiCl(2) (C8-C14). All metal complexes were characterized by IR spectroscopy and elemental analysis, and in the case of the palladium complexes, by (1)H and (13)C NMR spectroscopy. The crystal structures of C3, C4, C6, C10, and C12 were determined by X-ray crystallography, and revealed a distorted square geometry around the palladium centre, whereas for nickel, a distorted square-pyramidal geometry was adopted. The representative palladium complex (C3) was further reacted with AgBF(4) in acetonitrile affording the salt [L3Pd(CH(3)CN)][BF(4)] (C15) and the structure of this was confirmed by single-crystal X-ray diffraction. By contrast, carrying out the reaction in dichloromethane rather than acetonitrile, in the presence of malononitrile (CNCH(2)CN), resulted in the formation of the bimetallic palladium complex [L3Pd(CNCH(2)CN)PdL3]·2[BF(4)] (C16). Upon activation with diethylaluminium chloride, all the nickel complexes showed high activity for ethylene dimerization. Furthermore, the palladium complexes exhibited good activities in the vinyl-polymerization of norbornene upon activation with MAO. PMID:22020535

Zhang, Wenjuan; Wang, Youhong; Yu, Jiangang; Redshaw, Carl; Hao, Xiang; Sun, Wen-Hua



Thermodynamic properties of autunite, uranyl hydrogen phosphate, and uranyl orthophosphate from solubility and calorimetric measurements  

SciTech Connect

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.

Gorman-Lewis, Drew; Shareva, Tatiana; kubatko, Karrie-Ann; burns, Peter; Wellman, Dawn M.; McNamara, Bruce K.; szymanowski, jennifer; Navrotsky, Alexandra; Fein, Jeremy B.



Hydrothermal syntheses and structures of the uranyl tellurates AgUO{sub 2}(HTeO{sub 5}) and Pb{sub 2}UO{sub 2}(TeO{sub 6})  

SciTech Connect

Two uranyl tellurates, AgUO{sub 2}(HTeO{sub 5}) (1) and Pb{sub 2}UO{sub 2}(TeO{sub 6}) (2), were synthesized under hydrothermal conditions and were structurally, chemically, and spectroscopically characterized. 1 crystallizes in space group Pbca, a=7.085(2) A, b=11.986(3) A, c=13.913(4) A, V=1181.5(5) A{sup 3}, Z=8; 2 is in P2(1)/c, a=5.742(1) A, b=7.789(2) A, c=7.928(2) A, V=90.703(2) A{sup 3}, and Z=2. These are the first structures reported for uranyl compounds containing tellurate. The U{sup 6+} cations are present as (UO{sub 2}){sup 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{sub 6} octahedra. In 2, uranyl square bipyramids share each of their equatorial vertices with different TeO{sub 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. -- Graphical abstract: Two hydrothermally synthesized uranyl tellurates, AgUO{sub 2}(HTeO{sub 5}) and Pb{sub 2}UO{sub 2}(TeO{sub 6}), contain sheets built from uranyl pentagonal or square bipyramids, as well as tellurate octahedra. Display Omitted Research highlights: > Compounds AgUO{sub 2}(HTeO{sub 5}) and Pb{sub 2}UO{sub 2}(TeO{sub 6}) are the first uranyl tellurate compounds. > The structure of AgUO{sub 2}(HTeO{sub 5}) consists of sheets of uranyl pentagonal bipyramids and TeO{sub 6} octahedra. > The structure of Pb{sub 2}UO{sub 2}(TeO{sub 6}) contains sheets of TeO{sub 6} octahedra and uranyl square bipyramids.

Ling, Jie; Ward, Matthew [Department of Civil Engineering and Geological Science, University of Notre Dame, Notre Dame, IN 46556 (United States); Burns, Peter C., E-mail: pburns@nd.ed [Department of Civil Engineering and Geological Science, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States)



Macrocyclic ligands for uranium complexation: Progress report, August 15, 1987-present  

SciTech Connect

The synthesis of several macrocyclic ligands, designed by a computer modeling approach for the complexation of the uranyl ion, has now been completed and their structures established. Preliminary indicate that these macrocycles successfully complex the uranyl ion. Other synthetic efforts have led to a variety of intermediates suitable for final ring closure to the desired macrocycles, providing appreciable potential for variation of the macrocyclic peripheral atoms. A 1:1-uranyl ion complex of one of these precursor products has been shown to undergo a DMSO-induced rearrangement to a 2:1 uranyl ion to ligand complex, both structures having been established by single crystal x-ray data. 10 refs.

Potts, K.T.



Synthesis and characterization of a tetrathiafulvalene-salphen actinide complex.  


A new tetrathiafulvalene-salphen uranyl complex has been prepared. The system was designed to study the electronic coupling between actinides and a redox active ligand framework. Theoretical and experimental methods--including DFT calculations, single crystal X-ray analysis, cyclic voltammetry, NMR and IR spectroscopies--were used to characterize this new uranyl complex. PMID:23572119

Bejger, Christopher; Tian, Yong-Hui; Barker, Beau J; Boland, Kevin S; Scott, Brian L; Batista, Enrique R; Kozimor, Stosh A; Sessler, Jonathan L



Aging induced loss of complexity and dedifferentiation: consequences for coordination dynamics within and between brain, muscular and behavioral levels  

PubMed Central

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

Sleimen-Malkoun, Rita; Temprado, Jean-Jacques; Hong, S. Lee



Luminescent, magnetic and ferroelectric properties of noncentrosymmetric chain-like complexes composed of nine-coordinate lanthanide ions.  


Reaction of the chiral ligand (-)-4,5-pinenepyridyl-2-pyrazine (L) with Ln(hfac)3·2H2O precursors [hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate, Ln = Sm(3+) (1), Eu(3+) (2), Tb(3+) (3) and Dy(3+) (4)] in methanol solution led to the formation of four noncentrosymmetric lanthanide complexes with the general formula [Ln(hfac)3L]n·H2O. The single-crystal X-ray diffraction analyses revealed that they are isostructural and take a one-dimensional (1D) chain structure based on the Ln(hfac)3L repeating units, in which the nine-coordinate Ln(3+) ions reside in a tricapped trigonal prism (TTP) environment never reported in previous 1D chain lanthanide complexes. The investigations of their photophysical properties showed that complexes 1, and 3 exhibit characteristic emissions of Sm(3+), Eu(3+) and Tb(3+) ions with respective luminescent lifetime values of 0.065, 1.066 and 0.129 ms, while complex 4 does not display any emission. The different luminescent intensities and lifetimes among them were further discussed in detail. Moreover, the magnetic properties of complexes 1-4 were assessed with a special emphasis on the Dy(3+) complex 4. Alternating-current (ac) magnetic susceptibility measurements indicated that field-induced two-step slow magnetic relaxation processes were observed in 4, indicating the single-molecule magnet (SMM) behavior of 4. In addition, the noncentrosymmetric complexes 1-4 crystallizing in the same polar point group (Cs) exhibit both ferroelectric and nonlinear optical properties at room temperature. All these features make them multifunctional crystalline molecule materials. PMID:24002651

Li, Xi-Li; Chen, Chun-Lai; Xiao, Hong-Ping; Wang, Ai-Ling; Liu, Cai-Ming; Zheng, Xianjun; Gao, Li-Jun; Yang, Xiao-Gang; Fang, Shao-Ming



Synthesis, structures and properties of a series of manganese coordination complexes constructed from dicarboxylic fluorene derivatives  

SciTech Connect

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-Right-Pointing-Pointer The complexes 1-4 display different topological structures. Black-Right-Pointing-Pointer Thermogravimetric analysis show the complexes have remarkably high thermal stability.

Li Xing, E-mail: [State Key Laboratory Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang, 315211 (China); Zhao Xiuhua; Bing Yue; Zha Meiqin; Xie Hongzhen; Guo Zhiyong [State Key Laboratory Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang, 315211 (China)



Copper-glutathione complexes under physiological conditions: structures in solution different from the solid state coordination.  


The physiologically important copper complexes of oxidized glutathione have been examined by electron spin resonance (ESR) spectroscopy in aqueous solution at neutral pH. Low temperature measurements show that the Cu(II) binding site in oxidized glutathione has the same ligand arrangement as in copper complexes of S-methylglutathione, glutamine, glutamate and glycine. The site is composed of the amino nitrogens and the carboxyl oxygens of two gamma-glutamyl residues; there is no interaction with amide nitrogens, the sulphur bond or the glycyl carboxyl groups. At high metal to ligand ratios a binuclear species exists, in which each Cu(II) binds only to one gamma-glutamyl residue. The previously reported forbidden transition detected at g = 4 is due to non-specific aggregation and not to spin coupling of intramolecular sites. Liquid solution ESR spectra show the Cu(II)-glutathione complex has a lower mobility than the corresponding Cu(II)-S-methylglutathione species. From the degree of spectral anisotropy the complex with glutathione is calculated to exist as a dimer. These results demonstrate that the physiologically relevant complex between copper and oxidized glutathione in solution is completely different from the known solid state structure determined by crystallography. PMID:8574092

Pederson, J Z; Steinkühler, C; Weser, U; Rotilio, G



Association of uranyl with the cell wall of Pseudomonas fluorescens inhibits metabolism  

NASA Astrophysics Data System (ADS)

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.

Bencheikh-Latmani, Rizlan; Leckie, James O.



User centered design in complex healthcare workflows: the case of care coordination and care management redesign  

PubMed Central

We present the User Need Analysis process for the Integrated Care Coordination Information System (ICCIS) research project at Oregon Health & Science University (OHSU). The primary goal of the process was to select a mix of methodologies to perform user need analysis which would lead to generation of system requirements. The ICCIS Team developers would use these prioritized requirements to build the next generation of the ICCIS software that would help meet the overall goals of the care model. First, semi-structured User Discussion Guides and structured questioners were used to collect raw needs from Physicians, Nurses, IT and Administrative personal. Later Conjoint Analysis (CA) and Dimensional Analysis (DA) were used to generate emerging concepts and priorities from the discussions with the end-user community. PMID:20351819

Behkami, Nima A.; Dorr, David A.



Regulation of CTnDOT Conjugative Transfer Is a Complex and Highly Coordinated Series of Events  

PubMed Central

ABSTRACT CTnDOT is a 65-kb conjugative transposon that is found in Bacteroides spp., which are one of the more abundant members within the lower human gastrointestinal tract. CTnDOT encodes resistance to the antibiotics erythromycin and tetracycline (Tc). An interesting feature of CTnDOT is that exposure to low levels of Tc induces a cascade of events that ultimately results in CTnDOT conjugative transfer. However, Tc is apparently not a switch that activates transfer but rather a signal that appears to override a series of negative regulators that inhibit premature excision and transfer of CTnDOT. In this minireview, we summarize over 20 years of research that focused on elucidating the highly coordinated regulation of excision, mobilization, and transfer of CTnDOT. PMID:24169574

Waters, Jillian L.; Salyers, Abigail A.



Uranyl phthalocyanines show promise in the treatment of brain tumors  

NASA Technical Reports Server (NTRS)

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.

Frigerio, N. A.



Functionally distinct Gata3/Chd4 complexes coordinately establish T helper 2 (Th2) cell identity.  


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-?. 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

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



DOI: 10.1002/anie.200905797 Synthesis and Properties of a Fifteen-Coordinate Complex: The  

E-print Network

: The Thorium Aminodiboranate [Th(H3BNMe2BH3)4]** Scott R. Daly, Paula M. B. Piccoli, Arthur J. Schultz,* Tanya is extremely useful and is widely employed to describe the local chemical environ- ments of atoms. Originally] The complexes tetrakis(cyclopentadienyl)uranium [UCp4] and its thorium analogue [ThCp4] are each connected to 20

Girolami, Gregory S.


Molecular dynamics simulations of the structure and thermodynamics of carrier-assisted uranyl ion extraction.  


We present molecular dynamics simulations of interfaces relevant to the selective chemical extraction of uranyl ions from aqueous solution. These molecular-level simulations model ion transfer in the PUREX process and in synthetic, selective membranes. We first present simulations of water/oil interfaces modified by incorporation of tributyl phosphate (TBP) into the oil phase (hexane). A range of concentrations is examined, from a single TBP molecule to values close to those utilized in the PUREX process. The TBP molecules exhibit strong interfacial activity, and the interface broadens relative to the water/oil case with increasing TBP concentrations. Additional structural features, including radial distribution functions and orientational distributions, are examined to elucidate the molecular ordering at the interface; the interface structure changes substantially with increasing TBP concentration. Finally, free-energy profiles are computed for (1) a single TBP molecule and a single uranyl nitrate complex [UO2(NO3)2] across the water/oil interface and (2) a UO2(NO3)2.TBP2 complex across both water/oil and water/(oil+TBP) interfaces. The UO2(NO3)2 complex is strongly repelled from the water/oil interface, while the UO2(NO3)2.TBP2 complex exhibits interfacial activity that decreases with increasing TBP concentration. The UO2(NO3)2.TBP2 complex displays a net free-energy driving force for partitioning into the oil phase that increases with increasing TBP concentration. PMID:19845396

Jayasinghe, Manori; Beck, Thomas L



Coordination modes, spectral, thermal and biological evaluation of hetero-metal copper containing 2-thiouracil complexes  

NASA Astrophysics Data System (ADS)

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 ?S? 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 complexes were failed.

Masoud, Mamdouh S.; Soayed, Amina A.; El-Husseiny, Amel F.



Uranyl Precipitation by Pseudomonas aeruginosa via Controlled Polyphosphate Metabolism  

PubMed Central

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

Renninger, Neil; Knopp, Roger; Nitsche, Heino; Clark, Douglas S.; Keasling, Jay D.



Synthesis and coordination behavior of a bipyridine platinum(II) complex with thioglucose.  


A mononuclear platinum(II) complex with two monodentate-S H4tg(-) ligands, [Pt(H4tg-?S)2(bpy)] (1), was newly synthesized by the reaction of [PtCl2(bpy)] (bpy = 2,2'-bipyridyl) with NaH4tg (NaH4tg =1-thio-?-d-glucose sodium salt) in water. Complex 1 reacted with additional [PtCl2(bpy)] in water to give an S-bridged dinuclear complex, [Pt2(?2-H4tg-?(1)S:?(1)S)2(bpy)2](2+) ([2](2+)), in which a square-planar [Pt(H4tg)2(bpy)] unit binds to a [Pt(bpy)](2+) moiety through two thiolato groups. Treatments of 1 with Cu(2+) and Ni(2+) in water in the presence of bpy produced S-bridged dinuclear complexes [PtCu(?2-H4tg-?(1)S:?(2)O,S)2(bpy)2](2+) ([3](2+)) and [PtNi(?2-H4tg-?(1)S:?(2)O,S)2(bpy)2](2+) ([4](2+)), respectively, in which a square-planar [Pt(H4tg)2(bpy)] unit binds to a [M(bpy)](2+) (M = Cu(II), Ni(II)) moiety through two thiolato and two hydroxyl groups to form a chiral [M(N)2(O)2(S)2] octahedron with the ? configuration. On the other hand, similar treatment with Cd(2+) in the presence of bpy resulted in the formation of an S-bridged trinuclear complex, [Cd{Pt(?2-H4tg-?(1)S:?(2)O,S)(?2-H4tg-?(1)S:?(1)S)(bpy)}2](2+) ([5](2+)), in which each of two square-planar [Pt(H4tg)2(bpy)] units binds to a Cd(II) ion through two thiolato groups and one hydroxyl group to form a chiral [Cd(O)2(S)4] octahedron with the ? configuration. Of two geometrical configurations, syn and anti, which arise from the relative arrangement of two ?-D-pyranose moieties, [2](2+) adopts the syn configuration with symmetric bridging sulfur atoms, while [3](2+), [4](2+), and [5](2+) all have the anti configuration with R configurational bridging sulfur atoms. All of the complexes were fully characterized by electronic absorption, CD, and NMR spectroscopies, along with single-crystal X-ray crystallography. PMID:23577632

Tsuji, Takaaki; Kuwamura, Naoto; Yoshinari, Nobuto; Konno, Takumi



Coordination of Aza Heterocycles with Macroheterocyclic Metal Complexes in Amphiprotic Media: II. Kinetics of Outer-Sphere Ligand Exchange in Chromium(III) Tetrphenylporphyrinate  

Microsoft Academic Search

Rate constants and activation parameters for substitution of alcohols with aza heterocycles in the chromium(III) (acetate)tetraphenylporphyrinate complex were calculated. The nature of the leaving ligand significantly affects the activation parameters. Increased strength of the H bond in the outer coordination sphere of the macrocyclic complex decreases the substitution rate constant. The logarithms of the reaction rate constants linearly vary with

I. P. Trifonova; V. A. Burmistrov; A. S. Ocheretovyi; O. I. Koifman



Reactivity of coordinatively unsaturated bis(N-heterocyclic carbene) Pt(II) complexes toward H(2). Crystal structure of a 14-electron Pt(II) hydride complex.  


The reactivity toward H2 of coordinatively unsaturated Pt(II) complexes, stabilized by N-heterocyclic carbene (NHC) ligands, is herein analyzed. The cationic platinum complexes [Pt(NHC')(NHC)](+) (where NHC' stands for a cyclometalated NHC ligand) react very fast with H2 at room temperature, leading to hydrogenolysis of the Pt-CH2 bond and concomitant formation of hydride derivatives [PtH(NHC)2](+) or hydrido-dihydrogen complexes [PtH(H2)(NHC)2](+). The latter species release H2 when these compounds are subjected to vacuum. The X-ray structure of complex [PtH(IPr)2][SbF6] revealed its unsaturated nature, exhibiting a true T-shaped structure without stabilization by agostic interactions. Density functional theory calculations indicate that the binding and reaction of H2 in complexes [PtH(H2)(NHC)2](+) is more favored for derivatives bearing aryl-substituted NHCs (IPr, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene and IMes = 1,3-dimesityl-1,3-dihydro-2H-imidazol-2-ylidene) than for those containing tert-butyl groups (I(t)Bu). This outcome is related to the higher close-range steric effects of the I(t)Bu ligands. Accordingly, H/D exchange reactions between hydrides [PtH(NHC)2](+) and D2 take place considerably faster for IPr and IMes* derivatives than for I(t)Bu ones. The reaction mechanisms for both H2 addition and H/D exchange processes depend on the nature of the NHC ligand, operating through oxidative addition transition states in the case of IPr and IMes* or by a ?-complex assisted-metathesis mechanism in the case of I(t)Bu. PMID:24716606

Rivada-Wheelaghan, Orestes; Roselló-Merino, Marta; Ortuño, Manuel A; Vidossich, Pietro; Gutiérrez-Puebla, Enrique; Lledós, Agustí; Conejero, Salvador



Coordination of DNA replication and histone modification by the Rik1-Dos2 complex.  


Histone modification marks have an important role in many chromatin processes. During DNA replication, both heterochromatin and euchromatin are disrupted ahead of the replication fork and are then reassembled into their original epigenetic states behind the fork. How histone marks are accurately inherited from generation to generation is still poorly understood. In fission yeast (Schizosaccharomyces pombe), RNA interference (RNAi)-mediated histone methylation is cell cycle regulated. Centromeric repeats are transiently transcribed in the S phase of the cell cycle and are processed into short interfering RNAs (siRNAs) by the complexes RITS (RNA-induced initiation of transcriptional gene silencing) and RDRC (RNA-directed RNA polymerase complex). The small RNAs together with silencing factors-including Dos1 (also known as Clr8 and Raf1), Dos2 (also known as Clr7 and Raf2), Rik1 and Lid2-promote heterochromatic methylation of histone H3 at lysine 9 (H3K9) by a histone methyltransferase, Clr4 (refs 8-13). The methylation of H3K9 provides a binding site for Swi6, a structural and functional homologue of metazoan heterochromatin protein 1 (HP1). Here we characterize a silencing complex in fission yeast that contains Dos2, Rik1, Mms19 and Cdc20 (the catalytic subunit of DNA polymerase-?). This complex regulates RNA polymerase II (RNA Pol II) activity in heterochromatin and is required for DNA replication and heterochromatin assembly. Our findings provide a molecular link between DNA replication and histone methylation, shedding light on how epigenetic marks are transmitted during each cell cycle. PMID:21725325

Li, Fei; Martienssen, Rob; Cande, W Zacheus



Coordination of DNA Replication and Histone Modification by the Rik1-Dos2 Complex  

PubMed Central

Histone modification marks play an important role in many chromatin processes1,2. During DNA replication, both heterochromatin and euchromatin are disrupted ahead of the replication fork and then reassembled into their original epigenetic states behind the fork3,4. How the histone marks are faithfully inherited during each generation is still poorly understood. In fission yeast RNA interference (RNAi)-mediated histone methylation is cell-cycle regulated. Centromere repeats are transiently transcribed at S phase and processed into small interference RNAs (siRNAs) by RITS and RDRC complexes5-7. The small RNAs, in concert with silencing factors, including Dos1/Clr8, Dos2/Clr7, Rik1 and Lid2, promote heterochromatic H3K9 methylation by a histone methyltransferase, Clr48-13. H3K9 methylation serves as a binding site for Swi6, a structural and functional homolog of metazoan Heterochromatin Protein 1 (HP1)14. Here we characterize a silencing complex, which contains Dos2, Rik1, Mms19, and Cdc20 (DNA polymerase epsilon). The complex regulates RNA Pol II activity in heterochromatin, and is required for DNA replication and heterochromatin assembly. Our findings provide a molecular link between DNA replication and histone methylation, shedding light on how epigenetic marks are transmitted during each cell cycle. PMID:21725325

Li, Fei; Martienssen, Rob; Cande, W. Zacheus



Basicity of coordinating ligands in trivalent uranium and cerium metallocene complexes  

SciTech Connect

Although much is known about the affinity of various Lewis bases for transition metal centers, the chemical literature contains only scant information about the relative affinities of Lewis bases for lanthanide and actinide metal centers. In terms of ligand affinities for f-metal centers, traditional HSAB theory characterizes trivalent and tetravalent f-metal cations as ''hard'' acids, preferring to be coordinated to ''hard'' Lewis bases (e.g., nitrogen or oxygen donor ligands) rather than ''soft'' (e.g., phosphorous or sulfur donor ligands) Lewis bases. Recent work by Brennan and Stults, however, has shown that, trimethylphosphine has a much greater affinity than does pyridine for the metal center in (MeC/sub 5/H/sub 4/)/sub 3/U and in (MeC/sub 5/H/sub 4/)/sub 3/Ce. This work established the ligand displacement series PMe/sub 3/, is quantitatively displaced by trimethylphosphine oxide in both the uranium and cerium systems. In the cerium system, trimethylphosphine sulfide and dimethyl sulfoxide were also found to quantitatively displace PMe/sub 3/. Trimethylphosphine oxide was found to be by far the strongest ligand in both systems, quantitatively displacing all ligands studied in both systems, with one exception: in the (me/sub 3/SiC/sub 5/H/sub 4/)/sub 3/U system, t-butyl isocyanide is displaced, but not completely displaced, by OPME/sub 3/. 9 refs.

Fabiano, M.D.



Catenation control in the two-dimensional coordination polymers based on tritopic carboxylate linkers and azamacrocyclic nickel(II) complexes.  


Four new coordination polymer frameworks, namely [(NiL(1))(3)(BTB)(2)]·6H(2)O, [(NiL(2))(3)(BTB)(2)]·6H(2)O, [(NiL(3))(3)(BTB)(2)]·6H(2)O and [(NiL(2))(3)(BTC)(2)]·10.25H(2)O (L(1) = 1,4,8,11-tetraazacyclotetradecane, L(2) = 3-methyl-1,3,5,8,12-pentaazacyclotetradecane, L(3) = 3,10-dimethyl-1,3,5,8,10,12-hexaazacyclotetradecane, BTC(3-) = benzene-1,3,5-tricarboxylate, BTB(3-) = 4,4',4''-benzene-1,3,5-triyl-tribenzoate) were prepared in water-N,N-dimethylformamide solutions. The molecular and crystal structures of these compounds are compared to the related coordination polymers formed by nickel(II) macrocyclic cations to examine the effect of carboxylate linker size on the framework architecture. Luminescent properties of the complexes based on the BTB(3-) bridging ligand are also discussed. PMID:22266979

Lampeka, Yaroslaw D; Tsymbal, Liudmyla V; Barna, Andrij V; Shu?ga, Yulija L; Shova, Sergiu; Arion, Vladimir B



Reversible switching of the coordination modes of a pyridine-functionalized quinonoid zwitterion; its di- and tetranuclear palladium complexes.  


The coordination chemistry of a new functional quinonoid zwitterion (E)-3-oxo-4-((2-(pyridin-2-yl)ethyl)amino)-6-((2-(pyridin-2-yl)ethyl)iminio)cyclohexa-1,4-dienolate (2, H2L), in which a CH2CH2 spacer connects the N substituents of the quinonoid core with a pyridine group, was explored in Pd(II) chemistry. Different coordination modes have been observed, depending on the experimental conditions and the reagents. The reaction of H2L with [Pd(?-Cl)(dmba)]2 (dmba = o-C6H4CH2NMe2-C,N) afforded the dinuclear complex [{PdCl(dmba)}2(H2L)] (3) in which H2L acts as a NPy,NPy bidentate ligand. Deprotonation of this complex with NaH resulted in the formation of the dinuclear complex [{Pd(dmba)}2(?-L)] (4) in which a shift of the Pd(II) centers from the NPy sites to the N,O donor sites of the zwitterion core has occurred, resulting in a N2O2 tetradentate behavior of ligand L. Reaction of 4 with HCl regenerates 3 quantitatively. Chloride abstraction from 3 with AgOTf (OTf = trifluoromethanesulfonate) resulted in loss of one of the two dmba ligands and formation of an unusual tetranuclear Pd(II) complex, [{Pd(dmba)}(?-L)Pd]2(OTf)2 (5), in which two dinuclear entities have dimerized, one pyridine donor group from each dimer forming a bridge with the other dinuclear entity. This results in a N2, O2, NPy, NPy hexadentate behavior for the ligand L. Complexes 3 and 4 constitute an unprecedented reversible, switchable system where deprotonation or protonation promotes the reversible migration of the [Pd(dmba)](+) moieties, from the NPy sites in 3, to the N,O donor sites of the quinonoid core in 4, respectively. This switch modifies the extent of ?-delocalization involving the potentially antiaromatic quinonoid moiety and is accompanied by a significant color change, from red in 3 to green in 4. The presence of uncoordinated pyridine donor groups in 4 allowed the use of this complex for the preparation of the neutral tetranuclear complex [{Pd(dmba)}2(?-L){PdCl(dmba)}2] (6) in which 4 acts as a NPy,NPy-bidentate metalloligand toward two PdCl(dmba) moieties. Halide abstraction from 6 afforded the monocationic, tetranuclear complex [{Pd(dmba)}2(?-L){Pd(dmba)}2(?-Cl)]PF6 (7) in which the two Pd(dmba) moieties are connected by ligand L and a bridging chloride. By Cl/PF6 anion metathesis, it was possible to switch quantitatively from complex 6 to 7 and vice versa. All new compounds were unambiguously characterized by IR, NMR, and mass spectroscopy. Single-crystal X-ray diffraction is also available for molecules 2-5 and 7. PMID:24813619

Ghisolfi, Alessio; Waldvogel, Audrey; Routaboul, Lucie; Braunstein, Pierre



Electronic structure and slow magnetic relaxation of low-coordinate cyclic alkyl(amino) carbene stabilized iron(I) complexes.  


