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141.
Song YF Berry JF Bill E Bothe E Weyhermüller T Wieghardt K 《Inorganic chemistry》2007,46(6):2208-2219
Three new pentadentate, pendent arm macrocycles containing the 1,4,7-triazacyclononane-1,4-diacetate motif have been synthesized, and their coordination chemistry with Fe(III) has been investigated. Eight new octahedral Fe(III) complexes containing chloro, azido, or mu-oxo ligands have been synthesized, five of which have been characterized by X-ray crystallography. Spectroscopic characterization of these octahedral Fe(III) complexes by UV-vis, IR, electrochemistry, EPR, magnetic susceptibility, and zero-field M?ssbauer measurements firmly establishes the high-spin state of the iron in all complexes. Electrochemistry studies of the azido-Fe(III) complexes show that they can be reversibly oxidized to the corresponding Fe(IV) species at -20 degrees C, and Fe(II), Fe(III), and Fe(IV) species show characteristic IR and UV-vis profiles. Photolysis of one of the azido complexes was studied as a function of temperature (room temperature vs 77 K) and wavelength (480, 419, and 330 nm). Photoreduction to a high-spin Fe(II) species occurs under all conditions, which is proposed to be the dominant photochemical pathway generally available to high-spin ferric azido complexes. 相似文献
142.
Davies DM Murray C Berry M Orr-Ewing AJ Booker-Milburn KI 《The Journal of organic chemistry》2007,72(4):1449-1457
An in-depth study of the intramolecular [5 + 2] photocycloaddition of maleimides using tunable