Cyclic alkyl(amino) carbene stabilized two- and three-coordinate Fe(I) complexes, (cAAC)2FeCl (2) and [(cAAC)2Fe][B(C6F5)4] (3), respectively, were prepared and thoroughly studied by a bouquet of analytical techniques as well as theoretical calculations. Magnetic susceptibility and Mössbauer spectroscopy reveal the +1 oxidation state and S = 3/2 spin ground state of iron in both compounds. 2 and 3 show slow magnetic relaxation typical for single molecule magnets under an applied direct current magnetic field. The high-frequency EPR measurements confirm the S = 3/2 ground state with a large, positive zero-field splitting (?20.4 cm(-1)) and reveal easy plane anisotropy for compound 2. CASSCF/CASPT2/RASSI-SO ab initio calculations using the MOLCAS program package support the experimental results. PMID:25072104

Samuel, Prinson P; Mondal, Kartik Chandra; Amin Sk, Nurul; Roesky, Herbert W; Carl, Elena; Neufeld, Roman; Stalke, Dietmar; Demeshko, Serhiy; Meyer, Franc; Ungur, Liviu; Chibotaru, Liviu F; Christian, Jonathan; Ramachandran, Vasanth; van Tol, Johan; Dalal, Naresh S



DFT Study of the Reaction of a Two-Coordinate Iron(II) Dialkyl Complex with Molecular Oxygen.  


DFT studies are reported of a monomeric iron dialkyl for which oxygen atom insertion into metal-methyl bonds occurs with O2: FeMe2 + O2 ? Fe(OMe)2. Computation of the reaction coordinate implicates the intermediacy of Fe(III)-peroxo, Fe(VI)-dioxo, and Fe(IV)-oxo intermediates, connected by O2 oxidative addition and two methyl migration steps. Analysis of the reaction of O2 with d(6)-Fe(Me)2 indicates that oxy-insertion for this iron complex occurs with lower free energy barriers than competing homolytic/radical pathways, exploiting "spin-flip" processes via minimum energy crossing points (MECPs). PMID:25355170

Prince, Bruce M; Cundari, Thomas R; Tymczak, C J



Studies of the Antiproliferative Activity of Ruthenium (II) Cyclopentadienyl-Derived Complexes with Nitrogen Coordinated Ligands  

PubMed Central

Four cationic ruthenium(II) complexes with the formula [Ru(?5-C5H5)(PPh3)2]+, with L = 5-phenyl-1H-tetrazole (TzH) 1, imidazole (ImH) 2, benzo[1,2-b;4,3-b?] dithio-phen-2-carbonitrile (Bzt) 3, and [5-(2-thiophen-2-yl)-vinyl]-thiophene-2-carbonitrile] (Tvt) 4 were prepared and characterized in view to evaluate their potentialities as antitumor agents. Studies by Circular Dichroism indicated changes in the secondary structure of ct-DNA. Changes in the tertiary structure of pBR322 plasmid DNA were also observed in gel electrophoresis experiment and the images obtained by atomic force microscopy (AFM) suggest strong interaction with pBR322 plasmid DNA; the observed decreasing of the viscosity with time indicates that the complexes do not intercalate between DNA base pairs. Compounds 1, 2, and 3 showed much higher cytotoxicity than the cisplatin against human leukaemia cancer cells (HL-60 cells). PMID:20689715

Moreno, Virtudes; Lorenzo, Julia; Aviles, Francesc X.; Garcia, M. Helena; Ribeiro, Joao P.; Morais, Tania S.; Florindo, Pedro; Robalo, M. Paula



Coordination chemistry of cyclopropenylidene-stabilized phosphenium cations: synthesis and reactivity of Pd and Pt complexes.  


A straightforward synthesis of cyclopropenylidene-stabilized phosphenium cations 1?a-g through the reaction of [(iPr2N)2C3(+)Cl]BF4 with secondary phosphines is described. Their donor ability was evaluated by analysis of the CO stretching frequency in Rh complexes [RhCl(CO)L2](BF4)2 and electrochemical methods. The cyclopropenium ring induces a phosphite-type behavior that can be tuned by the other two substituents attached to the phosphorus atom. Despite of the positive charge that they bear, phosphenium cations 1?a-g still act as two-electron donor ligands, forming adducts with Pd(II) and Pt(II) precursors. Conversely, in the presence of Pd(0) species, an oxidative insertion of the Pd atom into the Ccarbene-phosphorus bond takes place, providing dimeric structures in which each Pd atom is bonded to a cyclopropenyl carbene while two dialkyl/diaryl phosphide ligands serve as bridges between the two Pd centers. The catalytic performance of the resulting library of Pt(II) complexes was tested; all of the cationic phosphines accelerated the prototype 6-endo-dig cyclization of 2-ethynyl-1,1'-biphenyl to afford pentahelicene. The best ligand 1?g was used in the synthesis of two natural products, chrysotoxene and epimedoicarisoside?A. PMID:24459090

Kozma, Agnes; Deden, Tobias; Carreras, Javier; Wille, Christian; Petuškova, Jekaterina; Rust, Jörg; Alcarazo, Manuel



Care Coordination for Children with Complex Special Health Care Needs: The Value of the Advanced Practice Nurse's Enhanced Scope of Knowledge and Practice  

PubMed Central

Efficiency and effectiveness of care coordination depends on a match between the needs of the population and the skills, scope of practice, and intensity of services provided by the care coordinator. There is limited existing literature that addresses the relevance of the APN role as a fit for coordination of care for children with SHCN. The objective of this paper is to describe the value of the advanced practice nurse’s (APN’s) enhanced scope of knowledge and practice for relationship-based care coordination in healthcare homes that serve children with complex special health care needs (SHCN). The TeleFamilies project is provided as an example of the integration of an APN care coordinator in a healthcare home for children with SHCN. PMID:22560803

Looman, Wendy S.; Presler, Elizabeth; Erickson, Mary M.; Garwick, Ann E.; Cady, Rhonda G.; Kelly, Anne M.; Finkelstein, Stanley M.



Coordination of uranium(VI) with N,N'-diethyl-N,N'-ditolyldipicolinamide  

NASA Astrophysics Data System (ADS)

Structural analyses of uranyl complexes with isomers of N,N'-diethyl-N,N'-ditolyl-dipicolinamide were carried out using IR spectroscopy and single crystal x-ray diffraction. From these analyses it was determined that complexation takes place through coordination with the carbonyl and pyridine nitrogen moieties. The uranium-oxygen and uranium-nitrogen bond distances for Et(p)TDPA are U(1)-O(1): 2.394(3), U(1)-O(2): 2.460(3), U(1)-N(1): 2.661(3) and for Et(o)TDPA U(1)-O(1): 2.415(5), U(1)-O(2): 2.432(4), and U(1)-N(1): 2.647(5).

Lapka, J. L.; Paulenova, A.; Zakharov, L. N.; Alyapyshev, M. Yu; Babain, V. A.



Extraction of uranyl, La(III), and Y(III) nitrates with a composite solid extractant based on a polymeric support impregnated with trialkylamine  

Microsoft Academic Search

Extraction of uranyl, La(III), and Y(III) nitrates from aqueous solutions containing 0–4 M sodium nitrate with a composite\\u000a solid extractant based on a polymeric support impregnated with trialkylamine (C7-C9) was studied. The extraction isotherms were analyzed assuming that La(III), Y(III), and uranyl nitrates are extracted with\\u000a the solid extractant in the form of complexes (R3NH)3[Ln(NO3)6] and (R3NH)2[UO2(NO3)4], respectively. The extraction

A. K. Pyartman; V. V. Lishchuk; V. A. Keskinov



Extraction of uranyl, La(III), and Y(III) nitrates with a composite solid extractant based on a polymeric support impregnated with trialkylmethylammonium nitrate  

Microsoft Academic Search

Extraction of uranyl, La(III), and Y(III) nitrates from aqueous solutions containing 0–4 M sodium nitrate with a composite\\u000a solid extractant based on a polymeric support impregnated with trialkylmethylammonium nitrate (Aliquat-336) was studied. The\\u000a extraction isotherms were analyzed assuming that uranyl, La(III), and Y(III) nitrates are extracted with the solid extractant\\u000a in the form of complexes (R4N)2[Ln(NO3)5] and (R4N)2[UO2(NO3)4], respectively. The

A. K. Pyartman; V. A. Keskinov; V. V. Lishchuk; A. V. Konstantinova; V. V. Belova



New near-wall models with dynamic subgrid scale closure for large eddy simulation in curvilinear coordinates for complex geometries  

NASA Astrophysics Data System (ADS)

This dissertation presents modifications and improvements to the dynamic subgrid scale model and introduces a new wall model. These are applied to the large eddy simulation technique in curvilinear coordinates. They are then validated and tested in three-dimensional complex geometries. The large eddy simulation method captures many scales of turbulence up to the grid size. A closure model is used to simulate subgrid turbulence. The Smagorinsky and dynamic subgrid models are presented and tested. The dynamic model overcomes many of the deficiencies of the Smagorinsky subgrid scale model. Spatial and temporal low-pass filters have been introduced in the dynamic subgrid scale model for numerical stability. No practical differences have been observed between the Smagorinsky and dynamic models. Several near-wall models are considered for the large eddy simulation technique. A local averaging technique makes these models applicable to complex geometries. A new model is introduced which overcomes planar averaging near the wall and captures ejection and sweep effects. Special treatment of inlet boundary conditions was introduced. These models have been implemented in a large eddy simulation computer program that uses a strongly conservative curvilinear coordinate formulation. The covariant projections are used as the dependent variables in a staggered methodology. The body fitted grids are advantageous in complex geometry descriptions. Results are validated in a lid driven cavity flow at Reynolds number of 10000. A single tube in a channel is simulated to show the applicability of the models to complex geometries with attachment and separation as well as end-wall effects. The shedding effect was captured and turbulence characteristics were acceptable. One million nodes were used in a large eddy simulation of a three-dimensional tube bundle at Reynolds number of 21700. Results are presented in the form of visualization and compared with available experimental data. The 'flapping' effect in the tube wake is captured. This dissertation shows the large eddy simulation technique may be used as a tool in predicting the unsteady behavior of flow in industrial applications.

Barsamian, Hagop Raffi



Electrochemistry and spectroelectrochemistry of indium(III) porphyrins. Reactions of five-coordinate ionic complexes  

SciTech Connect

The electrochemistry and spectroelectrochemistry of In(III) tetraphenyl- and octaethylporphyrins were investigated in nonaqueous media. Counterions on the In(III) complexes were either Cl/sup -/ or ClO/sub 4//sup -/. Each oxidized and reduced species was characterized by UV-visible spectroscopy, and ESR spectra were obtained for each of the generated cation and anion radicals. Singly oxidized species gave rise to ESR spectra with values of g approx. = 2.00 but with values of that varied between 16.8 and 221 G depending upon the nature of the porphyrin ring and the composition of the solvent-supporting electrolyte systems. Analysis of the ESR data indicated ..pi..-ring-centered reactions with a small amount of spin density residing upon the metal. 23 references, 6 figures, 5 tables.

Kadish, K.M.; Cornillion, J.L.; Cocolios, P.; Tabard, A.; Guilard, R.



Influence of the ?-coordinated arene on the anticancer activity of ruthenium(II) carbohydrate organometallic complexes  

PubMed Central

The synthesis and in vitro cytotoxicity of a series of RuII(arene) complexes with carbohydrate-derived phosphite ligands and various arene co-ligands is described. The arene ligand has a strong influence on the in vitro anticancer activity of this series of compounds, which correlates fairly well with cellular accumulation. The most lipophilic compound bearing a biphenyl moiety and a cyclohexylidene-protected carbohydrate is the most cytotoxic with unprecedented IC50 values for the compound class in three human cancer cell lines. This compound shows reactivity to the DNA model nucleobase 9-ethylguanine, but does not alter the secondary structure of plasmid DNA, indicating that other biological targets are responsible for its cytotoxic effect. PMID:24790955

Hanif, Muhammad; Meier, Samuel M.; Nazarov, Alexey A.; Risse, Julie; Legin, Anton; Casini, Angela; Jakupec, Michael A.; Keppler, Bernhard K.; Hartinger, Christian G.



A novel flow injection potentiometric graphite coated ion-selective electrode for the low level determination of uranyl ion  

Microsoft Academic Search

Solution studies on the binding properties of uranyl ion toward four different recently synthesized benzo-substituted macrocyclic diamides L1-L4 revealed the occurrence of a 1:1 complexation of the ligands with UO22+ ion, with a stability order of L2>L1>L4>L3. Consequently, L2 was used as a suitable neutral ionophore for the preparation of novel polymeric membrane (PME) and coated graphite (CGE) UO22+-selective electrodes.

Mojtaba Shamsipur; Farhang Mizani; Mir Fazlollah Mousavi; Naader Alizadeh; Kamal Alizadeh; Hossein Eshghi; Hassan Karami



An eight-coordinate vanadium thiolate complex with charge delocalization between V(V)-thiolate and V(IV)-thiyl radical forms.  


A six-coordinate oxovanadium(V) thiolate complex and an eight-coordinate non-oxovanadium thiolate complex, [PPh(4)][VO(PS3'')(OCH(3))] (1) and [NEt(4)][V(PS3'')(2)] (2) (PS3'' = P(C(6)H(3)-3-Me(3)Si-2-S)(3)(3-)), respectively, have been isolated and structurally characterized. The former belongs to a limited collection of oxovanadium(V) thiolate complexes. The latter has an unusual coordination number of eight. More importantly, its consensus electronic structure derived from its spectroscopic data should be considered as the resonance forms of V(V)-thiolate and V(IV)-thiyl radical species. This implies that V(IV)-thiyl radical can maintain a stable presence in biological systems. PMID:21438583

Chang, Ya-Ho; Su, Chia-Ling; Wu, Ru-Rong; Liao, Ju-Hsiou; Liu, Yi-Hung; Hsu, Hua-Fen



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.  


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

Ramírez, Flor de María; Varbanov, Sabi; Padilla, Juan; Bünzli, Jean-Claude G



Determination of uranyl incorporation into biogenic manganese oxides using x-ray absorption spectroscopy and scattering.  


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, UO2(2+) (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 (<0.3 mol % U, <1 microM U(VI) in solution), U(VI) is present as a strong bidentate surface complex. At high concentrations (>2 mol % U, >4 microM 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. PMID:16509317

Webb, S M; Fuller, C C; Tebo, B M; Bargar, J R



Yttrium and lanthanide complexes of ?-dialdehydes: synthesis, characterization, luminescence and electrochemistry of coordination compounds with the conjugate base of bromomalonaldehyde.  


Novel yttrium, europium and terbium coordination compounds having formulae [AsPh4][Ln(BrMA)4] (6LN), Ln(BrMA)3(bipyO2) (7Ln), Ln(NMA)3(phen) (8Ln) and Ln(NMA)3(terpy) (9Ln) (Ln = Y, Eu, Tb; BrMA = conjugate base of bromomalonaldehyde; bipyO2 = 2,2'-bipyridine-N,N'-dioxide; phen = 1,10-phenantroline; terpy = 2,2':6',2''-terpyridine) were synthesized and characterized by using spectroscopic and electrochemical techniques. Uncharged europium and, to a lesser extent, terbium complexes showed appreciable luminescence in the solid state upon excitation with UV light. Polymeric materials and ionic liquids containing BrMA and lanthanides were prepared and photoluminescence measurements were carried out. From an electrochemical point of view, europium(III) BrMA-complexes showed a quasi-reversible one-electron reduction process. The one electron transfer reaction Eu(III) to Eu(II) allowed the photoluminescence tuning of 8Eu deposited on the surface of a glassy carbon electrode. PMID:24819039

Bortoluzzi, Marco; Battistel, Dario; Roppa, Stefania; Daniele, Salvatore; Perosa, Alvise; Enrichi, Francesco



Engineering and Coordination of Regulatory Networks and Intracellular Complexes to Maximize Hydrogen Production by Phototrophic Microorganisms  

SciTech Connect

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 reductive pentose phosphate pathway, whose key enzyme is ribulose 1,5-biphosphate carboxylase/oxygenase (RubisCO). In addition to providing virtually all cellular carbon during autotrophic metabolism, RubisCO-mediated CO{sub 2} assimilation is also very important for nonsulfur purple photosynthetic bacteria under photoheterotrophic growth conditions since CO{sub 2} becomes the major electron sink under these conditions. In this work, Ensemble Modeling (EM) was developed to examine the behavior of CBB-compromised RubisCO knockout mutant strains of the nonsulfur purple photosynthetic bacterium Rhodobacter sphaeroides. Mathematical models of metabolism can be a great aid in studying the effects of large perturbations to the system, such as the inactivation of RubisCO. Due to the complex and highly-interconnected nature of these networks, it is not a trivial process to understand what the effect of perturbations to the metabolic network will be, or vice versa, what enzymatic perturbations are necessary to yield a desired effect. Flux distribution is controlled by multiple enzymes in the network, often indirectly linked to the pathways of interest. Further, depending on the state of the cell and the environmental conditions, the effect of a perturbation may center around how it effects the carbon flow in the network, the balancing of cofactors, or both. Thus, it is desirable to develop mathematical models to describe, understand, and predict network behavior. Through the development of such models, one may gain the ability to generate a set of testable hypotheses for system behavior.

James C. Liao



Controlling Magnetism by Light in Nanoscaled Heterostructures of Cyanometallate Coordination Networks: the role of increased complexity  

NASA Astrophysics Data System (ADS)

Nanometer-sized heterostructures of the Prussian blue analogues AjCok[Fe(CN)6]l.nH2O (Co-Fe PBA, with A = K, Rb) and RbaNib[Cr(CN)6]c.mH2O (Ni-Cr PBA) have been investigated, and new phenomena, not observed for the constituent bulk phases, have been observed.footnotetext D.M. Pajerowski, M.J. Andrus, J.E. Gardner, E.S. Knowles, M.W. Meisel, D.R. Talham, J. Am. Chem. Soc. 132 (2010) 4058.^,footnotetext M.F. Dumont, E.S. Knowles, A. Guiet, D.M. Pajerowski, A. Gomez, S.W. Kycia, M.W. Meisel, D.R. Talham, Inorg. Chem. 50 (2011) 4295.^,footnotetext D.M. Pajerowski, J.E. Gardner, M.J. Andrus, S. Datta, A. Gomez, S.W. Kycia, S. Hill, D.R. Talham, M.W. Meisel, Phys. Rev. B 82 (2010) 214405.^,footnotetext E.S. Knowles, M.F. Dumont, M.K. Peprah, M.W. Meisel, C.H. Li, M.J. Andrus, D.R. Talham, arxiv:1207.2623 (2012). A crucial aspect of the ability to photocontrol the persistent magnetism up to 70 K is the role of the strain coupling present at the interfaces between the nanoscaled regions of the constituents. Increasing the morphological complexity of the samples has the potential to provide materials possessing novel combinations of properties. In parallel, the interplay between long-range magnetic order and structural coherence is an important consideration in our attempts to design new systems. Open, unresolved issues will be discussed, and potential future paths will be sketched.

Meisel, Mark W.



A new hetero-bimetallic coordination polymer, cesium, and sodium complex of styphnate trihydrate [CsNa(TNR)(H 2 O) 3 ] n  

Microsoft Academic Search

A new hetero-bimetallic coordination polymer, cesium, and sodium complex of styphnate trihydrate [CsNa(TNR)(H2O)3]\\u000a n\\u000a (TNR: 2,4,6-trinitroresorcinol dianion, the dianion of styphnic acid) was synthesized. The title complex was characterized\\u000a by X-ray single crystal diffraction, element analysis, FT-IR, DSC, TG-DTG studies. In the title polymer molecule, the cesium\\u000a cation is coordinated by 13 oxygen atoms: three originated from the water molecule

Jun-Wei Liu; Jian-Guo Zhang; Tong-Lai Zhang; Hong Zheng; Li Yang; Kai-Bei Yu



Multispecies diffusion models: A study of uranyl species diffusion  

SciTech Connect

Rigorous numerical description of multi-species diffusion requires coupling of species, charge, and aqueous and surface complexation reactions that collectively affect diffusive fluxes. The applicability of a fully coupled diffusion model is, however, often constrained by the availability of species self-diffusion coefficients, as well as by computational complication for imposing charge conservation. In this study, several diffusion models with variable complexity in charge and species coupling were formulated and compared to describe reactive multi-species diffusion in groundwater. Diffusion of uranyl [U(VI)] species was used as an example in demonstrating the effectiveness of the models in describing multi-species diffusion. Numerical simulations found that a diffusion model with a single, common diffusion coefficient for all species was sufficient to describe multi-species U(VI) diffusion under steady-state condition of major chemical composition, but not under transient chemical conditions. Simulations revealed that a fully coupled diffusion model can be well approximated by a component-based diffusion model, which considers difference in diffusion coefficients between chemical components, but not between the species within each chemical component. This treatment significantly enhanced computational efficiency at the expense of minor charge conservation. The charge balance in the component-based diffusion model can be rigorously enforced, if necessary, by adding an artificial kinetic reaction term induced by the charge separation. The diffusion models were applied to describe U(VI) diffusive mass transfer in intragranular domains in two sediments collected from US Department of Energy's Hanford 300A where intragrain diffusion is a rate-limiting process controlling U(VI) adsorption and desorption. The grain-scale reactive diffusion model was able to describe U(VI) adsorption/desorption kinetics that has been described using a semi-empirical, multi-rate model. Compared with the multi-rate model, the diffusion models have the advantage to provide spatiotemporal speciation evolution within the diffusion domains.

Liu, Chongxuan; Shang, Jianying; Zachara, John M.



Metal ion as both a cofactor and a probe of metal-binding sites in a uranyl-specific DNAzyme: a uranyl photocleavage study  

PubMed Central

DNAzymes are known to bind metal ions specifically to carry out catalytic functions. Despite many studies since DNAzymes were discovered nearly two decades ago, the metal-binding sites in DNAzymes are not fully understood. Herein, we adopt uranyl photocleavage to probe specific uranyl-binding sites in the 39E DNAzyme with catalytically relevant concentrations of uranyl. The results indicate that uranyl binds between T23 and C25 in the bulge loop, G11 and T12 in the stem loop of the enzyme strand, as well as between T2.4 and G3 close to the cleavage site in the substrate strand. Control experiments using two 39E DNAzyme mutants revealed a different cleavage pattern of the mutated region. Another DNAzyme, the 8–17 DNAzyme, which has a similar secondary structure but shows no activity in the presence of uranyl, indicated a different uranyl-dependent photocleavage as well. In addition, a close correlation between the concentration-dependent photocleavage and enzymatic activities is also demonstrated. Together, these experiments suggest that uranyl photocleavage has been successfully used to probe catalytically relevant uranyl-binding sites in the 39E DNAzyme. As uranyl is the cofactor of the 39E DNAzyme as well as the probe, specific uranyl binding has now been identified without disruption of the structure. PMID:23939617

Cepeda-Plaza, Marjorie; Null, Eric L.; Lu, Yi




Microsoft Academic Search

Polynuclear complexes with complex uranium- oxygen configurations, where ; the uranyl bond has two mutually perpendicular directions, are investigated. The ; cubic modification of UOâ and UOâ(OHâ) was considered as ; complexes of uranyl bonds with three mutually perpendicular spatial directions. ; (R.V.J.);




Bioreduction of hydrogen uranyl phosphate: mechanisms and U(IV) products.  


The mobility of uranium (U) in subsurface environments is controlled by interrelated adsorption, redox, and precipitation reactions. Previous work demonstrated the formation of nanometer-sized hydrogen uranyl phosphate (abbreviated as HUP) crystals on the cell walls of Bacillus subtilis, a non-U(VI)-reducing, Gram-positive bacterium. The current study examined the reduction of this biogenic, cell-associated HUP mineral by three dissimilatory metal-reducing bacteria, Anaeromyxobacter dehalogenans strain K, Geobacter sulfurreducens strain PCA, and Shewanella putrefaciens strain CN-32, and compared it to the bioreduction of abiotically formed and freely suspended HUP of larger particle size. Uranium speciation in the solid phase was followed over a 10- to 20-day reaction period by X-ray absorption fine structure spectroscopy (XANES and EXAFS) and showed varying extents of U(VI) reduction to U(IV). The reduction extent of the same mass of HUP to U(IV) was consistently greater with the biogenic than with the abiotic material under the same experimental conditions. A greater extent of HUP reduction was observed in the presence of bicarbonate in solution, whereas a decreased extent of HUP reduction was observed with the addition of dissolved phosphate. These results indicate that the extent of U(VI) reduction is controlled by dissolution of the HUP phase, suggesting that the metal-reducing bacteria transfer electrons to the dissolved or bacterially adsorbed U(VI) species formed after HUP dissolution, rather than to solid-phase U(VI) in the HUP mineral. Interestingly, the bioreduced U(IV) atoms were not immediately coordinated to other U(IV) atoms (as in uraninite, UO2) but were similar in structure to the phosphate-complexed U(IV) species found in ningyoite [CaU(PO4)2·H2O]. This indicates a strong control by phosphate on the speciation of bioreduced U(IV), expressed as inhibition of the typical formation of uraninite under phosphate-free conditions. PMID:23634690

Rui, Xue; Kwon, Man Jae; O'Loughlin, Edward J; Dunham-Cheatham, Sarrah; Fein, Jeremy B; Bunker, Bruce; Kemner, Kenneth M; Boyanov, Maxim I



Optimization of a uranyl nitrate passive neutron counter  

SciTech Connect

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).

Rauch, Eric Benton [Los Alamos National Laboratory; Bracken, David [Los Alamos National Laboratory; West, James [Los Alamos National Laboratory; Freeman, Corey [Los Alamos National Laboratory; Newell, Matthew R [Los Alamos National Laboratory; Bourret, Steven C [Los Alamos National Laboratory; Rothrock, Richard B [Los Alamos National Laboratory; Ladd - Lively, Jennifer L [ORNL; Schuh, Denise [ORNL



Seven-coordinate iron and manganese complexes with acyclic and rigid pentadentate chelates and their superoxide dismutase activity.  


The reactions of seven-coordinate [Fe(III)(dapsox)(H(2)O)(2)]ClO(4).H(2)O (1), [Fe(II)(H(2)dapsox)(H(2)O)(2)](NO(3))(2).H(2)O (2), and [Mn(II)(H(2)dapsox)(CH(3)OH)(H(2)O)](ClO4)2(H2O) (3) complexes of the acyclic and rigid pentadentate H(2)dapsox ligand [H2dapsox = 2,6-diacetylpyridinebis(semioxamazide)] with superoxide have been studied spectrophotometrically, electrochemically, and by a submillisecond mixing UV/vis stopped-flow in dimethyl sulfoxide (DMSO). The same studies were performed on the seven-coordinate [Mn(II)(Me(2)[15]pyridinaneN(5))(H(2)O)(2)]Cl(2).H(2)O (4) complex with the flexible macrocyclic Me(2)[15]pyridinaneN(5) ligand (Me(2)[15]pyridinaneN(5) = trans-2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),14,16-triene), which belongs to the class of proven superoxide dismutase (SOD) mimetics. The X-ray crystal structures of 2-4 were determined. All complexes possess pentagonal-bipyramidal geometry with the pentadentate ligand in the equatorial plane and solvent molecules in the axial positions. The stopped-flow experiments in DMSO (0.06% of water) reveal that all four metal complexes catalyze the fast disproportionation of superoxide under the applied experimental conditions, and the catalytic rate constants are found to be (3.7 +/- 0.5) x 10(6), (3.9 +/- 0.5) x 10(6), (1.2 +/- 0.3) x 10(7), and (5.3 +/- 0.8) x 10(6) M(-1) s(-1) for 1-4, respectively. The cytochrome c McCord-Fridovich (McCF) assay in an aqueous solution at pH = 7.8 resulted in the IC(50) values (and corresponding kMcCF constants) for 3 and 4, 0.013 +/- 0.001 microM (1.9 +/- 0.2 x 10(8) M(-1) s(-1)) and 0.024 +/- 0.001 microM (1.1 +/- 0.3 x 10(8) M(-1) s(-1)), respectively. IC(50) values from a nitroblue tetrazolium assay are found to be 6.45 +/- 0.02 and 1.36 +/- 0.03 microM for 1 and 4, respectively. The data have been compared with those obtained by direct stopped-flow measurements and discussed in terms of the side reactions that occur under the conditions of indirect assays. PMID:17880209

Liu, Gao-Feng; Filipovi?, Milos; Heinemann, Frank W; Ivanovi?-Burmazovi?, Ivana



Uranyl peroxide enhanced nuclear fuel corrosion in seawater  

PubMed Central

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

Armstrong, Christopher R.; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E.; Burns, Peter C.; Navrotsky, Alexandra



Arf6 coordinates actin assembly through the WAVE complex, a mechanism usurped by Salmonella to invade host cells  

PubMed Central

ADP ribosylation factor (Arf) 6 anchors to the plasma membrane, where it coordinates membrane trafficking and cytoskeleton remodelling, but how it assembles actin filaments is unknown. By reconstituting membrane-associated actin assembly mediated by the WASP family veroprolin homolog (WAVE) regulatory complex (WRC), we recapitulated an Arf6-driven actin polymerization pathway. We show that Arf6 is divergent from other Arf members, as it was incapable of directly recruiting WRC. We demonstrate that Arf6 triggers actin assembly at the membrane indirectly by recruiting the Arf guanine nucleotide exchange factor (GEF) ARNO that activates Arf1 to enable WRC-dependent actin assembly. The pathogen Salmonella usurped Arf6 for host cell invasion by recruiting its canonical GEFs EFA6 and BRAG2. Arf6 and its GEFs facilitated membrane ruffling and pathogen invasion via ARNO, and triggered actin assembly by generating an Arf1–WRC signaling hub at the membrane in vitro and in cells. This study reconstitutes Arf6-dependent actin assembly to reveal a mechanism by which related Arf GTPases orchestrate distinct steps in the WRC cytoskeleton remodelling pathway. PMID:24085844

Humphreys, Daniel; Davidson, Anthony C.; Hume, Peter J.; Makin, Laura E.; Koronakis, Vassilis



Coordinated control of senescence by lncRNA and a novel T-box3 co-repressor complex  

PubMed Central

Cellular senescence is a crucial tumor suppressor mechanism. We discovered a CAPER?/TBX3 repressor complex required to prevent senescence in primary cells and mouse embryos. Critical, previously unknown roles for CAPER? in controlling cell proliferation are manifest in an obligatory interaction with TBX3 to regulate chromatin structure and repress transcription of CDKN2A-p16INK and the RB pathway. The IncRNA UCA1 is a direct target of CAPER?/TBX3 repression whose overexpression is sufficient to induce senescence. In proliferating cells, we found that hnRNPA1 binds and destabilizes CDKN2A-p16INK mRNA whereas during senescence, UCA1 sequesters hnRNPA1 and thus stabilizes CDKN2A-p16INK. Thus CAPER?/TBX3 and UCA1 constitute a coordinated, reinforcing mechanism to regulate both CDKN2A-p16INK transcription and mRNA stability. Dissociation of the CAPER?/TBX3 co-repressor during oncogenic stress activates UCA1, revealing a novel mechanism for oncogene-induced senescence. Our elucidation of CAPER? and UCA1 functions in vivo provides new insights into senescence induction, and the oncogenic and developmental properties of TBX3. DOI: PMID:24876127

Kumar P, Pavan; Emechebe, Uchenna; Smith, Richard; Franklin, Sarah; Moore, Barry; Yandell, Mark; Lessnick, Stephen L; Moon, Anne M



Coordinated control of senescence by lncRNA and a novel T-box3 co-repressor complex.  


Cellular senescence is a crucial tumor suppressor mechanism. We discovered a CAPER?/TBX3 repressor complex required to prevent senescence in primary cells and mouse embryos. Critical, previously unknown roles for CAPER? in controlling cell proliferation are manifest in an obligatory interaction with TBX3 to regulate chromatin structure and repress transcription of CDKN2A-p16INK and the RB pathway. The IncRNA UCA1 is a direct target of CAPER?/TBX3 repression whose overexpression is sufficient to induce senescence. In proliferating cells, we found that hnRNPA1 binds and destabilizes CDKN2A-p16INK mRNA whereas during senescence, UCA1 sequesters hnRNPA1 and thus stabilizes CDKN2A-p16INK. Thus CAPER?/TBX3 and UCA1 constitute a coordinated, reinforcing mechanism to regulate both CDKN2A-p16INK transcription and mRNA stability. Dissociation of the CAPER?/TBX3 co-repressor during oncogenic stress activates UCA1, revealing a novel mechanism for oncogene-induced senescence. Our elucidation of CAPER? and UCA1 functions in vivo provides new insights into senescence induction, and the oncogenic and developmental properties of TBX3. PMID:24876127

Kumar P, Pavan; Emechebe, Uchenna; Smith, Richard; Franklin, Sarah; Moore, Barry; Yandell, Mark; Lessnick, Stephen L; Moon, Anne M



Optical properties of ammonium uranyl fluoride characterized by photoluminescence and photoacoustic spectroscopy  

NASA Astrophysics Data System (ADS)

PL and PAS studies were performed on uranyl compounds viz. uranium oxalate, uranium fluoride and ammonium uranyl fluoride. PL and PAS spectrum of ammonium uranyl fluoride is being reported for the first time. Ammonium uranyl fluoride is blue shifted with respect to uranyl fluoride, as a result of ammonium bonding. The vibronic separations were determined in the excited state and the ground state using excitation/PA spectra and emission spectra respectively. Fluorescence decay data could be fitted only with biexponential decay in all of these compounds indicating the presence of two different environments in these compounds. Low temperature luminescence leads to enhancement in emission intensity and lifetime value. The temperature dependence studies of average fluorescence lifetimes of ammonium uranyl are described in this paper. Based on this studies activation energy value for ammonium uranyl fluoride at which 3? and 1? potential surfaces will cross is calculated.

Gupta, Santosh K.; Dhobale, A. R.; Natarajan, V.; Godbole, S. V.



Vibrational spectra of discrete UO22+ halide complexes in the gas phase  

SciTech Connect

The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases is frequently obfuscated by solvent interactions, that can alter ligand binding and spectroscopic properties. The approach taken in this study is to move the uranyl halide complexes into the gas phase where they are free from solvent interactions, and then interrogate their vibrational spectroscopy using infrared multiple photon dissociation (IRMPD). The spectra of cationic coordination complexes having the composition [UO2(X)(ACO)3]+ (X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric v3 UO2 frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter the binding in the complex. The v3 peak in the spectrum of the F-containing complex was ~ 10 cm-1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency was relatively insensitive to the identity of the halide, although a modest shift to the blue was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the v1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes were conducted by measuring the v3 UO2 frequencies of [UO2X3]-, where X = Cl-, Br- and I-. The trifluoro complex could not be photodissociated. In these negatively charged complexes, the UO2 v3 values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that dissociation energy decreased on the order F > Cl > Br > I.

Gary S. Groenewold; Michael J. van Stipdonk; Wibe A. de Jong; Jos Oomens; Garold L. Gresham



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)

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.

Sayin, Koray; Karaka?, Duran



Molecular tectonics: homochiral coordination networks based on combinations of a chiral neutral tecton with Hg(II), Cu(II) or Ni(II) neutral complexes as metallatectons.  


The use of compound 1 as an enantiomerically pure neutral and rigid organic linear tecton bearing two divergently oriented monodentate coordinating sites appended with two chiral centres of the same (S) configuration leads, in the presence of neutral metal complexes behaving either as a linear (Cu(hfac)2, Cu(OAc)2) or a V-shaped (HgCl2) 2-connecting node or a 4-connecting square node (NiCl2), to the formation of four homochiral 1- and 2-D coordination polymers. PMID:24276523

Larpent, Patrick; Jouaiti, Abdelaziz; Kyritsakas, Nathalie; Hosseini, Mir Wais



Structure and dynamics of aqueous solution of uranyl ions  

NASA Astrophysics Data System (ADS)

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.

Chopra, Manish; Choudhury, Niharendu



An infrared and Raman spectroscopic study of the uranyl micas  

NASA Astrophysics Data System (ADS)

Vibrational spectroscopy using a combination of infrared and Raman spectroscopy has been used to study the uranyl micas also known as the autunite minerals, of general formula M(UO 2) 2(XO 4) 2·8-12H 2O where M may be Ba, Ca, Cu, Fe 2+, Mg, Mn 2+ or 1/2(HAl) and X is As or P. Included in these minerals are autunite, metautunite, torbernite, meta-torbernite, meta-zeunerite, saléeite and sabugalite. Compared with the results of infrared spectroscopy, Raman microscopy shows excellent band separation enabling the separation and identification of bands attributed to (UO 2) 2+ units, PO 4 and AsO 4 units. Common to all spectra were bands at around 900 and 818 cm -1, attributed to the antisymmetric and symmetric stretching vibrations of the (UO 2) 2+ units. Water in autunites is in a highly structured arrangement in the interlayer of the uranyl micas. Water molecules are differentiated according to the strength of the hydrogen bonds formed between the water and the adjacent uranyl-phosphate or uranyl-arsenate surfaces and the hydration sphere of the interlayer cation.

Frost, Ray L.



Analysis of High Enriched Uranyl Nitrate Solution Containing Cadmium  

SciTech Connect

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.

S. S. Kim



Preparation and Reactions of the 1,1-Dithiolato Complexes of Ni(II). An Undergraduate Coordination Chemistry Experiment.  

ERIC Educational Resources Information Center

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…

Ballester, L.; Perpinan, M. F.



Charge asymmetry of the purple membrane measured by uranyl quenching of dansyl fluorescence.  

PubMed Central

Purple membrane was covalently labeled with 5-(dimethylamino) naphthalene-1-sulfonyl hydrazine (dansyl hydrazine) by carbodiimide coupling to the cytoplasmic surface (carboxyl-terminal tail: 0.7 mol/mol bacteriorhodopsin) or by periodate oxidation and dimethylaminoborane reduction at the extracellular surface (glycolipids: 1 mol/mol). In 2 mM acetate buffer, pH 5.6, micromolar concentrations of UO2 +(2) were found to quench the dansyl groups on the cytoplasmic surface (maximum = 26%), while little quenching was observed at the extracellular surface (maximum = 4%). Uranyl ion quenched dansyl hydrazine in free solution at much higher concentrations. Uranyl also bound tightly to unmodified purple membrane, (apparent dissociation constant = 0.8 microM) as measured by a centrifugation assay. The maximum stoichiometry was 10 mol/mol of bacteriorhodopsin, which is close to the amount of phospholipid phosphorus in purple membrane. The results were analyzed on the assumptions that UO2 +(2) binds in a 1:1 complex with phospholipid phosphate and that the dansyl distribution and quenching mechanisms are the same at both surfaces. This indicates a 9:1 ratio of phosphate between the cytoplasmic and extracellular surfaces. Thus, the surface change density of the cytoplasmic side of the membrane is more negative than -0.010 charges/A2. PMID:6733237

Renthal, R; Cha, C H



Uranyl interaction with the hydrated (1 1 1) nickel face: A periodic density functional theory investigation  

NASA Astrophysics Data System (ADS)

Periodic DFT calculations using plane waves basis sets with the GGA formalism were performed in order to study the behavior of the UO22+ uranyl ion at the water-Ni(1 1 1) interface. First, the adsorption of water molecules interacting with an optimized surface model has been studied. At low coverage, isolated water molecules adsorb preferentially on top of the surface nickel atoms, the plane defined by the H 2O molecule being almost parallel to the surface. When the water coverage increases from 1/9 ML to 2/3 ML (ML = monolayer coverage), hydrogen bonds are created leading to the formation of water hexamers, as suggested experimentally on Ni(1 1 1) and other metallic surfaces [A. Michaelides, A. Alavi, D.A. King, Physical Review B 69 (2004) 113404. M. Nakamura, M. Ito, Chemical Physics Letters 325 (2000) 293-298]. Higher water coverage induces the formation of an additional water layer physisorbed over the cyclic hexamers. In a second step, the behavior of UO22+ with respect to the hydrated Ni(1 1 1) face has been investigated. Evidence that two adsorption modes can take place was put forward: a first one with an outer sphere adsorption mechanism, where two water molecules of the uranyl ion first hydration shell are shared with four water hexamers, and a second one through a strong Ni-O -yle bond formation. Even though the second surface complex is energetically the most stable, the necessary activation energy to reach it makes it improbable.

Levesque, M.; Roques, J.; Domain, C.; Perron, H.; Veilly, E.; Simoni, E.; Catalette, H.



Vibrational Spectra of Discrete UO?²? Halide Complexes in the Gas Phase  

SciTech Connect

The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases is frequently obfuscated by solvent interactions that can alter ligand binding and spectroscopic properties. The approach taken in this study is to move the uranyl halide complexes into the gas phase where they are free from solvent interactions, and then interrogate their vibrational spectroscopy using infrared multiple photon dissociation (IRMPD). The spectra of cationic coordination complexes having the composition [UO?(X)(ACO)?]+ (where X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric ?? UO? frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo-octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter its binding in the complex. The ?? peak in the spectrum of the F-containing complex was 9 cm-1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency was relatively insensitive to the identity of the halide, although a modest shift to higher wavenumber was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the ?1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes [UO?X?]- (where X = Cl-, Br- and I-) compared the ?? UO? modes versus halide, and showed that the ?? values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that [UO?X?]--X. and [UO?X?].-X- dissociation energies decreased on the order F > Cl > Br > I. The trifluoro complex could not be photodissociated in these experiments.

Groenewold, G. S.; Van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; Gresham, Garold L.; Mcilwain, Michael



Cluster-Models for Uranyl(VI) Adsorption on alpha-Alumina  

SciTech Connect

Aqueous complexation, adsorption and redox chemistry of actinide species at mineral surfaces have significant impact on their transport and reactive behaviour in chemically and physically heterogeneous environments. The adsorption configurations and energies of micro-solvated uranyl dication, UO2 2+, on fully hydroxylated and H-deficient a-alumina (0001)-like finite cluster models were studied. The significant size of the models provides faithful representations of features that have emerged from periodic calculations, but most importantly, they afford us a systematic study of the preferred adsorption configurations, effect of secondary solvation shells and explicit treatment of the total charge. The energetics computed from the difference between the optimized structures and the appropriate reference states, point at a preference for inner sphere type complex.

Glezakou, Vassiliki Alexandra; De Jong, Wibe A.



Synthesis, X-ray crystal structures, thermal and electrochemical properties of thiosemicarbazidatodioxouranium(VI) complexes.  


The stable uranyl complexes, [UO(2)(L)C(9)H(19)OH], were obtained from 3,5-dichlorosalicyl-(L(I)) and salicyl-aldehyde-S-propyl-thiosemicarbazones (L(II)) with substituted-salicylaldehyde in nonyl alcohol. The structures of the complexes have been characterized by elemental analysis, IR, (1)H NMR, conductivity, magnetic moment measurements, cyclic voltammetry, thermal gravimetric analysis and single crystal X-ray diffraction technique. The U(VI) centre is seven-coordinated in a distorted pentagonal bipyramidal geometry. The relative orientations of the nonyl alcohol and S-propyl group in the title complexes are completely different due to different crystal packing. Electrochemical behaviors of the thiosemicarbazone ligands and the uranyl complexes were studied using cyclic voltammetry and square wave voltammetry. Redox processes of the compounds are significantly influenced by the central metal ions and the nature of substituents on the thiosemicarbazones, which are important factors in controlling the redox properties. In situ spectroelectrochemical studies were employed to determine the colors and spectra of electro-generated species of the complexes. PMID:20922238

Sahin, Musa; Koca, At?f; Ozdemir, Nam?k; Dinçer, Muharrem; Büyükgüngör, Orhan; Bal-Demirci, Tülay; Ulküseven, Bahri



Uranyl ion extraction with conventional PUREX/TRUEX ligands assessed by electroanalytical chemistry at micro liquid/liquid interfaces.  


The facilitated ion transfer (FIT) of uranyl or dioxouranium (UO(2)(2+)) was studied electrochemically using a micro interface between two immiscible electrolytic solutions (micro-ITIES) in order to evaluate the complexation stoichiometry and complexation constants (?) of two widely used ligands in spent fuel reprocessing: tributylphosphate (TBP) and octyl(phenyl)-N,N-diisobutylcarbamoylmethyl-phosphine oxide (CMPO). For the first time, discrete interfacial complexation reaction steps of varying uranyl to the two ligands ratios were resolved using the micro-ITIES hosted at the tip of a 25 ?m diameter glass capillary. Two stoichiometries for UO(2)NO(3)TBP(n)(+) were determined including n = 3 and 4 with ? values of 3.2 × 10(11) and 3.9 × 10(13), respectively. Subsequently, three distinct complexation reactions of CMPO with UO(2)(2+) were discovered corresponding to UO(2)NO(3)CMPO(2)(+), UO(2)NO(3)CMPO(3)(+), and UO(2)CMPO(5)(2+) whose respective complexation constants were determined to be 8.0 × 10(11), 8.8 × 10(14), and 6.5 × 10(32). The participation of nitrate anions in these complexation reactions is also discussed. PMID:21848323

Stockmann, Tom J; Ding, Zhifeng



Stereochemical control over Mn(II)-Thio versus Mn(II)-Oxy coordination in adenosine 5 prime -O-(1-thiodiphosphate) complexes at the active site of creatine kinase  

SciTech Connect

The stereochemical configurations of the Mn(II) complexes with the resolved epimers of adenosine 5{prime}-O-(1-thiodiphosphate) (ADP{alpha}S), bound at the active site of creatine kinase, have been determined in order to assess the relative strengths of enzymic stereoselectivity versus Lewis acid/base preferences in metal-ligand binding. Electron paramagnetic resonance (EPR) data have been obtained for Mn(II) in anion-stabilized, dead-end (transition-state analogue) complexes, in ternary enzyme-Mn{sup II}ADP{alpha}S complexes, and in the central complexes of the equilibrium mixture. The modes of coordination of Mn(II) at P{sub alpha} in the nitrate-stabilized, dead-end complexes with each epimer of ADP{alpha}S were ascertained by EPR measurements with (R{sub p})-({alpha}-{sup 17}O)ADP{alpha}S and (S{sub p})-({alpha}-{sup 17}O)ADP{alpha}S. A reduction in the magnitude of the {sup 55}Mn hyperfine coupling constant in the spectrum for the complex containing (S{sub p})-ADP{alpha}S is indicative of Mn(II)-thio coordination at P{sub alpha}. The results indicate that a strict discrimination for a unique configuration of the metal-nucleotide substrate is expressed upon binding of all of the substrates to form the active complex (or an analogue thereof). This enzymic stereoselectivity provides sufficient binding energy to overcome an intrinsic preference for the hard Lewis acid Mn(II) to coordinate to the hard Lewis base oxygen.

Smithers, G.W.; Sammons, R.D.; Goodhart, P.J.; LoBrutto, R.; Reed, G.H. (Univ. of Wisconsin, Madison (USA))



Multispecies diffusion models: A study of uranyl species diffusion  

NASA Astrophysics Data System (ADS)

Rigorous numerical description of multispecies diffusion requires coupling of species, charge, and aqueous and surface complexation reactions that collectively affect diffusive fluxes. The applicability of a fully coupled diffusion model is, however, often constrained by the availability of species self-diffusion coefficients, as well as by computational complication in imposing charge conservation. In this study, several diffusion models with variable complexity in charge and species coupling were formulated and compared to describe reactive multispecies diffusion in groundwater. Diffusion of uranyl [U(VI)] species was used as an example in demonstrating the effectiveness of the models in describing multispecies diffusion. Numerical simulations found that a diffusion model with a single, common diffusion coefficient for all species was sufficient to describe multispecies U(VI) diffusion under a steady state condition of major chemical composition, but not under transient chemical conditions. Simulations revealed that for multispecies U(VI) diffusion under transient chemical conditions, a fully coupled diffusion model could be well approximated by a component-based diffusion model when the diffusion coefficient for each chemical component was properly selected. The component-based diffusion model considers the difference in diffusion coefficients between chemical components, but not between the species within each chemical component. This treatment significantly enhanced computational efficiency at the expense of minor charge conservation. The charge balance in the component-based diffusion model can be enforced, if necessary, by adding a secondary migration term resulting from model simplification. The effect of ion activity coefficient gradients on multispecies diffusion is also discussed. The diffusion models were applied to describe U(VI) diffusive mass transfer in intragranular domains in two sediments collected from U.S. Department of Energy's Hanford 300A, where intragranular diffusion is a rate-limiting process controlling U(VI) adsorption and desorption. The grain-scale reactive diffusion model was able to describe U(VI) adsorption/desorption kinetics that had been previously described using a semiempirical, multirate model. Compared with the multirate model, the diffusion models have the advantage to provide spatiotemporal speciation evolution within the diffusion domains.

Liu, Chongxuan; Shang, Jianying; Zachara, John M.



Ezrin-anchored Protein Kinase A Coordinates Phosphorylation-dependent Disassembly of a NHERF1 Ternary Complex to Regulate Hormone-sensitive Phosphate Transport*  

PubMed Central

Congenital defects in the Na/H exchanger regulatory factor-1 (NHERF1) are linked to disordered phosphate homeostasis and skeletal abnormalities in humans. In the kidney, these mutations interrupt parathyroid hormone (PTH)-responsive sequestration of the renal phosphate transporter, Npt2a, with ensuing urinary phosphate wasting. We now report that NHERF1, a modular PDZ domain scaffolding protein, coordinates the assembly of an obligate ternary complex with Npt2a and the PKA-anchoring protein ezrin to facilitate PTH-responsive cAMP signaling events. Activation of ezrin-anchored PKA initiates NHERF1 phosphorylation to disassemble the ternary complex, release Npt2a, and thereby inhibit phosphate transport. Loss-of-function mutations stabilize an inactive NHERF1 conformation that we show is refractory to PKA phosphorylation and impairs assembly of the ternary complex. Compensatory mutations introduced in mutant NHERF1 re-establish the integrity of the ternary complex to permit phosphorylation of NHERF1 and rescue PTH action. These findings offer new insights into a novel macromolecular mechanism for the physiological action of a critical ternary complex, where anchored PKA coordinates the assembly and turnover of the Npt2a-NHERF1-ezrin complex. PMID:22628548

Wang, Bin; Means, Chris K.; Yang, Yanmei; Mamonova, Tatyana; Bisello, Alessandro; Altschuler, Daniel L.; Scott, John D.; Friedman, Peter A.



51V Solid-state NMR and Density-Functional Theory Studies of Eight-Coordinate Non-Oxo Vanadium Complexes: Oxidized Amavadin  

PubMed Central

SUMMARY Using 51V magic angle spinning solid-state NMR spectroscopy and Density Functional Theory calculations we have characterized the chemical shift and quadrupolar coupling parameters for two eight-coordinate vanadium complexes, [PPh4][V(V)(HIDPA)2] and [PPh4][V(V)(HIDA)2]; HIDPA = 2,2?-(hydroxyimino)dipropionate and HIDA = 2,2?-(hydroxyimino)diacetate. The coordination geometry under examination is the less common non-oxo eight coordinate distorted dodecahedral geometry that has not been previously investigated by solid-state NMR spectroscopy. Both complexes were isolated by oxidizing their reduced forms: [V(IV)(HIDPA)2]2- and [V(IV)(HIDA)2]2-. V(IV)(HIDPA)22- is also known as amavadin, a vanadium-containing natural product present in the Amanita muscaria mushroom and responsible for vanadium accumulation in nature. The quadrupolar coupling constants, CQ, are found to be moderate, 5.0 to 6.4 MHz while the chemical shift anisotropies are relatively small for vanadium complexes, ?420 and 360 ppm. The isotropic chemical shifts in the solid state are ?220 and ?228 ppm for the two compounds, and near the chemical shifts observed in solution. Presumably this is a consequence of the combined effects of the increased coordination number and the absence of oxo groups. Density Functional Theory calculations of the electric field gradient parameters are in good agreement with the NMR results while the chemical shift parameters show some deviation from the experimental values. Future work on this unusual coordination geometry and a combined analysis by solid-state NMR and Density Functional Theory should provide a better understanding of the correlations between experimental NMR parameters and the local structure of the vanadium centers. PMID:19421628

Ooms, Kristopher J.; Bolte, Stephanie E.; Baruah, Bharat; Choudhary, Muhammad Aziz; Crans, Debbie C.; Polenova, Tatyana



Protonation-induced paramagnetism. Structures and stabilities of six- and seven-coordinate complexes of Os(II) in singlet and triplet states: a density functional study.  


Li, Yeh, and Taube in 1993 (J. Am. Chem. Soc. 1993, 115, 10384) synthesized a number of complexes which can be formally regarded as protonated Os(II) species. Some of these were paramagnetic, in contrast to the diamagnetism of the closed shell 5d(6) Os(II) ions. This intriguing phenomenon is investigated theoretically using density functional theory. The geometries, stabilities, and electronic structures of a series of six- and seven-coordinate osmium complexes were studied in gas phase and aqueous solution using the B3P86 functional, in conjunction with the isodensity-polarized continuum model of solvation. The general formula for these complexes is [Os(NH(3))(4)H(L(1)(x)())(m)()(L(2)(y)())(n)()](()(x)()(+)(y)()(+3)+), where L(1) and L(2) = H(2)O, NH(3), CH(3)OH, CH(3)CN, Cl(-), and CN(-), which could be regarded as protonated Os(II) species or hydrides of Os(IV), although according to this work the osmium-hydrogen interaction is best described as a covalent Os(III)-H bond, in which the hydrogen is near-neutral. The ground states are generally found to be singlets, with low-lying triplet excited states. Solvation tends to favor the singlet states by as much as approximately 18 kcal mol(-)(1) in the 3+ ions, an effect which is proportional to the corresponding difference in molecular volumes. To have realistic estimates of the importance of spin-orbit coupling in these systems, the spin-orbit energy corrections were computed for triplet [Os(NH(3))(4)](2+), [Os(NH(3))(4)H](3+), and [Os(NH(3))(4)H(H(2)O)](3+), along with gas-phase Os and its ions as well as [Os(H(2)O)(6)](3+). The seven-coordinate triplet-state complex [Os(NH(3))(5)H(CH(3)OH)](3+), which had been successfully isolated by Li, Yeh, and Taube, is predicted to be a stable six-coordinate complex which strongly binds to a methanol molecule in the second coordination shell. The calculations further suggest that the singlet-triplet splitting would be very small, a few kilocalories per mole at most. The geometries and the electronic structures of the complexes are interpreted and rationalized in terms of Pauling's hybridization model in conjunction with conventional ligand field theory that effectively precludes the existence of true seven-coordinate triplet-state complexes of the above formula. PMID:11389632

Mylvaganam, K; Bacskay, G B; Hush, N S



First examples of ternary lanthanide succinate complexes: hydro-solvothermal syntheses and structures of lanthanide coordination polymers of succinic acid and 1,10-phenanthroline  

NASA Astrophysics Data System (ADS)

Three new supramolecular lanthanide coordination polymers, {[Eu(SA) 1.5(phen)]·H 2O} n ( 1), and [Ln(SA) 1.5(phen)] n [Ln=Er ( 2); Yb ( 3)] were obtained by hydro-solvothermal reactions of lanthanide chlorides with succinic acid (H 2SA) and 1,10-phenanthroline (phen), and characterized by single crystal X-ray diffraction, elemental analysis and IR spectrum. Complexes 1- 3 also have 2D networks which are further architectured to form 3D supramolecular structures by hydrogen bonds and ?-? aromatic interactions, of which 1 has 1D channels. The H 2SA ligands are all completely deprotonated and exhibit tetra- and pentadentate coordination modes in the titled complexes. The photoluminescence property of 1 was investigated.

Liu, Chong-Bo; Wen, Hui-Liang; Tan, Sheng-Shui



Selective separation of uranyl ion from TRU`s in a combined solvent extraction process using tetrahydrofuran-2,3,4,5-tetracarboxylic acid  

SciTech Connect

Selective partitioning of uranyl from transuranic elements in a solvent extraction system which employs a neutral organophosphorus extractant and an aqueous complexant has been demonstrated in a previous report. The extractant solution combines octyl(phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO), diamyl(amyl)phosphonate (or tributylphosphate), and di(t-butylcyclohexano)-18-crown-6 in Isopar L, and is designed for simultaneous removal of strontium, technetium, lanthanides and actinides from radioactive wastes. The aqueous complexant is tetrahydrofuran-2,3,4,5-tetracarboxylic acid (THFTCA). In this report, the separation of UO{sub 2}{sup 2+} from Np(IV), Eu(III), Am(III), and Pu(IV) using the Combined Process Solvent has been optimized. Potentiometric titration and NMR spectroscopic results describe the distribution of THFTCA into the organic phase as a function of acidity and [THFTCA]. Further potentiometric titration experiments have determined the stoichiometry and stability of uranyl complexes in the aqueous phase. The thermodynamic data indicate that the uranyl complexes are anomalously weak which partially accounts for the selectivity. Ternary complexes involving UO{sub 2}{sup 2+}, CMPO, and THFTCA in the extractant phase also appear to play a role. 13 refs., 6 figs., 1 tab.

Nash, K.L.; Horwitz, E.P.; Diamond, H.; Rickert, P.G.; Muntean, J.V.; Mendoza, M.D.; Giuseppe, G. di [Argonne National Lab., IL (United States)



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)

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 ?-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.

Inomata, Yoshie; Shibata, Akio; Yukawa, Yasuhiko; Takeuchi, Toshio; Moriwaki, Takao


Catalyst design for iron-promoted reductions: an iron disilyl-dicarbonyl complex bearing weakly coordinating ?2-(H-Si) moieties.  


Iron disilyl dicarbonyl complex 1, in which two H-Si moieties of the 1,2-bis(dimethylsilyl)benzene ligand were coordinated to the iron center in an ?(2)-(H-Si) fashion, was synthesized by the reaction of (?(4)-C6H8)Fe(CO)3 with 2 equiv. of 1,2-bis(dimethylsilyl)benzene under photo-irradiation. Complex 1 demonstrated high catalytic activity toward the hydrogenation of alkenes, the hydrosilylation of alkenes and the reduction of carbonyl compounds. PMID:24154529

Sunada, Yusuke; Tsutsumi, Hironori; Shigeta, Keisuke; Yoshida, Ryota; Hashimoto, Toru; Nagashima, Hideo



Synthesis of 2D polymeric dicyanamide bridged hexa-coordinated Cu(II) complex: Structural characterization, spectral studies and TDDFT calculation  

NASA Astrophysics Data System (ADS)

A rare 2D polymeric dicyanamide bridged hexa-coordinated copper(II) complex [Cu(L1?)(?1,5-dca)2]n (1) (L1? = 2-carboxypyrazine) has been synthesized from the reaction of Cu(NO3)2?6H2O, 2-pyrazinecarbonitrile (L1) and sodium dicyanamide (Nadca) in methanolic medium. Single crystal X-ray analysis reveals that the complex has a 2D infinite zigzag chain structure in which copper(II) ions are bridged by single dicyanamide ligand in an end-to-end fashion. Such 2-carboxypyrazine can be obtained on the way of metal-assisted nitrile hydrolysis which well connected with Cu(NO3)2?6H2O and dicyanamide (dca) to give rare 2D Cu(II) polymeric complex due to the flexibility in the coordination ability of the copper(II) ions within the polymeric chain. The geometry of the asymmetric unit of the complex was optimized in singlet state by DFT method with multilayer ONIOM model at doublet spin state accordance with repeating asymmetric unit only. The electronic spectrum of the complex is explained using TDDFT calculation.

Konar, Saugata; Saha, Urmila; Dolai, Malay; Chatterjee, Sudipta



Uranyl Soil Extraction and Fluorescence Enhancement by Nanoporous Silica Gel: pH effects  

Microsoft Academic Search

Nanoporous silica gel was employed to extract uranyl from contaminated soil and to enhance the fluorescence intensity and\\u000a lifetime. The fluorescence lifetime and intensity of uranyl ions absorbed within nanoporous silica gel was measured from pH 1–13.\\u000a The results show that the uranyl fluorescence intensity can be enhanced by approximately two orders of magnitude by the silica\\u000a nanoporous matrix from pH 4–12

Chien-Cheng Chen; Dmitry Pestov; Jean D. Nelson; John E. Anderson; Gary Tepper



Electrochemical uranyl cation biosensor with DNA oligonucleotides as receptor layer.  


The present study aims at the further development of the uranyl oligonucleotide-based voltammetric biosensor, which takes advantage of strong interaction between UO2(2+) and phosphate DNA backbone. Herein we report the optimization of working parameters of previously elaborated electrochemical DNA biosensor. It is shown that the sensor sensitivity is highly dependent on the oligonucleotide probe length and the incubation time of sensor in a sample solution. Consequently, the highest sensitivity was obtained for 10-nucleotide sequence and 60 min incubation time. The lower detection limit towards uranyl cation for developed biosensor was 30 nM. The influence of mixed monolayers and the possibility of developing a non-calibration device were also investigated. The selectivity of the proposed biosensor was significantly improved via elimination of adenine nucleobases from the DNA probe. Moreover, the regeneration procedure was elaborated and tested to prolong the use of the same biosensor for 4 subsequent determinations of UO2(2+). PMID:24334186

Jarczewska, Marta; Zió?kowski, Robert; Górski, ?ukasz; Malinowska, El?bieta



Mössbauer and FTIR spectroscopic studies of iron anthranilates: coordination, structure and some ecological aspects of iron complexation  

NASA Astrophysics Data System (ADS)

The data on the coordination and structure of iron(II) and iron(III) anthranilates in the solid state and in aqueous medium are presented and discussed, as studied using Mössbauer (for solid products and frozen solutions) and FTIR spectroscopy (for solid samples). Whereas, in slightly acidic nitrate solutions under aerobic conditions ferric ions can still be gradually reduced by anthranilic ( o-aminobenzoic) acid, which may have some ecological significance, in circumneutral media this process is retarded. Mössbauer parameters calculated for iron(II) and iron(III) anthranilates, as well as characteristic vibration modes of certain functional groups involved in coordination with iron cations are discussed. The FTIR data obtained for ferrous anthranilates, as compared to anthranilic acid, definitely exhibit the direct involvement of both the carboxylic and the amino groups of anthranilic acid in coordination with iron.

Kamnev, A. A.; Kuzmann, E.; Perfiliev, Yu. D.; Vankó, Gy.; Vértes, A.



Analysis of High Enriched Uranyl Nitrate Solution Containing Cadmium  

Microsoft Academic Search

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

Soon Sam Kim


A novel 3D heterometallic coordination complex with (3,4,5)-connected net topology: Synthesis, structure and luminescent property  

NASA Astrophysics Data System (ADS)

A novel three-dimensional Ag(I)-Pb(II) heteronuclear coordination polymer, namely [Ag2Pb2(BTC)2(H2O)2]n (1), where H3BTC = 1,3,5-benzenetricarboxyl acid, has been hydrothermally synthesized and structurally characterized by elemental analysis(EA), infrared spectroscopy(IR) and single crystal X-ray diffraction. The BTC3- ligand exhibits an interesting coordination mode to form a three-dimensional (3D) framework with a novel hexa-nodal (3,4,5)-connected net topology. The thermal stability and solid state fluorescence of 1 have also been investigated.

Sun, Qiao-Zhen; Yin, Yi-Biao; Chai, Li-Yuan; Liu, Hui; Hao, Peng-Fei; Yan, Xue-Ping; Guo, Yu-Qi



Determination of the solubility of uranyl metasilicate in the sorption of uranium by silica gel  

SciTech Connect

The process of the sorption of uranyl ions was treated as a chemical process of the conversion of solid silicic acid into uranium metasilicate, complicated by the dissolution of the latter in a solution of the complexant. The equilibrium of this process is determined by the ratio of the solubilities of uranylmetasilicate and silicic acid under the conditions of sorption. It was shown that the process of the absorption of uranium by silica gel is not complicated by the formation of uranium hydroxide: Its activity products over the sorption products, while varying over a wide range, remain considerably lower (by more than three orders of magnitude) than the known value of K/sub S//sup 0/(UO/sub 2/(OH)/sub 2/) = 1 x 10/sup -22/

Dushin, A.Yu.; Signalov, I.N.; Dushina, A.P.; Aleskovskii, V.B.



How are Centrosymmetric and Noncentrosymmetric Structures Achieved in Uranyl Borates?  

SciTech Connect

Four uranyl borates, UO{sub 2}B{sub 2}O{sub 4} (UBO-1), ?-(UO{sub 2}){sub 2}[B{sub 9}O{sub 14}(OH){sub 4}] (UBO-2), ?-(UO{sub 2}){sub 2}[B{sub 9}O{sub 14}(OH){sub 4}] (UBO-3), and (UO{sub 2}){sub 2}[B{sub 13}O{sub 20}(OH){sub 3}]·1.25H{sub 2}O (UBO-4), have been prepared from boric acid fluxes at 190 °C. UBO-3 and UBO-4 are centrosymmetric, whereas UBO-1 and UBO-2 are noncentrosymmetric (chiral and polar). These uranyl borates possess layered structures constructed from UO{sub 8} hexagonal bipyramids, BO{sub 3} triangles, and BO{sub 4} tetrahedra. In the case of UBO-4, clusters of BO{sub 3} triangles link the layers together to form open slabs with a thickness of almost 2 nm. The ability of uranyl borates to use very similar layers to yield both centrosymmetric and noncentrosymmetric layers is detailed in this work.

Wang, Shuao; Alekseev, Evgeny V.; Stritzinger, Jared T.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.



Developing predictive rules for coordination geometry from visible circular dichroism of copper(II) and nickel(II) ions in histidine and amide main-chain complexes.  


Circular dichroism (CD) spectroscopy in the visible region (vis-CD) is a powerful technique to study metal-protein interactions. It can resolve individual d-d electronic transitions as separate bands and is particularly sensitive to the chiral environment of the transition metals. Modern quantum chemical methods enable CD spectra calculations from which, along with direct comparison with the experimental CD data, the conformations and the stereochemistry of the metal-protein complexes can be assigned. However, a clear understanding of the observed spectra and the molecular configuration is largely lacking. In this study, we compare the experimental and computed vis-CD spectra of Cu(2+)-loaded model peptides in square-planar complexes. We find that the spectra can readily discriminate the coordination pattern of Cu(2+) bound exclusively to main-chain amides from that involving both main-chain amides and a side-chain (i.e. histidine side-chain). Based on the results, we develop a set of empirical rules that relates the appearance of particular vis-CD spectral features to the conformation of the complex. These rules can be used to gain insight into coordination geometries of other Cu(2+)- or Ni(2+)-protein complexes. PMID:25039600

Stanyon, Helen F; Cong, Xiaojing; Chen, Yan; Shahidullah, Nabeela; Rossetti, Giulia; Dreyer, Jens; Papamokos, George; Carloni, Paolo; Viles, John H



Synthesis, characterization, and in vitro evaluation of new coordination complexes of platinum(ii) and rhenium(i) with a ligand targeting the translocator protein (TSPO).  


The 18 kDa translocator protein (TSPO) is overexpressed in many types of cancers and is also abundant in activated microglial cells occurring in inflammatory neurodegenerative diseases. The TSPO-selective ligand 2-(8-(2-(bis-(pyridin-2-yl-methyl)amino)acetamido)-2-(4-chlorophenyl)H-imidazo[1,2-a]pyridin-3-yl)-N,N-dipropylacetamide (CB256), which fulfills the requirements of a bifunctional chelate approach, has been used to synthesize coordination complexes containing either Pt () or Re (), or both metal ions (). The new metal complexes showed a cellular uptake markedly greater than that of the precursor metallic compounds and were also able to induce apoptosis in C6 glioma cells. The good cytotoxicity of the free ligand CB256 towards C6, A2780, and A2780cisR tumor cell lines was attenuated after coordination of the dipicolylamine moiety to Pt while coordination of the imidazopyridine residue to Re reduces the affinity towards TSPO. The results of the present investigation are essential for the design of new imidazopyridine bifunctional chelate ligands targeted to TSPO. PMID:25069996

Margiotta, Nicola; Denora, Nunzio; Piccinonna, Sara; Laquintana, Valentino; Lasorsa, Francesco Massimo; Franco, Massimo; Natile, Giovanni



Magnetic Circular Dichroism Study of a Dicobalt(II) Complex with Mixed 5- and 6-Coordination: A Spectroscopic Model for Dicobalt(II) Hydrolases  

PubMed Central

The magnetic circular dichroism (MCD) study of [Co2(?-OH)(?-Ph4DBA)(TMEDA)2(OTf)], in which Ph4DBA is the dinucleating bis(carboxylate) ligand dibenzofuran-4,6-bis(diphenylacetate), is presented. This complex serves as an excellent spectroscopic model for a number of dicobalt(II) enzymes and proteins that have both the ?-hydroxo, ?-carboxylato bridging and asymmetric 6- and 5-coordination. The low-temperature MCD spectrum of the model complex shows bands at 490, 504, and 934 nm arising from d-d transitions on the 6-coordinate CoII and bands at 471, 522, 572, 594, and 638 nm arising from d-d transitions on the 5-coordinate CoII. The most intense MCD bands are at 504 and 572 nm for 6- and 5-coordinate CoII, respectively, and these two bands are found in the MCD spectra of dicobalt(II)-substituted methionine aminopeptidase from Escherichia coli (CoCoMetAP), glycerophosphodiesterase from Enterobacter aerogenes (CoCoGpdQ), aminopeptidase from Aeromonas proteolytica (CoCoAAP), and myohemerythrin from Themiste zostericola (CoCoMyoHry). These dicobalt(II)-substituted proteins are known to have one 5- and one 6-coordinate CoII bridged by one or two carboxylates and either a water or hydroxide. The uncertainty of the bridging water’s state of protonation is problematic, as this is a likely candidate for the attacking nucleophile in the dimetallohydrolases. Analysis of the variable-temperature variable-field (VTVH) MCD data determined that the CoII ions in the model complex are ferromagnetically coupled with a J of 3.0 cm?1. A comparison of all dicobalt(II) complexes and dicobalt(II)-substituted protein active sites with the ?-hydroxo/aqua, ?-carboxylato bridging motif reveals that J is either zero or negative (antiferromagnetic) in the ?-aqua systems and positive (ferromagnetic) in the ?-hydroxo systems. It was also determined that the CoII ions in CoCoAAP and CoCoMyoHry are ferromagnetically coupled, each with a J of 3.4 cm?1, which suggests that these ions have a ?-hydroxo bridging ligand. PMID:19691327

Larrabee, James A.; Johnson, W. Rainey; Volwiler, Adam S.



Synthesis and characterization of uranyl chromate sheet compounds containing edge-sharing dimers of uranyl pentagonal bipyramids  

SciTech Connect

Eight uranyl chromates have been crystallized from aqueous solution and characterized: Mg(H{sub 2}O){sub 6}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 2}(OH){sub 2}](H{sub 2}O){sub 3} (1), (NH{sub 4}){sub 2}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 2}(OH){sub 2}](H{sub 2}O){sub 3}, Rb{sub 2}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 2}(OH){sub 2}](H{sub 2}O){sub 3} (3), Cs[(UO{sub 2})(CrO{sub 4})(OH)]H{sub 2}O (4), Rb[(UO{sub 2})(CrO{sub 4})(OH)]H{sub 2}O (5) Co(H{sub 2}O){sub 4}(Co(H{sub 2}O){sub 6}){sub 2}[(UO{sub 2}){sub 4}(CrO{sub 4}){sub 6}(OH){sub 2}](H{sub 2}O){sub 4} (6), Li{sub 2}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 3}](H{sub 2}O){sub 7} (7), and Zn(H{sub 2}O){sub 6}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 3}](H{sub 2}O){sub 3} (8). The structural units of 1 through 8 each consist of a sheet of uranyl pentagonal bipyramids and (Cr(VI)O{sub 4}){sup 2-} tetrahedra. In each case two uranyl pentagonal bipyramids share an equatorial edge, giving a dimer that is linked into the sheet through vertex sharing with (Cr(VI)O{sub 4}){sup 2-} tetrahedra. The sheets are based upon three distinct sheet anion topologies, and the sheets based on a given anion topology can differ in the orientations of the non-bridging O atoms of (CrO{sub 4}){sup 2-} tetrahedra. The interlayers of these compounds contain either monovalent or divalent cations, as well as H{sub 2}O groups that are either bonded to the interlayer cation or are held in place by H bonding only. We explore the relationships between sheet topologies and interlayer configuration in these compounds. - Graphical abstract: Eight uranyl chromate compounds containing sheet structural units built from uranyl pentagonal bipyramids and (CrO{sub 4}){sup 2-} tetrahedra are reported. Relationships between sheet topologies and interstitial constituents is examined. Highlights: Black-Right-Pointing-Pointer Eight uranyl Cr(VI) compounds with sheet structural units are reported. Black-Right-Pointing-Pointer Relationships between the topology of the uranyl chromate sheets and interlayers are examined. Black-Right-Pointing-Pointer Uranyl and chromate polyhedra form a topologically novel sheet.

Unruh, Daniel K.; Baranay, Michelle; Pressprich, Laura; Stoffer, Megan [Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, IN 46556 (United States); Burns, Peter C., E-mail: [Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States)



Is macrocycle a synonym for kinetic inertness in Gd(III) complexes? Effect of coordinating and non-coordinating substituents on inertness and relaxivity of Gd(III) chelates with DO3A-like ligands  

PubMed Central

Gadolinium chelates with octadentate ligands are widely used as contrast agents for magnetic resonance imaging (MRI), with macrocyclic ligands based on DO3A being preferred for the high kinetic inertness of their Gd chelates. A major challenge in the design of new bifunctional MRI probes is the need to control the rotational motion of the chelate, which greatly affects its relaxivity. In this work we explored facile alkylation of a secondary amine in macrocyclic DO3A-like ligands to create a short, achiral linkage to limit the undesired internal motion of chelates within larger molecular constructs. The acetate moiety on the trans nitrogen was also replaced with either a bidentate (ethoxyacetate, L1 or methyl picolinate, L2) or bulky monodentate (methyl phosphonate, L3) donor arm to give octa- or heptadentate ligands, respectively. The resultant Gd(III) complexes were all monohydrated (q = 1) and exhibited water residency times that spanned 2 orders of magnitude (?M = 2190 ± 170, 3500 ± 90 and 12.7 ± 3.8 ns at 37 °C for GdL1, GdL2 and GdL3 respectively). Alkylation of the secondary amine with a non-coordinating biphenyl moiety resulted in coordinatively saturated q = 0 complexes of octadentate ligands L1 and L2. Relaxivities were limited by slow water exchange and/or lack of water co-ligand. All complexes showed decreased inertness compared to [Gd(DO3A)] despite higher ligand denticity, and inertness was further decreased upon N-alkylation. These results demonstrate that high kinetic inertness and in vivo safety of Gd chelates with macrocyclic ligands should not be generalized. PMID:23517079

Polasek, Miloslav; Caravan, Peter



Coordination chemistry with f-element complexes for an improved understanding of factors that contribute to extraction selectivity.  


Here, we highlight some recent accomplishments in f-element coordination chemistry aimed at probing the fundamental chemical differences between the 4f elements, lanthanides, and the 5f elements, actinides. The studies of particular interest are those that target improving our knowledge of fundamental chemistry to aid in increased selectivity for extractions of actinides. Two components key to understanding the challenges of actinide separations are detailed here, namely, previously described separation methods and recent investigations into the fundamental coordination chemistry of actinides. Both are aimed at probing the critical features necessary for improved selectivity of separations. This is considered a critical goal in the safe remediation of contaminated sites and reprocessing of nuclear fuel sources used in either civilian and noncivilian energy production. PMID:22838498

Gorden, Anne E V; DeVore, Michael A; Maynard, Branson A



Polymer complexes. LIV. Structural and spectral studies of supramolecular coordination polymers built from Ni(II), Fe(II) and Pd(II) with sulphadrug  

NASA Astrophysics Data System (ADS)

Polymer complexes of p-acrylamidyl sulphaguanidine (HL) with Ni(II), Fe(II) and Pd(II) salts have been prepared. The structures of the polymer complexes were elucidated using elemental analysis, 1H NMR, UV-Vis, IR spectroscopies, magnetic moment, molar conductance and thermal analysis. The polymer complexes were isolated in 1:1 and 1:2 (M:L) ratios. The solid monocomplexes (1:1) (M:L) were isolated in the general formula [Fe(HL)O 2SO 2(OH 2) 2]. The biscomplexes (1:2) (M:L) solid chelates found to have the general formula [Ni(HL) 2X 2] n (X = Cl -, Br -, I -, NO3-, NCS -), [Fe(HL)(en)(OSO 3)(OH 2)] n and [Ni(HL) 2(Py) 2] nX 2, while {[Pd(L)X] 2} n (1:1) (X = Cl - or Br -). In all the polymer complexes the ligand and anions were found to be coordinated to the Ni(II) and Fe(II) ions. The bidentate nature of the ligand is evident from IR spectra. The magnetic and spectroscopic data indicate a octahedral geometry for complexes. The thermal behaviour of these chelates shows that the hydrated complexes loss water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps.

El-Sonbati, A. Z.; Belal, A. A. M.; Diab, M. A.; Mohamed, R. H.



Directing Protons to the Dioxygen Ligand of a Ruthenium(II) Complex with Pendent Amines in the Second Coordination Sphere  

SciTech Connect

The activation and reduction of dioxygen (O2) by transition metal centers are key to a variety of biochemical and industrial processes. Efficient reduction of dioxygen to water is also important in the operation of fuel cells. These processes are typically proton-coupled electron transfer (PCET) reactions, requiring the coordinated movement of multiple protons and electrons. In biological systems, it is known that initial dioxygen bonding is facilitated by hydrogen bonding and proton delivery.

Tronic, Tristan A.; Rakowski DuBois, Mary; Kaminsky, Werner; Coggins, Michael K.; Liu, Tianbiao L.; Mayer, James M.



Spectroscopy, structure, and electrochemistry of transition metal complexes having [M2N2OS2] coordination sphere  

Microsoft Academic Search

Binuclear transition metal complexes of bicompartmental SNONS donors were synthesized and characterized by various physico-chemical techniques. Two different precursors with chloromethyl\\/formyl functionality at the 2 and 6 positions of phenolate ring are used to construct the ligands. The quinoxaline scaffolds provide SN donors incorporated at the 2 and 6 positions. Copper and zinc complexes are square pyramidal, whereas nickel and

Naveen V. Kulkarni; Gurunath S. Kurdekar; Srinivasa Budagumpi; Vidyanand K. Revankar



Characterization and Detection of Uranyl Ion Sorption on Silver Surfaces using Surface Enhanced Raman Spectroscopy  

Microsoft Academic Search

The study of the chemical behavior of uranyl species and its rapid detection is of primary environmental and non-proliferation concern. Herein we report on a surface enhanced Raman spectroscopic study of uranyl ion (UO22+) sorption onto the thermally vapor deposited silver particle surface. The ability of vibrational spectroscopy to characterize surface phenomenon and the remarkable sensitivity of the surface enhanced

Scott T Retterer; Sabrina M. Wells; Michael Sepaniak




EPA Science Inventory

The absorption of Uranyl (U) within the male Wistar rat was determined following oral gavage with uranyl nitrate solutions at seven different dosages. Gavage levels ranged from 0.003 to 45 mg U per kilogram body weight. Uranium tissue burdens were determined at 0.25, 0.5, 1, 2, 4...


Precipitation and Dissolution of Uranyl Phosphates in a Microfluidic Pore Structure  

NASA Astrophysics Data System (ADS)

The abiotic precipitation of uranium (U(VI)) was evaluated in a microfluidic pore structure (i.e. micromodel) to assess the efficacy of using a phosphate amendment to immobilize uranium in groundwater and mitigate the risk of this contaminant to potential down-gradient receptor sites. U(VI) was mixed transverse to the direction of flow with hydrogen phosphate (HPO42-), in the presence or absence of calcium (Ca2+) or sulfate (SO42-), in order to identify precipitation rates, the morphology and types of minerals formed, and the stability of these minerals to dissolution with and without bicarbonate (HCO3-) present. Raman backscattering spectroscopy and micro X-ray diffraction (?-XRD) results both showed that the only mineral precipitated was chernikovite (also known as hydrogen uranyl phosphate; UO2HPO4), even though the formation of other minerals were thermodynamically favored depending on the experimental conditions. Precipitation and dissolution rates varied with influent conditions. Relative to when only U(VI) and HPO42- were present, precipitation rates were 2.3 times slower when SO42- was present, and 1.4 times faster when Ca2+ was present. These rates were inversely related to the size of crystals formed during precipitation. Dissolution rates for chernikovite increased with increasing HCO3- concentrations, consistent with formation of uranyl carbonate complexes in aqueous solution, and they were the fastest for chernikovite formed in the presence of SO42-, and slowest for the chernikovite formed in the presence of Ca2+. These rates are related to the ratios of mineral-water interfacial area to mineral volume. Fluorescent tracer studies and laser confocal microscopy images showed that densely aggregated precipitates blocked pores and reduced permeability. The results suggest that changes in the solute conditions evaluated affect precipitation rates, crystal morphology, and crystal stability, but not mineral type.

Werth, C. J.; Fanizza, M.; Strathmann, T.; Finneran, K.; Oostrom, M.; Zhang, C.; Wietsma, T. W.; Hess, N. J.



Seven-coordinate Co(II), Fe(II) and six-coordinate Ni(II) amide-appended macrocyclic complexes as ParaCEST agents in biological media.  


The solution chemistry and solid-state structures of the Co(II), Fe(II), and Ni(II) complexes of 7,13-bis(carbamoylmethyl)-1,4,10-trioxa-7,13-diazacyclopentadecane (L) are reported as members of a new class of paramagnetic chemical exchange saturation transfer (paraCEST) MRI contrast agents that contain transition metal ions. Crystallographic data show that nitrogen and oxygen donor atoms of the macrocyclic ligand coordinate to the metal ions to generate complexes with distorted pentagonal bipyramidal geometry for [Co(L)]Cl2·2H2O or [Fe(L)](CF3SO3)2. The Ni(II) complex [Ni(L)](CF3SO3)2·H2O features a hexadentate ligand in a distorted octahedral geometry. The proton NMR spectra of all three complexes show highly dispersed and relatively sharp proton resonances. The complexes were further characterized by monitoring their dissociation under biologically relevant conditions including solutions containing phosphate and carbonate, ZnCl2, or acidic conditions. Solutions of the paraCEST agents in 20 mM N-(2-hydroxyethyl)piperazine-N'-ethanesulfonic acid (pH 7.4) and 100 mM NaCl showed highly shifted and intense CEST peaks at 59, 72, and 92 ppm away from bulk water for [Co(L)](2+), [Ni(L)](2+), and [Fe(L)](2+), respectively at 37 °C on a 11.7 T NMR spectrometer. CEST spectra with corresponding rate constants for proton exchange are reported in 4% agarose gel (w/w), rabbit serum, egg white, or buffered solutions. CEST phantoms of 4 mM complex in buffer, 4% agarose gel (w/w), or rabbit serum on a 4.7 T MRI scanner at 37 °C, are compared. The most substantial change was observed for the reactive [Ni(L)](2+), which showed reduced CEST contrast in rabbit serum and egg white. The complexes with the least highly shifted CEST peaks ([Co(L)](2+) and [Ni(L)](2+)) showed a reduction in CEST contrast in 4% agarose gel (w/w) compared to that in buffered solutions, while the CEST effect for [Fe(L)](2+) in 4% agarose gel (w/w) was not substantially different. PMID:24820102

Olatunde, Abiola O; Cox, Jordan M; Daddario, Michael D; Spernyak, Joseph A; Benedict, Jason B; Morrow, Janet R



Coordination of degrees of freedom and stabilization of task variables in a complex motor skill: expertise-related differences in cello bowing.  


Stringed instrument bowing is a complex sensorimotor skill, involving fine regulation of bow orientation and motion relative to the string. In this study, we characterize this skill in terms of stabilization of specific bow parameters as well as the underlying use and coordination of the degrees of freedom (DOF) of the right bowing arm. Age-matched samples of 10 advanced cellists and 10 cello novices took part in the study. Kinematic bow movement data were analyzed with respect to task variables suggested by the cello teaching literature: position and orientation of the bow relative to the string, bow velocity, and timing. Joint motion of the bowing arm was analyzed in terms of movement amplitude and inter-joint coordination (principal component analysis). As expected, novices showed poorer control of bowing parameters. In addition, novices differed markedly from advanced players in the use and coordination of the DOF of the bowing arm, with the elbow and wrist showing less overall movement and a reduced proportion of variance explained by the first principal component (PC1). In contrast, larger amounts of shoulder variance were explained by PC1 in novices compared to experts. Our findings support Bernstein's theory of graded skill acquisition, according to which early stages of motor skill learning are characterized by a "freezing" of movement DOF, while later learning stages exploit the DOF, possibly following a proximal-to-distal sequence, for improved task performance. PMID:23109087

Verrel, Julius; Pologe, Steven; Manselle, Wayne; Lindenberger, Ulman; Woollacott, Marjorie



Synthesis and structural characterization of heavier group 1 methyl tetrazolate complexes: New bridging coordination modes of the tetrazolate ligand  

Microsoft Academic Search

A series of sodium, potassium, rubidium, and cesium complexes of methyl tetrazolate was prepared and structurally characterized. Treatment of methyl tetrazole (MetetzH) with the group 1 hydroxides in water at ambient temperature afforded Na(Metetz)(H2O)2 (92%), K(Metetz) (92%), Rb(Metetz) (97%), and Cs(Metetz) (97%) as colorless solids after workup. These complexes were characterized by spectral and analytical methods, thermogravimetric analysis, and by

Selma Poturovic; Dongmei Lu; Mary Jane Heeg; Charles H. Winter



Isolable gold(I) complexes having one low-coordinating ligand as catalysts for the selective hydration of substituted alkynes at room temperature without acidic promoters.  


Hydration of a wide range of alkynes to the corresponding ketones has been afforded in high yields at room temperature by using gold(I)-phosphine complexes as catalyst, with no acidic cocatalysts required. Suitable substrates covering alkyl and aryl terminal alkynes, enynes, internal alkynes, and propargylic alcohols, including enantiopure forms, are cleanly transformed to the corresponding ketones in nearly quantitative yields. Acid-labile groups present in the substrates are preserved. The catalytic activity strongly depends on both the nature of the phosphine coordinated to the gold (I) center and the softness of the counteranion, the complex AuSPhosNTf(2) showing the better activity. A plausible mechanism for the hydration of alkynes through ketal intermediates is proposed on the basis of kinetic studies. The described catalytic system should provide an efficient alternative to mercury-based methodologies and be useful in synthetic programs. PMID:19170603

Leyva, Antonio; Corma, Avelino



Uranyl ion interaction at the water/NiO(100) interface: A predictive investigation by first-principles molecular dynamic simulations  

SciTech Connect

The behavior of the UO{sub 2}{sup 2+} uranyl ion at the water/NiO(100) interface was investigated for the first time using Born-Oppenheimer molecular dynamic simulations with the spin polarized DFT +U extension. A water/NiO(100) interface model was first optimized on a defect-free five layers slab thickness, proposed as a reliable surface model, with an explicit treatment of the solvent. Water molecules are adsorbed with a well-defined structure in a thickness of about 4 A above the surface. The first layer, adsorbed on nickel atoms, remains mainly in molecular form but can partly dissociate at 293 K. Considering low acidic conditions, a bidentate uranyl ion complex was characterized on two surface oxygen species (arising from water molecules adsorption on nickel atoms) with d{sub U-O{sub a{sub d{sub s{sub o{sub r{sub p{sub t{sub i{sub o{sub n}}}}}}}}}}}=2.39 A. This complex is stable at 293 K due to iono-covalent bonds with an estimated charge transfer of 0.58 electron from the surface to the uranyl ion.

Sebbari, Karim [EDF-R and D, Departement Materiaux et Mecanique des Composants, Les Renardieres, Ecuelles, 77818 Moret Sur Loing (France); Institut de Physique Nucleaire d'Orsay, Universite Paris-Sud, CNRS UMR 8608, 15 rue Georges Clemenceau, Batiment 100, 91406 Orsay Cedex (France); Roques, Jerome; Simoni, Eric [Institut de Physique Nucleaire d'Orsay, Universite Paris-Sud, CNRS UMR 8608, 15 rue Georges Clemenceau, Batiment 100, 91406 Orsay Cedex (France); Domain, Christophe [EDF-R and D, Departement Materiaux et Mecanique des Composants, Les Renardieres, Ecuelles, 77818 Moret Sur Loing (France)



A series of Zn-4f heterometallic coordination polymers and a zinc complex containing a flexible mixed donor dicarboxylate ligand.  


A new zinc compound, together with a corresponding series of Zn-4f heterometallic coordination polymers, namely, [Zn(H2PBDA)(PBDA)]n (1), {[Ln2(PBDA)2·2H2O] [Zn2(PBDA)2Cl2]}n [H2PBDA = 3-(pyridin-3-yl-oxy) benzene-1,2-dicarboxylic acid, and Ln = Pr(2), Nd(3), Eu(4), Gd(5), Dy(6), Ho(7), Er(8)] have been hydrothermally synthesized and characterized systematically. Polymers 2-8 feature two-dimensional (2D) 4,4 networks, containing the original 1D heterometallic double stranded chains composed of [Ln2Zn2(PBDA)2] entities. The extensive hydrogen bonding and ?-? stacking interactions were observed to stabilize the extended architectures. The luminescence emission spectra of the polymers vary depending on the lanthanide(III) ion present. Informative magnetic susceptibility measurements show that the same carboxylate bridging fashion of the PBDA ligand results in the different magnetic properties occurring within the heterometallic coordination polymers. In addition, polymer 6 exhibits an interesting slow magnetic relaxation behavior at lower temperatures. PMID:23549773

Feng, Xun; Feng, Yu-Quan; Liu, Lang; Wang, Li-Ya; Song, Hong-Liang; Ng, Seik-Weng



Tuning the electronic properties in ruthenium-quinone complexes through metal coordination and substitution at the bridge.  


A rare example of a mononuclear complex [(bpy)2 Ru(L(1) -H )](ClO4 ), 1(ClO4 ) and dinuclear complexes [(bpy)2 Ru(?-L(1) -2H )Ru(bpy)2 ](ClO4 )2 , 2(ClO4 )2 , [(bpy)2 Ru(?-L(2) -2H )Ru(bpy)2 ](ClO4 )2 , 3(ClO4 )2 , and [(bpy)2 Ru(?-L(3) -2H )Ru(bpy)2 ](ClO4 )2 , 4(ClO4 )2 (bpy=2,2'-bipyridine, L(1) =2,5-di-(isopropyl-amino)-1,4-benzoquinone, L(2) =2,5-di-(benzyl-amino)-1,4-benzoquinone, and L(3) =2,5-di-[2,4,6-(trimethyl)-anilino]-1,4-benzoquinone) with the symmetrically substituted p-quinone ligands, L, are reported. Bond-length analysis within the potentially bridging ligands in both the mono- and dinuclear complexes shows a localization of bonds, and binding to the metal centers through a phenolate-type "O(-) " and an immine/imminium-type neutral "N" donor. For the mononuclear complex 1(ClO4 ), this facilitates strong intermolecular hydrogen bonding and leads to the imminium-type character of the noncoordinated nitrogen atom. The dinuclear complexes display two oxidation and several reduction steps in acetonitrile solutions. In contrast, the mononuclear complex 1(+) exhibits just one oxidation and several reduction steps. The redox processes of 1(1+) are strongly dependent on the solvent. The one-electron oxidized forms 2(3+) , 3(3+) , and 4(3+) of the dinuclear complexes exhibit strong absorptions in the NIR region. Weak NIR absorption bands are observed for the one-electron reduced forms of all complexes. A combination of structural data, electrochemistry, UV/Vis/NIR/EPR spectroelectrochemistry, and DFT calculations is used to elucidate the electronic structures of the complexes. Our DFT results indicate that the electronic natures of the various redox states of the complexes in vacuum differ greatly from those in a solvent continuum. We show here the tuning possibilities that arise upon substituting [O] for the isoelectronic [NR] groups in such quinone ligands. PMID:24604718

Das, Hari Sankar; Schweinfurth, David; Fiedler, Jan; Khusniyarov, Marat M; Mobin, Shaikh M; Sarkar, Biprajit



Thiocyanate complexes of uranium in multiple oxidation states: a combined structural, magnetic, spectroscopic, spectroelectrochemical, and theoretical study.  


A comprehensive study of the complexes A4[U(NCS)8] (A = Cs, Et4N, (n)Bu4N) and A3[UO2(NCS)5] (A = Cs, Et4N) is described, with the crystal structures of [(n)Bu4N]4[U(NCS)8]·2MeCN and Cs3[UO2(NCS)5]·O0.5 reported. The magnetic properties of square antiprismatic Cs4[U(NCS)8] and cubic [Et4N]4[U(NCS)8] have been probed by SQUID magnetometry. The geometry has an important impact on the low-temperature magnetic moments: at 2 K, ?eff = 1.21 ?B and 0.53 ?B, respectively. Electronic absorption and photoluminescence spectra of the uranium(IV) compounds have been measured. The redox chemistry of [Et4N]4[U(NCS)8] has been explored using IR and UV-vis spectroelectrochemical methods. Reversible 1-electron oxidation of one of the coordinated thiocyanate ligands occurs at +0.22 V vs Fc/Fc(+), followed by an irreversible oxidation to form dithiocyanogen (NCS)2 which upon back reduction regenerates thiocyanate anions coordinating to UO2(2+). NBO calculations agree with the experimental spectra, suggesting that the initial electron loss of [U(NCS)8](4-) is delocalized over all NCS(-) ligands. Reduction of the uranyl(VI) complex [Et4N]3[UO2(NCS)5] to uranyl(V) is accompanied by immediate disproportionation and has only been studied by DFT methods. The bonding in [An(NCS)8](4-) (An = Th, U) and [UO2(NCS)5](3-) has been explored by a combination of DFT and QTAIM analysis, and the U-N bonds are predominantly ionic, with the uranyl(V) species more ionic that the uranyl(VI) ion. Additionally, the U(IV)-NCS ion is more ionic than what was found for U(IV)-Cl complexes. PMID:25072532

Hashem, Emtithal; Platts, James A; Hartl, František; Lorusso, Giulia; Evangelisti, Marco; Schulzke, Carola; Baker, Robert J



Eight- and six-coordinated Mn(II) complexes of heteroaromatic alcohol and aldehyde: Crystal structure, spectral, magnetic, thermal and antibacterial activity studies  

NASA Astrophysics Data System (ADS)

Crystal, molecular and electronic structure of new manganese(II) compounds: [Mn(2-CH2OHpy)2(NO3)2] (1), [Mn(4-CHO-5-MeIm)2(NO3)2] (2) and [Mn(4-CHO-5-MeIm)2Cl2] (3), where 2-hydroxymethylpyridine (2-CH2OHpy) and 5(4)-carbaldehyde-4(5)-methylimidazole (5(4)-CHO-4(5)-MeIm), have been characterised using X-ray, spectroscopic, magnetic and TG/DTG data. In compounds 1 and 2, the Mn(II) ion is eight-coordinated forming distorted pseudo-dodecahedron, that is rather unusual for the manganese(II) complexes, whereas in 3 the Mn(II) ion environment is a distorted octahedron. The high coordination number (CN = 8) of 1 and 2 results from bidentate character of the nitrate ligands. The X-band EPR spectra of compounds 2 and 3 exhibit fine structure signals resulting from zero-field splitting (ZFS) of the spin states for high spin d5 Mn(II), whereas for 1 the broad isotropic signals were observed. The estimation of ZFS for individual Mn(II) ions was carried out for all compounds using DFT calculations. The free ligands and their manganese(II) complexes have been tested in vitro against gram-positive and gram-negative bacteria in order to assess their antimicrobial properties.

Jab?o?ska-Wawrzycka, Agnieszka; Barszcz, Barbara; Zienkiewicz, Ma?gorzata; Hodorowicz, Maciej; Jezierska, Julia; Stadnicka, Katarzyna; Lechowicz, ?ukasz; Kaca, Wies?aw



Cobalt(II) chloride complexes with 1,1'-dimethyl-4,4'-bipyrazole featuring first- and second-sphere coordination of the ligand.  


In catena-poly[[dichloridocobalt(II)]-?-(1,1'-dimethyl-4,4'-bipyrazole-?(2)N(2):N(2'))], [CoCl2(C8H10N4)]n, (1), two independent bipyrazole ligands (Me2bpz) are situated across centres of inversion and in tetraaquabis(1,1'-dimethyl-4,4'-bipyrazole-?N(2))cobalt(II) dichloride-1,1'-dimethyl-4,4'-bipyrazole-water (1/2/2), [Co(C8H10N4)2(H2O)4]Cl2·2C8H10N4·2H2O, (2), the Co(2+) cation lies on an inversion centre and two noncoordinated Me2bpz molecules are also situated across centres of inversion. The compounds are the first complexes involving N,N'-disubstituted 4,4'-bipyrazole tectons. They reveal a relatively poor coordination ability of the ligand, resulting in a Co-pyrazole coordination ratio of only 1:2. Compound (1) adopts a zigzag chain structure with bitopic Me2bpz links between tetrahedral Co(II) ions. Interchain interactions occur by means of very weak C-H...Cl hydrogen bonding. Complex (2) comprises discrete octahedral trans-[Co(Me2bpz)2(H2O)4](2+) cations formed by monodentate Me2bpz ligands. Two equivalents of additional noncoordinated Me2bpz tectons are important as `second-sphere ligands' connecting the cations by means of relatively strong O-H...N hydrogen bonding with generation of doubly interpenetrated pcu (?-Po) frameworks. Noncoordinated chloride anions and solvent water molecules afford hydrogen-bonded [(Cl(-))2(H2O)2] rhombs, which establish topological links between the above frameworks, producing a rare eight-coordinated uninodal net of {4(24).5.6(3)} (ilc) topology. PMID:24594715

Domasevitch, Konstantin V



Coordination chemistry of dinucleating P2N2S ligands: preparation and characterization of cationic palladium complexes.  


The thioethers (4-tert-butyl-2,6-bis((2-(diphenylphosphino)ethylimino)methyl)phenyl)(tert-butyl)sulfane (tBuL3) and (4-tert-butyl-2,6-bis((2-(diphenylphosphino)ethylamino)methyl)phenyl)(tert-butyl)sulfane (tBuL4) react readily with [Pd(NCMe)2Cl2] to give the dinuclear palladium thiophenolate complexes [(L3)Pd2(Cl)2]+ and [(L4)Pd2(micro-Cl)]2+ (HL3=2,6-bis((2-(diphenylphosphino)ethylimino)methyl)-4-tert-butylbenzenethiol, HL4=2,6-bis((2-(diphenylphosphino)ethylamino)methyl)-4-tert-butylbenzenethiol). The chlorides in could be replaced by neutral (MeCN) and anionic ligands (NCS-, N3-, I-, CN-) to give the dinuclear PdII complexes [(L3)Pd2(NCMe)2]3+, [(L3)Pd2(SCN)2]+, [(L3)Pd2(N3)2]+, [(L3)Pd2(I)2]+, and [(L3)Pd2(CN)2]+. The acetonitrile ligands in are readily hydrated to give the corresponding amidato complex [(L3)Pd2(NHCOMe)]2+. All complexes were isolated as perchlorate salts and studied by infrared, 1H, and 31P NMR spectroscopy. In addition, complexes [ClO4].EtOH, [ClO4]2, [ClO4], [ClO4].EtOH, and [ClO4]2.MeCN.MeOH have been characterized by X-ray crystallography. The dipalladium complex was found to catalyse the vinyl-addition polymerization of norbornene in the presence of MAO (methylalumoxane) and B(C6F5)3/AlEt3. PMID:17160174

Siedle, Gabriel; Lassahn, Paul-Gerhard; Lozan, Vasile; Janiak, Christoph; Kersting, Berthold



Complex Regulation of Symbiotic Functions Is Coordinated by MucR and Quorum Sensing in Sinorhizobium meliloti? †  

PubMed Central

In Sinorhizobium meliloti, the production of exopolysaccharides such as succinoglycan and exopolysaccharide II (EPS II) enables the bacterium to invade root nodules on Medicago sativa and establish a nitrogen-fixing symbiosis. While extensive research has focused on succinoglycan, less is known concerning the regulation of EPS II or the mechanism by which it mediates entrance into the host plant. Previously, we reported that the ExpR/Sin quorum-sensing system is required to produce the symbiotically active low-molecular-weight fraction of this exopolysaccharide. Here, we show that this system induces EPS II production by increasing expression of the expG-expC operon, encoding both a transcriptional regulator (ExpG) and a glycosyl transferase (ExpC). ExpG derepresses EPS II production at the transcriptional level from MucR, a RosR homolog, while concurrently elevating expression of expC, resulting in the synthesis of the low-molecular-weight form. While the ExpR/Sin system abolishes the role of MucR on EPS II production, it preserves a multitude of other quorum-sensing-independent regulatory functions which promote the establishment of symbiosis. In planktonic S. meliloti, MucR properly coordinates a diverse set of bacterial behaviors by repressing a variety of genes intended for expression during symbiosis and enhancing the bacterial ability to induce root nodule formation. Quorum sensing precisely modulates the functions of MucR to take advantage of both the production of symbiotically active EPS II as well as the proper coordination of bacterial behavior required to promote symbiosis. PMID:21057009

Mueller, Konrad; Gonzalez, Juan E.



Using low-frequency IR spectra for the unambiguous identification of metal ion-ligand coordination sites in purpose-built complexes.  


One of the aims of our long-term research is the identification of metal ion-ligand coordination sites in bioinspired metal ion-C- or N-protected amino acid (histidine, tyrosine, cysteine or cystine) complexes immobilised on the surface of chloropropylated silica gel or Merrifield resin. In an attempt to reach this goal, structurally related, but much simpler complexes have been prepared and their metal ion-ligand vibrations were determined from their low-frequency IR spectra. The central ions were Mn(II), Co(II), Ni(II) or Cu(II) and the ligands (imidazole, isopropylamine, monosodium malonate) were chosen to possess only one-type of potential donor group. The low-frequency IR spectra were taken of the complexes for each ion-ligand combination and the typical metal ion-functional group vibration bands were selected and identified. The usefulness of the obtained assignments is demonstrated on exemplary immobilised metal ion-protected amino acid complexes. PMID:24316539

Varga, Gábor; Csendes, Zita; Peintler, Gábor; Berkesi, Ottó; Sipos, Pál; Pálinkó, István



Synthesis, molecular structure and norbornene polymerization behavior of three-coordinate nickel(I) complexes with chelating anilido-imine ligands.  


Reaction of lithium salts of anilido-imine ligands bearing bulky substituentes on the nitrogen donor atoms with trans-chloro(phenyl)bis(triphenylphosphane)nickel(II) results in the formation of two rare three-coordinate nickel(I) complexes [(Ar1N=CHC6H4NAr2)Ni(I)PPh3] (1: Ar1 = Ar2 = 2,6-i-Pr2C6H3; 2: Ar1 = 2,6-Me2C6H3, Ar2 = 2,6-i-Pr2C6H3). The molecular structures of complexes 1 and 2 have been confirmed by single crystal X-ray analyses. These two complexes exhibit paramagnetic properties as measured by their EPR and 1H NMR spectra. After being activated with methylaluminoxane (MAO) these complexes could polymerize norbornene to afford addition-type polynorbornene (PNB) with high molecular weight M(w) (10(6) g mol(-1)), catalytic activities being high, up to 2.82 x 10(7) g(PNB) mol(-1)(Ni) h(-1). PMID:16718342

Wang, Hai-Yu; Meng, Xia; Jin, Guo-Xin



Synthesis and characterization of uranyl chromate sheet compounds containing edge-sharing dimers of uranyl pentagonal bipyramids  

NASA Astrophysics Data System (ADS)

Eight uranyl chromates have been crystallized from aqueous solution and characterized: Mg(H 2O) 6[(UO 2) 2(CrO 4) 2(OH) 2](H 2O) 3 ( 1), (NH 4) 2[(UO 2) 2(CrO 4) 2(OH) 2](H 2O) 3, Rb 2[(UO 2) 2(CrO 4) 2(OH) 2](H 2O) 3 ( 3), Cs[(UO 2)(CrO 4)(OH)]H 2O ( 4), Rb[(UO 2)(CrO 4)(OH)]H 2O ( 5) Co(H 2O) 4(Co(H 2O) 6) 2[(UO 2) 4(CrO 4) 6(OH) 2](H 2O) 4 ( 6), Li 2[(UO 2) 2(CrO 4) 3](H 2O) 7 ( 7), and Zn(H 2O) 6[(UO 2) 2(CrO 4) 3](H 2O) 3 ( 8). The structural units of 1 through 8 each consist of a sheet of uranyl pentagonal bipyramids and (Cr(VI)O 4) 2- tetrahedra. In each case two uranyl pentagonal bipyramids share an equatorial edge, giving a dimer that is linked into the sheet through vertex sharing with (Cr(VI)O 4) 2- tetrahedra. The sheets are based upon three distinct sheet anion topologies, and the sheets based on a given anion topology can differ in the orientations of the non-bridging O atoms of (CrO 4) 2- tetrahedra. The interlayers of these compounds contain either monovalent or divalent cations, as well as H 2O groups that are either bonded to the interlayer cation or are held in place by H bonding only. We explore the relationships between sheet topologies and interlayer configuration in these compounds.

Unruh, Daniel K.; Baranay, Michelle; Pressprich, Laura; Stoffer, Megan; Burns, Peter C.



Zinc(II) and Cadmium(II) complexes with N4-coordinate pyrazole based ligand: Syntheses, characterization and structure  

NASA Astrophysics Data System (ADS)

A series of six new mononuclear zinc(II) complexes of the type [Zn(X)(dbdmp)]Y (1-6) (X = N3-/NCO-/NCS-, Y = ClO4-/PF6-, and dbdmp = N,N-diethyl-N?,N?-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)ethane-1,2-diamine), two binuclear cadmium(II) complexes [{Cd(dbdmp)}2(?-N3)2](Y)2 (7-8) and three mononuclear cadmium(II) complexes [Cd(NCO)(dbdmp)]Y (Y = ClO4-/PF6-) (9-10) and [Cd(NCS)2(dbdmp)] (11) have been synthesized and characterized by physico-chemical methods. Crystal structures of the complexes [Zn(N3)(dbdmp)]ClO4 (1), [{Cd(dbdmp)}2(?-N3)2](ClO4)2 (7), [Cd(NCO)(dbdmp)]ClO4 (9) and [Cd(NCS)2(dbdmp)] (11) have been solved by single crystal X-ray diffraction studies and showed that [Zn(N3)(dbdmp)]ClO4 (1) and [Cd(NCO)(dbdmp)]ClO4 (9) have distorted trigonal bipyramidal geometry, [Cd(NCS)2(dbdmp)] (11) and [(dbdmp)Cd(?-N3)]2(ClO4)2 (7) have distorted octahedral geometry.

Solanki, Ankita; Sadhu, Mehul H.; Kumar, Sujit Baran; Mitra, Partho



Influence of the coordination environment of zinc(II) complexes of designed Mannich ligands on phosphatase activity: a combined experimental and theoretical study.  


A mononucleating (HL(1)) and a dinucleating (HL(2)) "end-off" compartmental ligand have been designed and synthesized by controlled Mannich reaction using p-cresol and bis(2-methoxyethyl)amine, and their formation has been rationalized. Six complexes have been prepared on treating HL(1) and HL(2) with Zn(II)X2 (X = Cl(-), Br(-), I(-)) with the aim to investigate their hydrolytic activity on phosphoester bond cleavage. Interestingly, the mononucleating ligand was observed to yield dinuclear complexes, [Zn2(L(1))2X2] (1-3), while the potential dinucleating ligand generated mononuclear complexes, [Zn(HL(2))X2] (4-6). Four (1-4), out of six complexes studied, were characterized by single-crystal X-ray diffraction (XRD): the Zn ion exhibits trigonal bipyramidal and tetrahedral coordination spheres in the di- and mononuclear complex, respectively. The hydrolytic kinetics, followed spectrophotometrically with 4-nitrophenylphosphate (4-NPP) in buffered dimethylformamide (DMF) (97.5% DMF, v/v) because of solubility reasons, under excess substrate conditions (substrate:complex = 20:1), indicated that the complexes enormously accelerate the rate of phosphomonoester hydrolysis with first order rate constants (kcat) in the range 2-10 s(-1) at 25 °C. In each case kinetic data analyses have been run by Michaelis-Menten treatment. The efficacy in the order of conversion of substrate to product (p-nitrophenolate ion) follows the trend 1 > 2 > 3 > 4 > 5 > 6, and the ratio of kcat of an analogous dinuclear to mononuclear complex is ?2. An electrospray ionization-mass spectrometry (ESI-MS) study has revealed the dissociation of the centrosymmetric dinuclear complex to two mononuclear species instead of a syn-cooperative catalysis. Density functional theory (DFT) calculations have been performed to rationalize our proposed mechanistic pathway for phosphatase activity. The comparative analysis concludes the following facts under experimental conditions: (1) the halide bound to the active site affects the overall rate in the order: Cl(-) > Br(-) > I(-) regardless of nuclearity; (2) dinuclear complexes prevail over the mononuclear ones. PMID:24354306

Sanyal, Ria; Guha, Averi; Ghosh, Totan; Mondal, Tapan Kumar; Zangrando, Ennio; Das, Debasis



Uranium-nitrogen multiple bonding: the case of a four-coordinate uranium(VI) nitridoborate complex.  


Reaction of the azidoborate salt [N(n-Bu)(4)][(C(6)F(5))(3)B(N(3))] ([N(n-Bu)(4)][1]) with the uranium(III) tris(anilide) complex (THF)U(N[t-Bu]Ar)(3) (2; THF = tetrahydrofuran; Ar = 3,5-Me(2)C(6)H(3)) results in formation of the paramagnetic uranium(V) nitridoborate complex [N(n-Bu)(4)][(C(6)F(5))(3)BNU(N[t-Bu]Ar)(3)] ([N(n-Bu)(4)][3]). Chemical oxidation of [N(n-Bu)(4)][3] is facile and provides the diamagnetic uranium(VI) nitridoborate complex (C(6)F(5))(3)BNU(N[t-Bu]Ar)(3) (3). [N(n-Bu)(4)][3] and 3 are the first nitridoborate complexes of uranium and were characterized by multinuclear NMR spectroscopy, single crystal X-ray diffraction methods, and elemental analysis. The X-ray crystal structures of [N(n-Bu)(4)][3] and 3 reveal extremely short UN(nitrido) distances (1.916(4) A and 1.880(4) A, respectively). Density functional theory was used to calculate the optimized structure of the truncated model (C(6)F(5))(3)BNU(N[Me]Ph)(3); the procedure was carried out similarly for several other relevant complexes featuring UN multiple bonds. Bond multiplicities based on Nalewajski-Mrozek valence indices were calculated, the results of which suggest that the UN(nitrido) interaction in 3 is close to a full triple bond. PMID:19341243

Fox, Alexander R; Cummins, Christopher C



Coordination and fluorescence of the intracellular Zn2+ probe [2-methyl-8-(4-toluenesulfonamido)-6-quinolyloxy]acetic acid (Zinquin A) in ternary Zn2+ complexes.  


A potentiometric study of the coordination of the fluorophore, 2-methyl-8-(4-toluenesulfonamido)-6-quinolyloxyacetic acid, (1)LH(2) (the intracellular Zn(2+) probe, Zinquin A) in its deprotonated form, (1)L(2)(-), in Zn(2+) ternary complexes, [Zn(n)L(1)L](n) (where n is the charge of (n)L) at 298.2 K in 50% aqueous ethanol (v/v) and I = 0.10 (NaClO(4)), shows that the formation of [Zn(n)L(1)L](n) from [Zn(n)L]((2+)(n)(+) is characterized by log(K(5)/dm(3) mol(-1)) = 8.23 +/- 0.05, 4.36 +/- 0.18, 8.45 +/- 0.10, 10.00 +/- 0.06, 11.53 +/- 0.06 and 5.92 +/- 0.15, respectively, where (n)L = (2)L - (6)L and (7)L(3-) are 1,4,7,10-tetraazacyclododecane, 1,4,8,11-tetraazacyclotetradecane, 1,4,7-triazacyclononane, 1,5,9-triazacyclododecane, tris(2-aminoethyl)amine and nitrilotriacetate, respectively, and K(5) is the stepwise complexation constant. Dissociation of a hydroxo proton from triethanolamine, (8)L, occurs in the formation of [Zn(8)LH(-1)](+) that subsequently forms [Zn(8)LH(-1)(1)L](-) for which log(K(5)/dm(3) mol(-1)) = 9.87 +/- 0.08. The variation of K(5) and the 5-fold variation of quantum yield of (1)L(2)(-) as its coordination environment changes in Zn(2+) ternary complexes are discussed with reference to the use of (1)L(2-) in the detection of intracellular Zn(2+). PMID:12656623

Hendrickson, Kym M; Geue, Jason P; Wyness, Oska; Lincoln, Stephen F; Ward, A David



Escherichia coli Response to Uranyl Exposure at Low pH and Associated Protein Regulations  

PubMed Central

Better understanding of uranyl toxicity in bacteria is necessary to optimize strains for bioremediation purposes or for using bacteria as biodetectors for bioavailable uranyl. In this study, after different steps of optimization, Escherichia colicells were exposed to uranyl at low pH to minimize uranyl precipitation and to increase its bioavailability. Bacteria were adapted to mid acidic pH before exposure to 50 or 80 µM uranyl acetate for two hours at pH?3. To evaluate the impact of uranium, growth in these conditions were compared and the same rates of cells survival were observed in control and uranyl exposed cultures. Additionally, this impact was analyzedby two-dimensional differential gel electrophoresis proteomics to discover protein actors specifically present or accumulated in contact with uranium.Exposure to uranium resulted in differential accumulation of proteins associated with oxidative stress and in the accumulation of the NADH/quinone oxidoreductase WrbA. This FMN dependent protein performs obligate two-electron reduction of quinones, and may be involved in cells response to oxidative stress. Interestingly, this WrbA protein presents similarities with the chromate reductase from E. coli, which was shown to reduce uranyl in vitro. PMID:24587082

Khemiri, Arbia; Carriere, Marie; Bremond, Nicolas; Ben Mlouka, Mohamed Amine; Coquet, Laurent; Llorens, Isabelle; Chapon, Virginie; Jouenne, Thierry; Cosette, Pascal; Berthomieu, Catherine



Escherichia coli response to uranyl exposure at low pH and associated protein regulations.  


Better understanding of uranyl toxicity in bacteria is necessary to optimize strains for bioremediation purposes or for using bacteria as biodetectors for bioavailable uranyl. In this study, after different steps of optimization, Escherichia coli cells were exposed to uranyl at low pH to minimize uranyl precipitation and to increase its bioavailability. Bacteria were adapted to mid acidic pH before exposure to 50 or 80 µM uranyl acetate for two hours at pH?3. To evaluate the impact of uranium, growth in these conditions were compared and the same rates of cells survival were observed in control and uranyl exposed cultures. Additionally, this impact was analyzed by two-dimensional differential gel electrophoresis proteomics to discover protein actors specifically present or accumulated in contact with uranium.Exposure to uranium resulted in differential accumulation of proteins associated with oxidative stress and in the accumulation of the NADH/quinone oxidoreductase WrbA. This FMN dependent protein performs obligate two-electron reduction of quinones, and may be involved in cells response to oxidative stress. Interestingly, this WrbA protein presents similarities with the chromate reductase from E. coli, which was shown to reduce uranyl in vitro. PMID:24587082

Khemiri, Arbia; Carrière, Marie; Bremond, Nicolas; Ben Mlouka, Mohamed Amine; Coquet, Laurent; Llorens, Isabelle; Chapon, Virginie; Jouenne, Thierry; Cosette, Pascal; Berthomieu, Catherine



Enhanced Adsorption and Recovery of Uranyl Ions by NikR Mutant-Displaying Yeast  

PubMed Central

Uranium is one of the most important metal resources, and the technology for the recovery of uranyl ions (UO22+) from aqueous solutions is required to ensure a semi-permanent supply of uranium. The NikR protein is a Ni2+-dependent transcriptional repressor of the nickel-ion uptake system in Escherichia coli, but its mutant protein (NikRm) is able to selectively bind uranyl ions in the interface of the two monomers. In this study, NikRm protein with ability to adsorb uranyl ions was displayed on the cell surface of Saccharomyces cerevisiae. To perform the binding of metal ions in the interface of the two monomers, two metal-binding domains (MBDs) of NikRm were tandemly fused via linker peptides and displayed on the yeast cell surface by fusion with the cell wall-anchoring domain of yeast ?-agglutinin. The NikRm-MBD-displaying yeast cells with particular linker lengths showed the enhanced adsorption of uranyl ions in comparison to the control strain. By treating cells with citrate buffer (pH 4.3), the uranyl ions adsorbed on the cell surface were recovered. Our results indicate that the adsorption system by yeast cells displaying tandemly fused MBDs of NikRm is effective for simple and concentrated recovery of uranyl ions, as well as adsorption of uranyl ions. PMID:24970221

Kuroda, Kouichi; Ebisutani, Kazuki; Iida, Katsuya; Nishitani, Takashi; Ueda, Mitsuyoshi



Characterization and catechole oxidase activity of a family of copper complexes coordinated by tripodal pyrazole-based ligands  

Microsoft Academic Search

A family of tripodal pyrazole-based ligands has been synthesized by a condensation reaction between 1-hydroxypyrazoles and aminoalcohols. The diversity was introduced both on the substituents of the pyrazole ring and on the side chain. The corresponding copper(II) complexes have been prepared by reaction with CuCl2 in tetrahydrofuran. They have been characterized by EPR, UV spectroscopy and cyclic voltammetry. The absence

R. Marion; M. Zaarour; N. A. Qachachi; N. M. Saleh; F. Justaud; D. Floner; O. Lavastre; F. Geneste



Dinuclear Cu(I) complexes of 1,2,4,5-tetra(7-azaindolyl)benzene: persistent 3-coordinate geometry, luminescence, and reactivity.  


Five Cu(I) complexes [Cu2(ttab)(CH3CN)2][BF4]2 (1), [Cu(2)(ttab)(PPh3)2][BF4]2 (2), [Cu2(ttab)I2] (3), [Cu2(ttab)(I3)2] (4), and [Cu2(ttab)(I)BF4]n (5) with 1,2,4,5-tetra(7-azaindolyl)benzene (ttab) have been synthesized and characterized. The structures of compound 1, 2, 4, and 5 have been determined by single-crystal X-ray diffraction analyses, which established that 1, 2, and 4 are discrete dinuclear Cu2 compounds while compound 5 is a 1D coordination polymer with the I- ligand bridging two dinuclear Cu2 units. The ttab ligand in all four complexes adopts a 1,3-chelation mode. The Cu(I) center in all complexes is three-coordinate. Close contact between the Cu(I) center and the benzene ring in the ttab ligand was observed in all four structures, which is believed to play a role in stabilizing the three-coordinate geometry of the Cu(I) center. The crystals of 1, 2, and 5 contain channels in the lattice that host solvent molecules such as CH2Cl2 and toluene. Fluorescent measurements established that, in solution, compounds 1-3 display weak blue luminescence which originates from the ttab but is significantly red-shifted and has a much lower emission intensity, compared to the free ttab ligand. The application of compound 1 in C-N cross-coupling reactions was examined by using the reaction of phenyl halides with imidazole as a model system. For the reaction with phenyl iodide, 1 was found to be as effective a catalyst as the CuI/1,10-phenanthroline system. For the reaction with phenyl bromide, 1 is less effective than the CuI/1,10-phenanthroline system. Compound 1 reacts with O2 gas, as established by UV-vis spectra, but the oxidized products have not been characterized. PMID:16841988

Zhao, Shu-Bin; Wang, Rui-Yao; Wang, Suning



Syntheses, structures, and photoluminescence of d 10 coordination architectures: From 1D to 3D complexes based on mixed ligands  

NASA Astrophysics Data System (ADS)

Six new compounds, namely, {[Cd 3(Himpy) 3(tda) 2]·3H 2O} n ( 1), {[Zn 3(bipy) 2(tda) 2(H 2O) 2]·4H 2O} n ( 2), {[Cd 3(bipy) 3(tda) 2]·4H 2O} n ( 3), {[Cd 3(tda) 2(H 2O) 3Cl]·H 2O} n ( 4), {[Zn 2(tz)(tda)(H 2O) 2]·H 2O} n ( 5) and {[Cd 7(pz)(tda) 4(OAc)(H 2O) 7]·3H 2O} n ( 6) [H 3tda = 1H-1,2,3-triazole-4,5-dicarboxylic acid, Himpy = 2-(1H-imidazol-2-yl)pyridine, bipy = 2,2'-bipyridine, Htz = 1H-1,2,4-triazole, H 2pz = piperazine] have been prepared under hydrothermal condition and characterized by elemental analyses, infrared spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analyses. Compound 1 is a 1D column-like structure and displays a 3D supramolecular network via the ?···? stacking interaction. The compounds 2 and 3 exhibit similar 2D layer-like structure, which further extend to 3D supermolecular structure by the ?···? stacking interaction. All of compounds 4- 6 display 3D framework with diverse topology constructed from the tda 3- ligands in different coordination modes and secondary ligands (or bridging atom) connecting metal ions. Furthermore, the thermal stabilities and photoluminescent properties of compounds 1- 6 were studied.

Yuan, Gang; Shao, Kui-Zhan; Du, Dong-Ying; Wang, Xin-Long; Su, Zhong-Min



Designed single-step synthesis, structure, and derivative textural properties of well-ordered layered penta-coordinate silicon alcoholate complexes.  


The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. Here the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes through a novel transesterification mechanism is reported. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building units (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na(+)-O(2-) ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10?)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na(+) counter-ions as a result of unique atomic arrangement in its structure. However, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7?m(2) ?g(-1) for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal-organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity. PMID:24737615

Li, Xiansen; Michaelis, Vladimir K; Ong, Ta-Chung; Smith, Stacey J; Griffin, Robert G; Wang, Evelyn N



Interactions of bacterial flagellar chaperone-substrate complexes with FlhA contribute to co-ordinating assembly of the flagellar filament.  


Assembly of the bacterial flagellar filament is strictly sequential; the junction proteins, FlgK and FlgL, are assembled at the distal end of the hook prior to the FliD cap, which supports assembly of as many as 30?000 FliC molecules into the filament. Export of these proteins requires assistance of flagellar chaperones: FlgN for FlgK and FlgL, FliT for FliD and FliS for FliC. The C-terminal cytoplasmic domain of FlhA (FlhAC ), a membrane component of the export apparatus, provides a binding-site for these chaperone-substrate complexes but it remains unknown how it co-ordinates flagellar protein export. Here, we report that the highly conserved hydrophobic dimple of FlhAC is involved in the export of FlgK, FlgL, FliD and FliC but not in proteins responsible for the structure and assembly of the hook, and that the binding affinity of FlhAC for the FlgN/FlgK complex is slightly higher than that for the FliT/FliD complex and about 14-fold higher than that for the FliS/FliC complex, leading to the proposal that the different binding affinities of FlhAC for these chaperone/substrate complexes may confer an advantage for the efficient formation of the junction and cap structures at the tip of the hook prior to filament formation. PMID:24325251

Kinoshita, Miki; Hara, Noritaka; Imada, Katsumi; Namba, Keiichi; Minamino, Tohru



Synthesis of bis(m-phenylene)-32-crown-10-based discrete rhomboids driven by metal-coordination and complexation with paraquat.  


Two bis(m-phenylene)-32-crown-10 derivatives containing two pyridyl or carboxyl groups were made. They were used to prepare three bis(m-phenylene)-32-crown-10-based discrete rhomboids by coordination-driven self-assembly with high yields. The formation of these crown ether-based rhomboids was confirmed by NMR, UV-vis, CSI-TOF-MS, and elemental analysis. The complexation of these crown ether-based assemblies with paraquat (N,N'-dimethyl-4,4'-bipyridinium) was studied. The complexation of neutral bis(crown ether) rhomboid 1 with paraquat was found to be statistical with a 1:2 stoichiometry. The average apparent association constant K(av) of the complexation of rhomboid 1 with paraquat was found to be about 8.8(+/-0.8) x 10(3) M(-1) in acetone, about 17 times higher than the reported association constant value for the complexation of the corresponding simple bis(m-phenylene)-32-crown-10 with paraquat. This is possibly because the carboxylate groups provide additional noncovalent interactions between the host and guest. No obvious complexation was observed between the cationic rhomboids and paraquat when studied by NMR, UV-vis, and CSI-TOF-MS analysis. This could be attributed to the combination of the charge repulsion between cationic pyridinium rings and cationic platinum atoms and the weak pi-pi stacking and charge transfer interactions between the phenyl rings and the pyridinium rings caused by the electron-withdrawing effect of the cationic platinum atoms. PMID:19382765

Zhu, Kelong; He, Jiuming; Li, Shijun; Liu, Ming; Wang, Feng; Zhang, Mingming; Abliz, Zeper; Yang, Hai-bo; Li, Ning; Huang, Feihe



Kinetic and mechanistic investigation of the substitution reactions of four and five co-ordinated rhodium stibine complexes with a bulky phosphite.  


The substitution reaction of trans-[Rh(Cl)(CO)(SbPh3)2] (1) with tris(2,4-di-tert-butylphenyl)phosphite (2,4-TBPP) to form trans-[Rh(Cl)(CO)(2,4-TBPP)2] (4) in two consecutive steps has been investigated by UV-vis stopped-flow spectrophotometry. The experiments were performed in dichloromethane and in ethyl acetate, at 298 K and 268 K respectively for the first reaction step, and for the second reaction step over a temperature range from 278 to 313 K in both solvents. The first step is very fast (up to 1630 s(?1)) and on the limit of what is observable with the stopped-flow technique. Introduction of the five-coordinate complex trans-[Rh(Cl)(CO)(SbPh3)3] (2) in equilibrium with (1), by adding an excess SbPh3, led to a significant decrease in overall reaction rate for the formation of the intermediate trans-[Rh(Cl)(CO)(SbPh3)2(2,4-TBPP)] (3). Activation parameters for the second substitution reaction, in which 3 is converted to 4, has been determined as ?H‡ = 22.85 ± 0.17 and 28.38 ± 0.10 kJ mol(?1) and ?S‡ = ?144.7 ± 0.6 and ?100.9 ± 0.4 J mol(?1) K(?1) for CH2Cl2 and EtOAc respectively, supporting an associative pathway. A strongly coordinating solvent promotes both reactions. In all reaction steps a strong tendency for stibines to promote 5-coordinated, fairly stable intermediates is manifested. PMID:23942428

Hennion, Clare; Jonasson, Klara J; Wendt, Ola F; Roodt, Andreas



Five-coordinate nickel(II) complexes with carboxylate anions and derivatives of 1,5,9-triazacyclododec-1-ene: structural and 1H NMR spectroscopic studies.  


The hydroxo complexes [Ni2(mcN3)2(mu-OH)2]2(PF6)2[mcN3 = 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene (Me3-mcN3) or 2,4,4,9-tetramethyl-1,5,9-triazacyclododec-1-ene (Me4-mcN3)] react with the corresponding carboxylic acid [HA = benzoic (Hbz), salicylic (Hsal) or acetylsalicylic (Hacsal) acid] to give five-coordinate nickel(II) complexes of the type [Ni(mcN3)(A)](PF6). The complexes have been studied by spectroscopic methods (IR, UV-Vis and 1H NMR). In acetone solution they exhibit isotropically shifted 1H NMR resonances. The full assignment of these resonances has been made using one- and two-dimensional 1H NMR techniques. The single-crystal structures of [Ni(Me4-mcN3)(bz)](PF6), [Ni(Me4-mcN3)(sal)](PF6) and[Ni(Me4-mcN3)(acsal)](PF6) have been established by X-ray diffraction. PMID:15605152

Santana, M Dolores; Lozano, A Abel; Garcia, Gabriel; Lopez, Gregorio; Perez, Jose



The strong-field tripodal phosphine donor, [PhB(CH2PiPr2)3]-, provides access to electronically and coordinatively unsaturated transition metal complexes.  


This paper introduces a sterically encumbered, strong-field tris(diisopropylphosphino)borate ligand, [PhBP(iPr)(3)] ([PhBP(iPr)(3)] = [PhB(CH(2)P(i)Pr(2))(3)](-)), to probe aspects of its conformational and electronic characteristics within a host of complexes. To this end, the Tl(I) complex, [PhBP(iPr)(3)]Tl (1), was synthesized and characterized in the solid-state by X-ray diffraction analysis. This precursor proves to be an effective transmetallating agent, as evidenced by its reaction with the divalent halides FeCl(2) and CoX(2) (X = Cl, I) to produce the monomeric, 4-coordinate, high-spin derivatives [PhBP(iPr)(3)]FeCl (2) and [PhBP(iPr)(3)]CoX (X = Cl (3), I (4)) in good yield. Complexes 2-4 were each characterized by X-ray diffraction analysis and shown to be monomeric in the solid-state. For conformational and electronic comparison within a system exhibiting higher than 4-coordination, the 16-electron ruthenium complexes [[PhBP(iPr)(3)]Ru(mu-Cl)](2) (5) and [[PhBP(3)]Ru(mu-Cl)](2) (6) were prepared and characterized ([PhBP(3)] = [PhB(CH(2)PPh(2))(3)](-)). The chloride complexes 2 and 3 reacted with excess CO to afford the divalent, monocarbonyl adducts [PhBP(iPr)(3)]FeCl(CO) (7) and [PhBP(iPr)(3)]CoCl(CO) (8), respectively. Reaction of 4 with excess CO resulted in the monovalent, dicarbonyl product [PhBP(iPr)(3)]Co(I)(CO)(2) (9). Complexes 5 and 6 also bound CO readily, providing the octahedral, 18-electron complexes [PhBP(iPr)(3)]RuCl(CO)(2) (10) and [PhBP(3)]RuCl(CO)(2) (11), respectively. Dimers 5 and 6 were broken up by reaction with trimethylphosphine to produce the mono-PMe(3) adducts [PhBP(iPr)(3)]RuCl(PMe(3)) (12) and [PhBP(3)]RuCl(PMe(3)) (13). Stoichiometric oxidation of 3 with dioxygen provided the 4-electron oxidation product [PhB(CH(2)P(O)(i)Pr(2))(2)(CH(2)P(i)Pr(2))]CoCl (14), while exposure of 3 to excess oxygen results in the 6-electron oxidation product [PhB(CH(2)P(O)(i)Pr(2))(3)]CoCl (15). Complexes 2 and 4 were characterized via cyclic voltammetry to compare their redox behavior to their [PhBP(3)] analogues. Complex 4 was also studied by SQUID magnetization and EPR spectroscopy to confirm its high-spin assignment, providing an interesting contrast to its previously described low-spin relative, [PhBP(3)]CoI. The difference in spin states observed for these two systems reflects the conformational rigidity of the [PhBP(iPr)(3)] ligand by comparison to [PhBP(3)], leaving the former less able to accommodate a JT-distorted electronic ground state. PMID:12924878

Betley, Theodore A; Peters, Jonas C



Three-component reaction of tautomeric amidines with 3-ferrocenylmethylidene-2,4-pentanedione. Formation of polymeric coordination complexes of potassium ferrocenyl-(hexahydro)pyrimidoxides.  


Acetamidine hydrochloride and p-aminobenzamidine dihydrochloride interact with 3-ferrocenylmethylidene-2,4-pentanedione at 80-82 °C in the presence of K2CO3 in the water-alcohol medium in two tautomeric forms (the amidoimine and enediamine ones) with formation of mixtures of pyrimidine and piperidone derivatives and polymeric coordination complexes of potassium ferrocenyl(hexahydro)pyrimidoxides. The structure of the resultant compounds is elucidated on the basis of IR, 1H- and 13C-NMR spectroscopy, mass spectrometry and elemental analysis data. The crystal structures of 6-ferrocenyl-4-hydroxy-4-methyl-2-piperidone, potassium 6-ferrocenyl-4-methyl-2-methylidene(hexahydro)pyrimidin-4-oxide and 2-(4-aminophenyl)-4-ferrocenyl-6-methyl-pyrimidine were determined by X-ray analysis of suitable single crystals. PMID:24362624

Klimova, Elena I; Flores-Alamo, Marcos; Klimova, Tatiana; Maya, Sandra Cortez; Beletskaya, Irina P



Binuclear Pt-Tl bonded complex with square pyramidal coordination around Pt: a combined multinuclear NMR, EXAFS, UV-Vis, and DFT/TDDFT study in dimethylsulfoxide solution.  


The structure and bonding of a new Pt-Tl bonded complex formed in dimethylsulfoxide (dmso), (CN)(4)Pt-Tl(dmso)(5)(+), have been studied by multinuclear NMR and UV-vis spectroscopies, and EXAFS measurements in combination with density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations. This complex is formed following the equilibrium reaction Pt(CN)(4)(2-) + Tl(dmso)(6)(3+) ? (CN)(4)Pt-Tl(dmso)(5)(+) + dmso. The stability constant of the Pt-Tl bonded species, as determined using (13)C NMR spectroscopy, amounts to log K = 2.9 ± 0.2. The (NC)(4)Pt-Tl(dmso)(5)(+) species constitutes the first example of a Pt-Tl bonded cyanide complex in which the sixth coordination position around Pt (in trans with respect to the Tl atom) is not occupied. The spectral parameters confirm the formation of the metal-metal bond, but differ substantially from those measured earlier in aqueous solution for complexes (CN)(5)Pt-Tl(CN)(n)(H(2)O)(x)(n-) (n = 0-3). The (205) Tl NMR chemical shift, ? = 75 ppm, is at extraordinary high field, while spin-spin coupling constant, (1)J(Pt-Tl) = 93 kHz, is the largest measured to date for a Pt-Tl bond in the absence of supporting bridging ligands. The absorption spectrum is dominated by two strong absorption bands in the UV region that are assigned to MMCT (Pt ? Tl) and LMCT (dmso ? Tl) bands, respectively, on the basis of MO and TDDFT calculations. The solution of the complex has a bright yellow color as a result of a shoulder present on the low energy side of the band at 355 nm. The geometry of the (CN)(4)Pt-Tl core can be elucidated from NMR data, but the particular stoichiometry and structure involving the dmso ligands are established by using Tl and Pt L(III)-edge EXAFS measurements. The Pt-Tl bond distance is 2.67(1) Å, the Tl-O bond distance is 2.282(6) Å, and the Pt-C-N entity is linear with Pt-C and Pt···N distances amounting to 1.969(6) and 3.096(6) Å, respectively. Geometry optimizations on the (CN)(4)Pt-Tl(dmso)(5)(+) system by using DFT calculations (B3LYP model) provide bond distances in excellent agreement with the EXAFS data. The four cyanide ligands are located in a square around the Pt atom, while the Tl atom is coordinated in a distorted octahedral fashion with the metal being located 0.40 Å above the equatorial plane described by four oxygen atoms of dmso ligands. The four equatorial Tl-O bonds and the four cyano ligands around the Pt atom are arranged in an alternate geometry. The coordination environment around Pt may be considered as being square pyramidal, where the apical position is occupied by the Tl atom. The optimized geometry of (CN)(4)Pt-Tl(dmso)(5)(+) is asymmetrical (C(1) point group). This low symmetry might be responsible for the unusually large NMR linewidths observed due to intramolecular chemical exchange processes. The nature of the Pt-Tl bond has been studied by MO analysis. The metal-metal bond formation in (CN)(4)Pt-Tl(dmso)(5)(+) can be simply interpreted as the result of a Pt(5d(z(2)))(2) ? Tl(6s)(0) donation. This bonding scheme may rationalize the smaller thermodynamic stability of this adduct compared to the related complexes with (CN)(5)Pt-Tl entity, where the linear C-Pt-Tl unit constitutes a very stable bonding system. PMID:21639126

Purgel, Mihály; Maliarik, Mikhail; Glaser, Julius; Platas-Iglesias, Carlos; Persson, Ingmar; Tóth, Imre



DFT 2H quadrupolar coupling constants of ruthenium complexes: a good probe of the coordination of hydrides in conjuction with experiments.  


Transition metal (TM) hydrides are of great interest in chemistry because of their reactivity and their potential as catalysts for hydrogenation reactions. 2H solid-state NMR can be used in order to get information about the local environment of hydrogen atoms, and more particularly the coordination mode of hydrides in such complexes. In this work we will show that it is possible to establish at the level of density functional theory (DFT) a viable methodological strategy that allows the determination of 2H NMR parameters, namely the quadrupolar coupling constant (C(Q)) respectively the quadrupolar splitting (deltanuQ) and the asymmetry parameter (etaQ). The reliability of the method (B3PW91-DFT) and basis set effects have been first evaluated for simple organic compounds (benzene and fluorene). A good correlation between experimental and theoretical values is systematically obtained if the large basis set cc-pVTZ is used for the computations. 2H NMR properties of five mononuclear ruthenium complexes (namely Cp*RuD3(PPh3), Tp*RuD(THT)2, Tp*RuD(D2)(THT) and Tp*RuD(D2)2 and RuD2(D2)2(PCy3)2) which exhibit different ligands and hydrides involved in different coordination modes (terminal-H or eta2-H2), have been calculated and compared to previous experimental data. The results obtained are in excellent agreement with experiments. Although 2H NMR spectra are not always easy to analyze, assistance by quantum chemistry calculations allows unambiguous assignment of the signals of such spectra. As far as experiments can be achieved at very low temperatures in order to avoid dynamic effects, this hybrid theoretical/experimental tool may give useful insights in the context of the characterization of ruthenium surfaces or nanoparticles with solid-state NMR. PMID:19842483

del Rosal, Iker; Gutmann, Torsten; Maron, Laurent; Jolibois, Franck; Chaudret, Bruno; Walaszek, Bernadeta; Limbach, Hans-Heinrich; Poteau, Romuald; Buntkowsky, Gerd



Identical extraction behavior and coordination of trivalent or hexavalent f-element cations using ionic liquid and molecular solvents.  


The extraction of both UO2(2+) and trivalent lanthanide and actinide ions (Am3+, Nd3+, Eu3+) by dialkylphosphoric or dialkylphosphinic acids from aqueous solutions into the ionic liquid, 1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide has been studied and compared to extractions into dodecane. Radiotracer partitioning measurements show comparable patterns of distribution ratios for both the ionic liquid/aqueous and dodecane/aqueous systems, and the limiting slopes at low acidity indicate the partitioning of neutral complexes in both solvent systems. The metal ion coordination environment, elucidated from EXAFS and UV-visible spectroscopy measurements, is equivalent in the ionic liquid and dodecane solutions with coordination of the uranyl cation by two hydrogen-bonded extractant dimers, and of the trivalent cations by three extractant dimers. This is the first definitive report of a system where both the biphasic extraction equilibria and metal coordination environment are the same in an ionic liquid and a molecular organic solvent. PMID:15909044

Cocalia, Violina A; Jensen, Mark P; Holbrey, John D; Spear, Scott K; Stepinski, Dominique C; Rogers, Robin D



Influence of uranyl speciation and iron oxides on uranium biogeochemical redox reactions  

SciTech Connect

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO{sub 2}{sup 2+} and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO{sub 2}. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl-calcium-carbonato complexes, and ferrihydrite on the rate and extent of uranium reduction in complex geochemical systems.

Stewart, B.D.; Amos, R.T.; Nico, P.S.; Fendorf, S.



Distributed intelligent real-time technique for coordinated multi-agents autonomous path planning among moving complex obstacles  

NASA Astrophysics Data System (ADS)

This paper is concerned with the difficult and interesting problem of real-time planning and efficient motion control of rigid multi-robot systems to dynamically avoid moving obstacles and/or robots as these move. Most techniques described so far in the literature deal with the simpler problem of generating (generally off-line) a path among stationary obstacles. For practical purposes, however, obstacles are not always static and most interesting environments are in general not known precisely and/or time varying. Motivated by the fact that robots capable of maneuvering among moving obstalces will be capable of accomplishing a much larger and more versatile class of tasks, and as a result of our current and past research investigations over the years, we present an innovative approach and tackle the problem from a different angle. The proposed method follows upon our previous work which employs a notion of complex potential fields representation, and involves the use of state variables which preserve the Newman Boundary condition of such complex potential fields while allowing mobile robots to autonomously and dynamically avoid each other as well as other moving obstacles. In the heart of the technique is the exploitation of the powerful and fundamental tool of conformal mapping to derive the path solution for obstacles of arbitrary shapes. The advantage this novel approach offers over traditional formulations is its handling of both static and arbitrary moving obstacles/multi-robots. To the author's best knowledge, the proposed technique is the only proposed approach in the literature for real-time mobile robots motion control and obstacles avoidance which not only guarantees the reaching of the robot's goal under some conditions but also focuses on the means by which both the obstacles positions and orientations can elegantly and efficiently be dealt with when these latter continuously change with time.

Megherbi, Dalila B.



Role of galactolipid biosynthesis in coordinated development of photosynthetic complexes and thylakoid membranes during chloroplast biogenesis in Arabidopsis.  


The galactolipids monogalactosyldiacylglycerol (MGDG) and digalactosyldiacylglycerol (DGDG) are the predominant lipids in thylakoid membranes and indispensable for photosynthesis. Among the three isoforms that catalyze MGDG synthesis in Arabidopsis thaliana, MGD1 is responsible for most galactolipid synthesis in chloroplasts, whereas MGD2 and MGD3 are required for DGDG accumulation during phosphate (Pi) starvation. A null mutant of Arabidopsis MGD1 (mgd1-2), which lacks both galactolipids and shows a severe defect in chloroplast biogenesis under nutrient-sufficient conditions, accumulated large amounts of DGDG, with a strong induction of MGD2/3 expression, during Pi starvation. In plastids of Pi-starved mgd1-2 leaves, biogenesis of thylakoid-like internal membranes, occasionally associated with invagination of the inner envelope, was observed, together with chlorophyll accumulation. Moreover, the mutant accumulated photosynthetic membrane proteins upon Pi starvation, indicating a compensation for MGD1 deficiency by Pi stress-induced galactolipid biosynthesis. However, photosynthetic activity in the mutant was still abolished, and light-harvesting/photosystem core complexes were improperly formed, suggesting a requirement for MGDG for proper assembly of these complexes. During Pi starvation, distribution of plastid nucleoids changed concomitantly with internal membrane biogenesis in the mgd1-2 mutant. Moreover, the reduced expression of nuclear- and plastid-encoded photosynthetic genes observed in the mgd1-2 mutant under Pi-sufficient conditions was restored after Pi starvation. In contrast, Pi starvation had no such positive effects in mutants lacking chlorophyll biosynthesis. These observations demonstrate that galactolipid biosynthesis and subsequent membrane biogenesis inside the plastid strongly influence nucleoid distribution and the expression of both plastid- and nuclear-encoded photosynthetic genes, independently of photosynthesis. PMID:22978702

Kobayashi, Koichi; Narise, Takafumi; Sonoike, Kintake; Hashimoto, Haruki; Sato, Naoki; Kondo, Maki; Nishimura, Mikio; Sato, Mayuko; Toyooka, Kiminori; Sugimoto, Keiko; Wada, Hajime; Masuda, Tatsuru; Ohta, Hiroyuki



Brightly phosphorescent, environmentally responsive hydrogels containing a water-soluble three-coordinate gold(I) complex.  


Stimuli-responsive phosphorescent hydrogel microspheres have been synthesized by incorporating a water-soluble phosphorescent Au(I) complex, Na(8)[Au(TPPTS)(3)], TPPTS = tris(3,3',3''-trisulfonatophenyl)phosphine, into the polymer network of poly(N-isopropylacrylamide) (PNIPAM). Remarkable sensitization of the Au-centered emission takes place in the resulting phosphorescent hydrogels (by up to 2 orders of magnitude!) compared to that of the gold complex alone in pure water. Results of pH- and temperature-dependent luminescence titrations show that the sensitization is further magnified at physiological conditions, which is desirable for biomedical applications that will include bioimaging and drug delivery. The physical properties of PNIPAM microgels are not negatively impacted by the presence of the gold luminophore, as the colloidal crystallinity and phase transition properties remain intact. Phosphorescent microspheres have been further cross-linked by covalently bonding to neighboring particles, leading to brightly phosphorescent/high-water-content crystalline hydrogel networks with more stable crystallinity vs microgel soft crystals. These gel networks exhibit the same green phosphorescence seen in the hydrogel microspheres and pure Na(8)[Au(TPPTS)(3)] aqueous solutions with a broad unstructured profile and peak maximum at ?525 nm. Dehydration leads to further emission sensitization and gradual blue shifts that can be fine-tuned to ultimately reach a turquoise emission at ?490 nm in the freeze-dried form of the gel, corresponding to the emission of single crystals of Na(8)[Au(TPPTS)(3)], in agreement with the photoinduced Jahn-Teller distorted excited state model we reported earlier. Remarkable sensitivity to temperature and pH takes place in the emission enhancement with particularly favorable results at physiological conditions. The work herein represents a unique example of a stimulus-responsive phosphorescent hydrogel from a transition metal-based as opposed to lanthanide-based phosphor in an aqueous medium. PMID:20836534

Marpu, Sreekar; Hu, Zhibing; Omary, Mohammad A



Measurement of extreme hyperfine fields in two-coordinate high-spin fe(2+) complexes by mössbauer spectroscopy: essentially free-ion magnetism in the solid state.  


Mössbauer studies of three two-coordinate linear high-spin Fe(2+) compounds, namely, Fe{N(SiMe3)(Dipp)}2 (1) (Dipp = C6H3-2,6-(i)Pr2), Fe(OAr')2 (2) [Ar' = C6H3-2,6-(C6H3-2,6-(i)Pr2)2], and Fe{C(SiMe3)3}2 (3), are presented. The complexes were characterized by zero- and applied-field Mössbauer spectroscopy (1-3), as well as zero- and applied-field heat-capacity measurements (3). As 1-3 are rigorously linear, the distortion(s) that might normally be expected in view of the Jahn-Teller theorem need not necessarily apply. We find that the resulting very large unquenched orbital angular momentum leads to what we believe to be the largest observed internal magnetic field to date in a high-spin iron(II) compound, specifically +162 T in 1. The latter field is strongly polarized along the directions of the external field for both longitudinal and transverse field applications. For the longitudinal case, the applied field increases the overall hyperfine splitting consistent with a dominant orbital contribution to the effective internal field. By contrast, 2 has an internal field that is not as strongly polarized along a longitudinally applied field and is smaller in magnitude at ca. 116 T. Complex 3 behaves similarly to complex 1. They are sufficiently self-dilute (e.g., Fe···Fe distances of ca. 9-10 Å) to exhibit varying degrees of slow paramagnetic relaxation in zero field for the neat solid form. In the absence of EPR signals for 1-3, we show that heat-capacity measurements for one of the complexes (3) establish a geff value near 12, in agreement with the principal component of the ligand electric field gradient being coincident with the z axis. PMID:25368962

Bryan, Aimee M; Lin, Chun-Yi; Sorai, Michio; Miyazaki, Yuji; Hoyt, Helen M; Hablutzel, Annelise; LaPointe, Anne; Reiff, William M; Power, Philip P; Schulz, Charles E



Coordination and Processing of DNA Ends During Double-Strand Break Repair: The Role of the Bacteriophage T4 Mre11/Rad50 (MR) Complex  

PubMed Central

The in vivo functions of the bacteriophage T4 Mre11/Rad50 (MR) complex (gp46/47) in double-strand-end processing, double-strand break repair, and recombination-dependent replication were investigated. The complex is essential for T4 growth, but we wanted to investigate the in vivo function during productive infections. We therefore generated a suppressed triple amber mutant in the Rad50 subunit to substantially reduce the level of complex and thereby reduce phage growth. Growth-limiting amounts of the complex caused a concordant decrease in phage genomic recombination-dependent replication. However, the efficiencies of double-strand break repair and of plasmid-based recombination-dependent replication remained relatively normal. Genetic analyses of linked markers indicated that double-strand ends were less protected from nuclease erosion in the depleted infection and also that end coordination during repair was compromised. We discuss models for why phage genomic recombination-dependent replication is more dependent on Mre11/Rad50 levels when compared to plasmid recombination-dependent replication. We also tested the importance of the conserved histidine residue in nuclease motif I of the T4 Mre11 protein. Substitution with multiple different amino acids (including serine) failed to support phage growth, completely blocked plasmid recombination-dependent replication, and led to the stabilization of double-strand ends. We also constructed and expressed an Mre11 mutant protein with the conserved histidine changed to serine. The mutant protein was found to be completely defective for nuclease activities, but retained the ability to bind the Rad50 subunit and double-stranded DNA. These results indicate that the nuclease activity of Mre11 is critical for phage growth and recombination-dependent replication during T4 infections. PMID:23979587

Almond, Joshua R.; Stohr, Bradley A.; Panigrahi, Anil K.; Albrecht, Dustin W.; Nelson, Scott W.; Kreuzer, Kenneth N.



Ultrafiltration of uranyl peroxide nanoclusters for the separation of uranium from aqueous solution.  


Uranyl peroxide cluster species were produced in aqueous solution by the treatment of uranyl nitrate with hydrogen peroxide, lithium hydroxide, and potassium chloride. Ultrafiltration of these cluster species using commercial sheet membranes with molecular mass cutoffs of 3, 8, and 20 kDa (based on polyethylene glycol) resulted in U rejection values of 95, 85, and 67% by mass, respectively. Ultrafiltration of untreated uranyl nitrate solutions using these membranes resulted in virtually no rejection of U. These results demonstrate the ability to use the filtration of cluster species as a means for separating U from solutions on the basis of size. Small-angle X-ray scattering, Raman spectroscopy, and electrospray ionization mass spectrometry confirmed the presence of uranyl peroxide cluster species in solution and were used to characterize their size, shape, and dispersity. PMID:24313601

Wylie, Ernest M; Peruski, Kathryn M; Weidman, Jacob L; Phillip, William A; Burns, Peter C



The application of time-resolved luminescence spectroscopy to a remote uranyl sensor  

SciTech Connect

Time resolved luminescence spectroscopy is an effective method for the determination of a wide range of uranyl concentrations in aqueous samples. We have applied this technique to the development of a remote sensing device using fiber optic cables coupled with a micro flow cell in order to probe for uranyl in aqueous samples. This sensor incorporates a Nafion membrane through which UO{sub 2}{sup 2+} can diffuse in to a reaction/analysis chamber which holds phosphoric acid, a reagent which enhances the uranyl luminescence intensity and lifetime. With this device, anionic and fluorescing organic interferences could be eliminated, allowing for the determination of uranyl over a concentration range of 10{sup 4} to 10{sup {minus}9}M. 17 refs., 5 figs.

Varineau, P.T.; Duesing, R.; Wangen, L.E.



Analysis of Enriched Uranyl Nitrate in Nested Annular Tank Array  

SciTech Connect

Two series of experiments were performed at the Rocky Flats Critical Mass Laboratory during the 1980s using highly enriched (93%) uranyl nitrate solution in annular tanks. [1, 2] Tanks were of typical sizes found in nuclear production plants. Experiments looked at tanks of varying radii in a co-located set of nested tanks, a 1 by 2 array, and a 1 by 3 array. The co-located set of tanks had been analyzed previously [3] as a benchmark for inclusion within the International Handbook of Evaluated Criticality Safety Benchmark Experiments. [4] The current study represents the benchmark analysis of the 1 by 3 array of a series of nested annular tanks. Of the seventeen configurations performed in this set of experiments, twelve were evaluated and nine were judged as acceptable benchmarks.

John D. Bess; James D. Cleaver



A Raman spectroscopic study of the uranyl phosphate mineral bergenite  

NASA Astrophysics Data System (ADS)

Raman spectroscopy at 298 and 77 K of bergenite has been used to characterise this uranyl phosphate mineral. Bands at 995, 971 and 961 cm -1 (298 K) and 1006, 996, 971, 960 and 948 cm -1 (77 K) are assigned to the ?1(PO 4) 3- symmetric stretching vibration. Three bands at 1059, 1107 and 1152 cm -1 (298 K) and 1061, 1114 and 1164 cm -1 (77 K) are attributed to the ?3(PO 4) 3- antisymmetric stretching vibrations. Two bands at 810 and 798 cm -1 (298 K) and 812 and 800 cm -1 (77 K) are attributed to the ?1 symmetric stretching vibration of the (UO 2) 2+ units. Bands at 860 cm -1 (298 K) and 866 cm -1 (77 K) are assigned to the ?3 antisymmetric stretching vibrations of the (UO 2) 2+ units. U sbnd O bond lengths in uranyls, calculated using the wavenumbers of the ?1 and ?3(UO 2) 2+ vibrations with empirical relations by Bartlett and Cooney, are in agreement with the X-ray single crystal structure data. Bands at (444, 432, 408 cm -1) (298 K), and (446, 434, 410 and 393 cm -1) (77 K) are assigned to the split doubly degenerate ?2(PO 4) 3- in-plane bending vibrations. The band at 547 cm -1 (298 K) and 549 cm -1 (77 K) are attributed to the ?4(PO 4) 3- out-of-plane bending vibrations. Raman bands at 3607, 3459, 3295 and 2944 cm -1 are attributed to water stretching vibrations and enable the calculation of hydrogen bond distances of >3.2, 2.847, 2.740 and 2.637 Å. These bands prove the presence of structurally nonequivalent hydrogen bonded water molecules in the structure of bergenite.

Frost, Ray L.; ?ejka, Ji?í; Ayoko, Godwin A.; Weier, Matt



Two-dimensional (14)N HYSCORE spectroscopy of the coordination geometry of ligands in dimanganese di-?-oxo mimics of the oxygen evolving complex of photosystem II.  


We use two-dimensional hyperfine sublevel correlation (HYSCORE) spectroscopy to investigate the coordination geometry of the nitrogen ligands of biomimetic models of the oxygen-evolving complex of photosystem II. In the 2D HYSCORE spectroscopy study, [(bpy)(2)Mn(III)(?-O)(2)Mn(IV)(bpy)(2)](ClO(4))(3) (bpy, 2,2'-bipyridine) () and [H(2)O(terpy)Mn(III)(?-O)(2)Mn(IV)(terpy)OH(2)](NO(3))(3) (terpy = 2,2':6',2?-terpyridine) () exhibit electron-nuclear hyperfine interactions that depend on both the oxidation state of the manganese ion and the geometry of the nitrogen ligand. We observe four types of (14)N hyperfine interactions corresponding to the Mn(iii) and Mn(iv) ion of each mixed-valence complex and the equatorial and axial geometry of the ligand, respectively. The strongest and the weakest hyperfine interactions arise from the axial and equatorial ligands of the Mn(iii) ion, respectively. The hyperfine interactions of intermediate strength are due to the axial and equatorial ligands of the Mn(iv) ion. Based on the results of this study, we assign the location and ligand geometry of the Mn(iii) ion of the tetranuclear manganese-calcium-oxo cluster in the S(2) state of photosystem II. PMID:22491172

Chatterjee, Ruchira; Milikisiyants, Sergey; Lakshmi, K V



Enantioseparation of dansyl amino acids and dipeptides by chiral ligand exchange capillary electrophoresis based on Zn(II)-L-hydroxyproline complexes coordinating with ?-cyclodextrins.  


A chiral ligand exchange capillary electrophoresis (CLE-CE) method using Zn(II) as the central ion and L-4-hydroxyproline as the chiral ligand coordinating with ?-cyclodextrin (?-CD) was developed for the enantioseparation of amino acids (AAs) and dipeptides. The effects of various separation parameters, including the pH of the running buffer, the ratio of Zn(II) to L-4-hydroxyproline, the concentration of complexes and cyclodextrins (CDs) were systematically investigated. After optimization, it has been found that eight pairs of labeled AAs and six pairs of labeled dipeptides could be baseline-separated with a running electrolyte of 100.0mM boric acid, 5.0mM ammonium acetate, 3.0mM Zn(II), 6.0mM L-hydroxyproline and 4.0mM ?-CD at pH 8.2. The quantitation of AAs and dipeptides was conducted and good linearity (r(2)?0.997) and favorable repeatability (RSD?3.6%) were obtained. Furthermore, the proposed method was applied in determining the enantiomeric purity of AAs and dipeptides. Meanwhile, the possible enantiorecognition mechanism based on the synergistic effect of chiral metal complexes and ?-CD was explored and discussed briefly. PMID:25220143

Mu, Xiaoyu; Qi, Li; Qiao, Juan; Yang, Xinzheng; Ma, Huimin



Bond valence sums in coordination chemistry. The calculation of the oxidation state of samarium in complexes containing samarium bonded only to oxygen.  


A simple method is presented for calculating the oxidation state of Sm in complexes where Sm is bonded only to O ligands. A total of 88 SmO(n)() fragments with n = 4-12 were retrieved from the Cambridge Structural Database and were analyzed using the bond valence sum (BVS) method. New R(0) values for Sm(II)-O of 2.116(21) A and for Sm(III)-O of 2.055(13) A were derived. The average R(0) value of 2.086 A gives a good approximation of the oxidation state of the Sm ion, either +2 or +3, from the observed distances without any assumptions. The Sm-O distances for +2 and +3 complexes with coordination numbers of 4-11 are tabulated and reflect the requirement that the BVS must equal the oxidation state. The distances for CN = 12 were not included because of problems with the reported crystal structures. Several X-ray structure determinations where the BVS and the oxidation state did not agree are discussed. PMID:12691581

Palenik, Gus J



Reactions of coordinated dinitrogen. 8. Formation of ammonia by protonation of a molybdenum-dinitrogen complex and isolation and characterization of the molybdenum-containing product  

SciTech Connect

This is the first reported conversion of metal-coordinated dinitrogen into ammonia in which the fate of the metal has been determined. This reaction is shown in the following equation, where triphos = PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/ and L = PPh/sub 3/:2Mo(N/sub 2/)/sub 2/(triphos)(L) + 8HBr ..-->.. 2NH/sub 4/Br + 2MoBr/sub 3/(triphos) + 3N/sub 2/ + 2L. The metal complex which is a new subclass of bis(dinitrogen) complexes of molybdenum, reacted in tetrahydrofuran (THF) solution with anhydrous hydrogen bromide to produce ammonium bromide. No hydrazine or hydrazinium bromide was detected among the reaction products. Ammonium bromide was detected by infrared spectroscopy among the reaction products after solvent and excess HBr had been removed in vacuo. The yield of ammonia was determined quantitatively by the indophenol method after either aqueous, nonaqueous (ethanol), or two-phase (dichloromethane-water) extraction of ammonium bromide from the residue. The molybdenum-containing product slowly decomposed during the dichloromethane-water extraction step. Isolation of pure MoBr/sub 3/(triphos) was carried out in a separate experiment in which only N/sub 2/ evolution was measured. All volatiles were removed from the reaction vessel and the resulting yellow solid was washed with ethanol and dried. Its identity was confirmed by elemental analysis.

Baumann, J.A.; George, T.A.



Processing coordination ambiguity.  


We examined temporarily ambiguous coordination structures such as put the butter in the bowl and the pan on the towel. Minimal Attachment predicts that the ambiguous noun phrase the pan will be interpreted as a noun-phrase coordination structure because it is syntactically simpler than clausal coordination. Constraint-based theories assume that interpretations are the result of a constraint-satisfaction process, which predicts that frequency or context can bias the parser to initially pursue a more complex interpretation.The results showed an initial preference for noun-phrase coordination, despite the fact that sentential coordination is more frequent in imperative structures. These data suggest that the parser uses a syntactic simplicity heuristic for building initial structural analyses. PMID:21313991

Engelhardt, Paul E; Ferreira, Fernanda



Role of Axial Base Coordination in Isonitrile Binding and Chalcogen Atom Transfer to Vanadium(III) Complexes.  


The enthalpy of oxygen atom transfer (OAT) to V[(Me3SiNCH2CH2)3N], 1, forming OV[(Me3SiNCH2CH2)3N], 1-O, and the enthalpies of sulfur atom transfer (SAT) to 1 and V(N[t-Bu]Ar)3, 2 (Ar = 3,5-C6H3Me2), forming the corresponding sulfides SV[(Me3SiNCH2CH2)3N], 1-S, and SV(N[t-Bu]Ar)3, 2-S, have been measured by solution calorimetry in toluene solution using dbabhNO (dbabhNO = 7-nitroso-2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-diene) and Ph3SbS as chalcogen atom transfer reagents. The V-O BDE in 1-O is 6.3 ± 3.2 kcal·mol(-1) lower than the previously reported value for 2-O and the V-S BDE in 1-S is 3.3 ± 3.1 kcal·mol(-1) lower than that in 2-S. These differences are attributed primarily to a weakening of the V-Naxial bond present in complexes of 1 upon oxidation. The rate of reaction of 1 with dbabhNO has been studied by low temperature stopped-flow kinetics. Rate constants for OAT are over 20 times greater than those reported for 2. Adamantyl isonitrile (AdNC) binds rapidly and quantitatively to both 1 and 2 forming high spin adducts of V(III). The enthalpies of ligand addition to 1 and 2 in toluene solution are -19.9 ± 0.6 and -17.1 ± 0.7 kcal·mol(-1), respectively. The more exothermic ligand addition to 1 as compared to 2 is opposite to what was observed for OAT and SAT. This is attributed to less weakening of the V-Naxial bond in ligand binding as opposed to chalcogen atom transfer and is in keeping with structural data and computations. The structures of 1, 1-O, 1-S, 1-CNAd, and 2-CNAd have been determined by X-ray crystallography and are reported. PMID:25280113

Majumdar, Subhojit; Stauber, Julia M; Palluccio, Taryn D; Cai, Xiaochen; Velian, Alexandra; Rybak-Akimova, Elena V; Temprado, Manuel; Captain, Burjor; Cummins, Christopher C; Hoff, Carl D



Cadmium(II) iodide and thiocyanate complexes adopted by polycyclic 1,4-bis(pyridazin-4-yl)benzene: interplay of coordination and ?-? stacking interactions.  


New complexes containing the 1,4-bis(pyridazin-4-yl)benzene ligand, namely diaquatetrakis[1,4-bis(pyridazin-4-yl)benzene-?N(2)]cadmium(II) hexaiodidodicadmate(II), [Cd(C14H10N4)4(H2O)2][Cd2I6], (I), and poly[[?-1,4-bis(pyridazin-4-yl)benzene-?(2)N(2):N(2')]bis(?-thiocyanato-?(2)N:S)cadmium(II)], [Cd(NCS)2(C14H10N4)]n, (II), demonstrate the adaptability of the coordination geometries towards the demands of slipped ?-? stacking interactions between the extended organic ligands. In (I), the discrete cationic [Cd-N = 2.408?(3) and 2.413?(3)?Å] and anionic [Cd-I = 2.709?(2)-3.1201?(14)?Å] entities are situated across centres of inversion. The cations associate via complementary O-H...N(2') hydrogen bonding [O...N = 2.748?(4) and 2.765?(4)?Å] and extensive triple ?-? stacking interactions between pairs of pyridazine and phenylene rings [centroid-centroid distances (CCD) = 3.782?(4)-4.286?(3)?Å] to yield two-dimensional square nets. The [Cd2I6](2-) anions reside in channels generated by packing of successive nets. In (II), the Cd(II) cation lies on a centre of inversion and the ligand is situated across a centre of inversion. A two-dimensional coordination array is formed by crosslinking of linear [Cd(?-NCS)2]n chains [Cd-N = 2.3004?(14)?Å and Cd-S = 2.7804?(5)?Å] with N(2):N(2')-bidentate organic bridges [Cd-N = 2.3893?(12)?Å], which generate ?-? stacks by double-slipped interactions between phenylene and pyridazine rings [CCD = 3.721?(2)?Å]. PMID:23459341

Degtyarenko, Anna S; Domasevitch, Konstantin V



Comparative studies of mononuclear Ni(II) and UO2(II) complexes having bifunctional coordinated groups: Synthesis, thermal analysis, X-ray diffraction, surface morphology studies and biological evaluation  

NASA Astrophysics Data System (ADS)

Two Schiff base ligands derived from condensation of phthalaldehyde and o-phenylenediamine in 1:2 (L1) and 2:1 (L2) having bifunctional coordinated groups (NH2 and CHO groups, respectively) and their metal complexes with Ni(II) and UO2(II) have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibilities and spectral data (IR, 1H NMR, mass and solid reflectance) as well as thermal, XRPD and SEM analysis. The formula [Ni(L1)Cl2]·2.5H2O, [UO2(L1)(NO3)2]·2H2O, [Ni(L2)Cl2]·1.5H2O and [UO2(L2)(NO3)2] have been suggested for the complexes. The vibrational spectral data show that the ligands behave as neutral ligands and coordinated to the metal ions in a tetradentate manner. The Ni(II) complexes are six coordinate with octahedral geometry and the ligand field parameters: Dq, B, ? and LFSE were calculated while, UO2(II) complexes are eight coordinate with dodecahedral geometry and the force constant, FUsbnd O and bond length, RUsbnd O were calculated. The thermal decomposition of complexes ended with metal chloride/nitrate as a final product and the highest thermal stability is displayed by [UO2(L2)(NO3)2] complex. The X-ray powder diffraction data revealed the formation of nano sized crystalline complexes. The SEM analysis provides the morphology of the synthesized compounds and SEM image of [UO2(L2)(NO3)2] complex exhibits nano rod structure. The growth-inhibiting potential of the ligands and their complexes has been assessed against a variety of bacterial and fungal strains.

Fahem, Abeer A.



Comparative studies of mononuclear Ni(II) and UO2(II) complexes having bifunctional coordinated groups: synthesis, thermal analysis, X-ray diffraction, surface morphology studies and biological evaluation.  


Two Schiff base ligands derived from condensation of phthalaldehyde and o-phenylenediamine in 1:2 (L(1)) and 2:1 (L(2)) having bifunctional coordinated groups (NH(2) and CHO groups, respectively) and their metal complexes with Ni(II) and UO(2)(II) have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibilities and spectral data (IR, (1)H NMR, mass and solid reflectance) as well as thermal, XRPD and SEM analysis. The formula [Ni(L(1))Cl(2)]·2.5H(2)O, [UO(2)(L(1))(NO(3))(2)]·2H(2)O, [Ni(L(2))Cl(2)]·1.5H(2)O and [UO(2)(L(2))(NO(3))(2)] have been suggested for the complexes. The vibrational spectral data show that the ligands behave as neutral ligands and coordinated to the metal ions in a tetradentate manner. The Ni(II) complexes are six coordinate with octahedral geometry and the ligand field parameters: D(q), B, ? and LFSE were calculated while, UO(2)(II) complexes are eight coordinate with dodecahedral geometry and the force constant, F(U-O) and bond length, R(U-O) were calculated. The thermal decomposition of complexes ended with metal chloride/nitrate as a final product and the highest thermal stability is displayed by [UO(2)(L(2))(NO(3))(2)] complex. The X-ray powder diffraction data revealed the formation of nano sized crystalline complexes. The SEM analysis provides the morphology of the synthesized compounds and SEM image of [UO(2)(L(2))(NO(3))(2)] complex exhibits nano rod structure. The growth-inhibiting potential of the ligands and their complexes has been assessed against a variety of bacterial and fungal strains. PMID:22197356

Fahem, Abeer A



6. Coordination and control.  


Any complex operation requires a system for management. In most societies, disaster management is the responsibility of the government. Coordination and control is a system that provides the oversight for all of the disaster management functions. The roles and responsibilities of a coordination and control centre include: (1) planning; (2) maintenance of inventories; (3) activation of the disaster response plan; (4) application of indicators of function; (5) surveillance; (6) information management; (7) coordination of activities of the BSFs; (8) decision-making; (9) priority setting; (10) defining overarching goal and objectives for interventions; (11) applying indicators of effectiveness; (12) applying indicators of benefit and impact; (13) exercising authority; (14) managing resources; (15) initiating actions; (16) preventing influx of unneeded resources; (17) defining progress; (18) providing information; (19) liasing with responding organisations; and (20) providing quality assurance. Coordination and control is impossible without communications. To accomplish coordination and control, three factors must be present: (1) mandate; (2) power and authority; and (3) available resources. Coordination and control is responsible for the evaluation of the effectiveness and benefits/impacts of all interventions. Coordination and control centres (CCCs) are organised hierarchically from the on-scene CCCs (incident command) to local provincial to national CCCs. Currently, no comprehensive regional and international CCCs have been universally endorsed. Systems such as the incident command system, the unified command system, and the hospital incident command system are described as are the humanitarian reform movement and the importance of coordination and control in disaster planning and preparedness. PMID:24785803



Standard test methods for chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solutions  

E-print Network

1.1 These test methods cover procedures for the chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solution to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Determination of Uranium 7 Specific Gravity by Pycnometry 15-20 Free Acid by Oxalate Complexation 21-27 Determination of Thorium 28 Determination of Chromium 29 Determination of Molybdenum 30 Halogens Separation by Steam Distillation 31-35 Fluoride by Specific Ion Electrode 36-42 Halogen Distillate Analysis: Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 43 Determination of Chloride and Bromide 44 Determination of Sulfur by X-Ray Fluorescence 45 Sulfate Sulfur by (Photometric) Turbidimetry 46 Phosphorus by the Molybdenum Blue (Photometric) Method 54-61 Silicon by the Molybdenum Blue (Photometric) Method 62-69 Carbon by Persulfate Oxidation-Acid Titrimetry 70 Conversion to U3O8 71-74 Boron by ...

American Society for Testing and Materials. Philadelphia



Controlled synthesis of racemic indenyl rare-earth metal complexes via the cooperation between the intramolecular coordination of donor atoms and a bridge.  


The reactions of Me2Si(C9H6CH2CH2-DG)2 (DG = NMe2 (1), CH2NMe2 (2), OMe (3), and N(CH2CH2)2O (4)) with [(Me3Si)2N]3RE(?-Cl)Li(THF)3 in toluene afforded a series of racemic divalent rare-earth metal complexes: {?(5):?(1):?(5):?(1)-Me2Si(C9H5CH2CH2-DG)2}RE (DG = NMe2, RE = Yb (6) and Eu (7); DG = CH2NMe2, RE = Yb (8), Eu (9), and Sm (10); DG = OMe, RE = Yb (11) and Eu (12); DG = N(CH2CH2)2O, RE = Yb (13) and Eu (14)). Similarly, the racemic divalent rare-earth metal complexes {?(5):?(1):?(5):?(1)-Me2Si(C9H5CH2CH2CH2NMe2)(C9H5CH2CH2OMe)}RE (RE = Yb (15) and Eu (16)) were also obtained. The reaction of Me2Si(C9H5CH2CH2OMe)2Li2 with NdCl3 gave a racemic dimeric neodymium chloride {?(5):?(1):?(5)-Me2Si(C9H5CH2CH2OMe)2NdCl}2 (17), whereas the reaction of Me2Si(C9H5CH2CH2NMe2)2Li2 with SmCl3 afforded a racemic dinuclear samarium chloride bridged by lithium chloride {?(5):?(1):?(5):?(1)-Me2Si(C9H5CH2CH2NMe2)2SmCl}2(?-LiCl) (18). Further reaction of complex 18 with LiCH2SiMe3 provided an unexpected rare-earth metal alkyl complex {?(5):?(1):?(5):?(1):?-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Sm (19) through the activation of an sp(3) C-H bond ?-adjacent to the nitrogen atom. Complexes 19 and {?(5):?(1):?(5):?(1):?-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Y (20) were also obtained by one-pot reactions of Me2Si(C9H5CH2CH2NMe2)2Li2 with RECl3 followed by treatment with LiCH2SiMe3. All compounds were fully characterized by spectroscopic methods and elemental analysis. Complexes 6-10 and 14-20 were further characterized by single-crystal X-ray diffraction analysis. All of the prepared rare-earth metal complexes were racemic, suggesting that racemic organo rare-earth metal complexes could be controllably synthesized by the cooperation between a bridge and the intramolecular coordination of donor atoms. PMID:23697923

Zhou, Shuangliu; Wu, Zhangshuan; Zhou, Lingmin; Wang, Shaowu; Zhang, Lijun; Zhu, Xiancui; Wei, Yun; Zhai, Jinhua; Wu, Jie



cis -Diaminedichloroplatinum(II) complexes reversibly bound to water-soluble polyaspartamide carriers for chemotherapeutic applications. II: Platinum coordination to ethylenediamine ligands attached to poly(ethylene oxide)-grafted carrier polymers  

Microsoft Academic Search

In continuation of previous investigations aiming at the development of macromolecular metal complexes for biomedical use, this communication describes poly(alkylene oxide)-grafted polymeric platinum complexes. The platinum-containing macromolecules are obtained from presynthesized polyaspartamide carriers bearing poly(ethylene\\/propylene oxide) side chains and hydroxyethyl side groups as hydrosolubilizing units in addition to ethylenediamine side group terminals for metal coordination. Platination is brought about by

Eberhard W. Neuse; Gregg Caldwell; Axel G. Perlwitz



Synthesis of the stable UO2I2, the last of the uranyl dihalides. X-ray crystal structure of [UO2I2(py)3].  


Treatment of UO2(OTf)2 with pure Me3SiI led to the quantitative formation of UO2I2 (1). This compound dissolved in pyridine and thf to give the red adducts [UO2I2L3][L = py (2) or thf (3)], which were also obtained from the metathetical reaction of UO2(OTf)2 and KI. The crystal structure of has been determined. The uranyl diiodide complexes - are thermally quite stable, providing that strictly anhydrous conditions are employed. PMID:15045105

Berthet, Jean-Claude; Nierlich, Martine; Ephritikhine, Michel



Six-coordinate high-spin iron(ii) complexes with bidentate PN ligands based on 2-aminopyridine - new Fe(ii) spin crossover systems.  


Several new octahedral iron(ii) complexes of the type [Fe(PN(R)-Ph)2X2] (X = Cl, Br; R = H, Me) containing bidentate PN(R)-Ph (R = H, Me) (1a,b) ligands based on 2-aminopyridine were prepared. (57)Fe Mössbauer spectroscopy and magnetization studies confirmed in all cases their high spin nature at room temperature with magnetic moments very close to 4.9?B reflecting the expected four unpaired d-electrons in all these compounds. While in the case of the PN(H)-Ph ligand an S = 2 to S = 0 spin crossover was observed at low temperatures, complexes with the N-methylated analog PN(Me)-Ph retain an S = 2 spin state also at low temperatures. Thus, [Fe(PN(H)-Ph)2X2] (2a,3a) and [Fe(PN(Me)-Ph)2X2] (2b,3b) adopt different geometries. In the first case a cis-Cl,P,N-arrangement seems to be most likely, as supported by various experimental data derived from (57)Fe Mössbauer spectroscopy, SQUID magnetometry, UV/Vis, Raman, and ESI-MS as well as DFT and TDDFT calculations, while in the case of the PN(Me)-Ph ligand a trans-Cl,P,N-configuration is adopted. The latter is also confirmed by X-ray crystallography. In contrast to [Fe(PN(Me)-Ph)2X2] (2b,3b), [Fe(PN(H)-Ph)2X2] (2a,3a) is labile and undergoes rearrangement reactions. In CH3OH, the diamagnetic dicationic complex [Fe(PN(H)-Ph)3](2+) (5) is formed via the intermediacy of cis-P,N-[Fe(?(2)-P,N-PN(H)-Ph)2(?(1)-P-PN(H)-Ph)(X)](+) (4a,b) where one PN ligand is coordinated in a ?(1)-P-fashion. In CH3CN the diamagnetic dicationic complex cis-N,P,N-[Fe(PN(H)-Ph)2(CH3CN)2](2+) (6) is formed as a major isomer where the two halide ligands are replaced by CH3CN. PMID:24695811

Holzhacker, Christian; Calhorda, Maria José; Gil, Adrià; Carvalho, Maria Deus; Ferreira, Liliana P; Stöger, Berthold; Mereiter, Kurt; Weil, Matthias; Müller, Danny; Weinberger, Peter; Pittenauer, Ernst; Allmaier, Günter; Kirchner, Karl



An Al/P-based frustrated Lewis pair as an efficient ambiphilic ligand: coordination of boron trihalides, rearrangement, and formation of HBX? complexes (X = Br, I).  


The Al/P-based frustrated Lewis pair (FLP) Mes2P-C(?CH-Ph)-Al(CMe3)2 (1) reacted with boron halides BX3 (X = F, Cl, Br, I) as an ambiphilic ligand to form complexes (2-5) in which the boron atoms were coordinated to phosphorus and one of the halogen atoms to aluminum. Nonplanar five-membered heterocycles resulted that had five different ring atoms (AlCPBX). The distance of the bridging halogen atoms to the AlCPB plane increased steadily with the radius of the halogen atoms. Only the BF3 adduct showed a dynamic behavior in solution at room temperature with equivalent tert-butyl or mesityl groups in the NMR spectra, while in other cases, the rigid conformation led to the magnetic inequivalence of the substituents at Al and P with well-resolved signals for each group. The BBr3 and BI3 complexes underwent in solution at room temperature a spontaneous stereoselective rearrangement with the concomitant release of isobutene. The obtained products, Mes2P-(?-C?CH-Ph)(?-HBX2)-AlX(CMe3) (6 and 7) may be viewed as unique adducts of a modified new Al/P-based FLP, Mes2P-C(?CH-Ph)-AlX(CMe3) (X = Br, I), with dihalogenboranes, HBX2. The trapped boranes are either completely unknown (X = I) or unstable in the free form. Quantum-chemical calculations suggest an ionic rearrangement mechanism via the formation of a borenium cation, ?-hydride elimination, and hydride transfer. The bromine migration from boron to aluminum corresponds to a formal suprafacial 1,3-sigmatropic rearrangement. PMID:25144381

Uhl, Werner; Appelt, Christian; Wollschläger, Agnes; Hepp, Alexander; Würthwein, Ernst-Ulrich



Uranyl nitrate-exposed rat alveolar macrophages cell death: Influence of superoxide anion and TNF ? mediators  

SciTech Connect

Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 ?M). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO{sub 3} 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO{sub 3}. We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O{sub 2}{sup ?}). At high doses it provokes the secretion of TNF? and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O{sub 2}{sup ?} may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O{sub 2}{sup ?} may be blocked, prevailing damage to DNA by the TNF? route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium?related diseases. -- Highlights: ? Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ? At low doses uranyl nitrate induces generation of superoxide anion. ? At high doses uranyl nitrate provokes secretion of TNF?. ? Uranyl nitrate induces apoptosis through all the range of doses tested.

Orona, N.S. [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina)] [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); Tasat, D.R., E-mail: [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); School of Dentistry, University of Buenos Aires, M. T. de Alvear 2142 (1122), Buenos Aires (Argentina)



A complex containing two transcription factors regulates peroxisome proliferation and the coordinate induction of beta-oxidation enzymes in Saccharomyces cerevisiae.  

PubMed Central

Expression of the POX1 gene, which encodes peroxisomal acyl coenzyme A oxidase in the yeast Saccharomyces cerevisiae, is tightly regulated and can be induced by fatty acids such as oleate. Previously we have shown that this regulation is brought about by interactions between trans-acting factor(s) and an upstream activating sequence (UAS1) in the POX1 promoter. We recently identified and isolated a transcription factor, Oaf1p, that binds to the UAS1 of POX1 and mediates its induction. A screening strategy has been developed and used to identify eight S. cerevisiae mutants, from three complementation groups, that are defective in the oleate induction of POX1. Characterization of one such mutant led to the identification of Oaf2p, a protein that is 39% identical to Oaf1p. Oaf1p and Oaf2p form a protein complex that is required for the activation of POX1 and FOX3 and for proliferation of peroxisomes. We propose a model in which these two transcription factors heterodimerize and mediate this activation process. The mutants that we have isolated, and further identification of the corresponding defective genes, provide us with an opportunity to characterize the mechanisms involved in the coordinate regulation of peroxisomal beta-oxidation enzymes. PMID:8972187

Karpichev, I V; Luo, Y; Marians, R C; Small, G M



Preparative enantioseparation of ?-blocker drugs by counter-current chromatography using dialkyl L-tartrate as chiral selector based on borate coordination complex.  


Counter-current chromatography (CCC) was applied for preparative enantioseparation of three ?-blocker drugs, including propranolol, pindolol and alprenolol. The two-phase solvent system was composed of chloroform-0.05 mol L(-1) acetate buffer containing 0.10 mol L(-1) boric acid (1:1, v/v), in which 0.10 mol L(-1) di-n-hexyl L-tartrate was added in the organic phase as chiral selector. Influence factors in the enantioseparation of propranolol were investigated. The chromatographic retention mechanism based on borate coordination complex was proposed. 116 mg of racemic propranolol was completely enantioseparated using conventional high speed CCC in a single run, yielding 48 mg of (+)-propranolol with HPLC purity of 98.9% and 47 mg of (-)-propranolol with HPLC purity of 96.3%. Recovery for propranolol enantiomers from CCC fractions was in the range of 75-82%. pH-zone-refining CCC was also successfully applied in enantioseparation of propanolol and it was found that 356 mg of racemic propranolol could be completely enantioseparated. 145 mg of (+)-enantiomer with HPLC purity of 95.6% and 148 mg of (-)-enantiomer with HPLC purity of 98.2% were recovered from pH-zone-refining mode. Separation mechanism about chiral separation by pH-zone-refining CCC was discussed. PMID:23021635

Tong, Shengqiang; Zheng, Ye; Yan, Jizhong; Guan, Yi-Xin; Wu, Chunyan; Lei, Wenyu



Polyamine macrocycles incorporating a phenolic function: their synthesis, basicity, and coordination behavior toward metal cations. Crystal structure of a binuclear nickel complex.  


The synthesis and characterization of two new polyazamacrocycles, 1,4,7,10-tetraaza[12](2,6)phenolphane (L1) and 1,4,7,10,13-pentaaza[15](2,6)phenolphane (L2), are reported. Both ligands incorporate the 2,6-phenolic unit within the cyclic framework. The basicity behavior and the ligational properties of L1 and L2 toward Ni(II), Zn(II), and Cu(II) were determined by means of potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, I = 0.15 mol dm-3). UV spectra were used to understand the role of the phenolic function in the stabilization of the cations. L1 and L2 behave as pentaprotic bases under the experimental conditions used. The UV spectra showed that the deprotonation of the phenolic function occurs at low pH values for both ligands, giving rise to the simultaneous presence of positive and (one) negative charges on the macrocycle. While L1 forms only mononuclear complexes, L2 can also form binuclear species with all the metal ions investigated. In the mononuclear species of both ligands, one nitrogen atom close to the phenol remains unbound. The UV spectra revealed that the phenol, bridging the two metal ions in phenolate form, plays an important role in the stabilization of the binuclear complexes of L2. The coordination sphere of the two metals is completed by adding a secondary ligand such as water molecules or OH-, in any case preferring substrates able to bridge the two close metal ions. These results are confirmed by the crystal structure of [Ni2(C16H28ON5)(H2O)2Cl2]Cl.H2O.CH3OH (space group P21/a, a = 14.821(5) A, b = 10.270(4) A, c = 17.663(6) A, beta = 108.87(3) degrees, V = 2544(2) A3, Z = 4, R1 = 0.0973, wR2 = 0.2136). This structure displays a Ni(II) binuclear complex of L2 in which the phenolic oxygen and a chlorine ion bridge the two close Ni(II) ions. PMID:12526528

Dapporto, P; Formica, M; Fusi, V; Micheloni, M; Paoli, P; Pontellini, R; Romani, P; Rossi, P



The first case of an actinide polyrotaxane incorporating cucurbituril: a unique 'dragon-like' twist induced by a specific coordination pattern of uranium.  


In situ assembly of a cucurbituril-based pseudorotaxane and a uranyl nitrate precursor under hydrothermal conditions affords the first actinide polyrotaxane with a unique 'dragon-like' twist, which is induced by the specific coordination pattern of uranium and stabilized by hydrogen bonding between the ?(1)-mode carboxylate group and adjacent methylene moieties of CB[6]. PMID:24572934

Mei, Lei; Wu, Qun-yan; Liu, Cai-ming; Zhao, Yu-liang; Chai, Zhi-fang; Shi, Wei-qun



Tritium gettering from air with hydrogen uranyl phosphate  

SciTech Connect

The managers of all tritium facilities now worry about their emissions into the atmosphere. The only method for cleaning tritium out of air is to catalyze the formation of tritiated water which is adsorbed, along with the overwhelming bulk of naturally occurring water vapor, on a zeolite molecular sieve. This method generally costs several million dollars for a small system, because of the necessary steel ducting, compressors and holding tanks. We have long had the dream of finding another getter that might be cheaper to use and would, hopefully, not make tritiated water (HTO). In a previous paper, we discovered that hydrogen uranyl phosphate (HUP, with the formula HUO/sub 2/PO/sub 4/ x 4H/sub 2/O) getters 1 ppM of tritium gas out of moist air. This makes HUP the first known ''direct'' tritium getter to work in air. However, the tritium enters a hydroxyl network within the HUP, so that it is effectively still in ''water'' form within the HUP. Worse yet, we found up to 10% tritiated water formed during the previous gettering experiments. HUP is unusual in possessing the exceptionally low vapor pressure of 0.6 torr water vapor at 298/sup 0/K. This allows HUP to be used in fairly dry environments. 14 refs., 3 figs., 2 tabs.

Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, T.T.



Determination of trace uranyl ion by thermoresponsive porphyrin-terminated polymeric sensor.  


Uranyl ion exists at trace levels in the environment and can cause severe adverse effects to human health. Therefore, it is desirable to develop analytical methods that can determine the trace uranyl ion in aqueous medium. We report here a new method using a thermo-responsive polymeric fluorescent sensor. Specifically, 5,10,15,20-tetrakis(4-carboxyphenyl)-porphyrin terminated poly(N-isopropylacrylamide) (TCPP-PNIPAM) was synthesized by controlled free radical polymerization for the detection of uranyl ion. The maximum fluorescence intensity at ~658nm of TCPP-PNIPAM increases with molecular weights and is also closely related to the temperature. The polymeric sensor is sensitive to pH (1.0~5.0) with a fast responsive time (~3min). Under optimized experimental conditions, the sensor exhibits a stable response for uranyl ion with high selectivity over a concentration range from 1.0×10(-3) to 1.0×10(-7)mol/L. For the trace uranyl ion (such as 1.0×10(-8) or 10(-9)mol/L), the determination could be successfully achieved after concentrating 100 times by centrifugation above 32°C. The properties enable the polymeric sensor to have great potential for environmental application. PMID:25281093

Shu, Xiaowen; Wang, Yingjie; Zhang, Shuang; Huang, Li; Wang, Shuao; Hua, Daoben



Stepwise radial complexation from the outer layer to the inner layer of a dendritic ligand: a phenylazomethine dendrimer with an inverted coordination sequence.  


A para-substituted phenylazomethine dendrimer () coordinates to Lewis acids in a stepwise radial fashion from the inner layer to the outer layer. The inversion of this coordination sequence was achieved for the first time by just changing the substitution position of the phenylazomethine group from the para position to the meta position (). PMID:25177753

Albrecht, Ken; Sakane, Noriko; Yamamoto, Kimihisa



Preliminary experiments on the reduction of the uranyl ion to uraninite by carbonaceous substances  

USGS Publications Warehouse

An aqueous solution of uranyl sulfate containing a suspension of subbituminous coal has been heated at 210 C for three days. Examination of the coal at the end of the experiment showed it to contain 31.8 percent uranium recognizable as uraninite by a sharp, strong X-ray diffraction pattern. A similar experiment with degraded spruce wood also led to the formation of uraninite but in lesser quantity and with broader lines in the X-ray diffraction pattern. The ability of coal or wood to reduce the uranyl ion is a critical factor in the correlation of studies of uraniferous coals containing the uranyl ion with studies of uraninite-bearing coalified wood from the Colorado Plateau. Although these results are based an preliminary experiments, they are extremely important geochemically and warrant the development of the series of controlled studies that are proposed.

Breger, Irving A.; Moore, Richard T.



Iron (II) sorption to mineral surfaces in uranyl and silicate rich media  

SciTech Connect

Abstract - The unique composition of the Yucca Mountain repository site, which contains large concentrations of silicate in an oxidative environment, has required extensive research into compound formation involving uranium and iron(II) under such conditions. The possibility of uranium leakage from within the containment vessels into the near-field ground water, as well as iron leaching from the vessel itself, necessitates study of the individual contributions of these elements for compound formation. By mimicking the known silicate concentration found in surrounding ground water and varying concentrations of both uranyl and iron(II), subsequent precipitation of uranyl silicate phases has shown evidence of iron(II) sorption to the available sites on the mineral surface. The mineralization seems to be driven by the formation of uranyl silicate, in contrast to iron(III)-control of precipitation in the oxidated system. We present characterization of this system using ICP-AES/MS, EDAX, XRD, and single-crystal X-ray diffraction.

Tyler A. Sullens; Cynthia-May S. Gong; Kenneth R. Czerwinski



Uranyl precipitation by biomass from an enhanced biological phosphorus removal reactor.  


Heavy metal and radionuclide contamination presents a significant environmental problem worldwide. Precipitation of heavy metals on membranes of cells that secrete phosphate has been shown to be an effective method of reducing the volume of these wastes, thus reducing the cost of disposal. A consortium of organisms, some of which secrete large quantities of phosphate, was enriched in a laboratory-scale sequencing batch reactor performing Enhanced Biological Phosphorus Removal, a treatment process widely used for removing phosphorus. Organisms collected after the aerobic phase of this process secreted phosphate and precipitated greater than 98% of the uranyl from a 1.5 mM uranyl nitrate solution when supplemented with an organic acid as a carbon source under anaerobic conditions. Transmission electron microscopy, energy dispersive x-ray spectroscopy, and fluorescence spectroscopy were used to identify the precipitate as membrane-associated uranyl phosphate, UO2HPO4. PMID:12051646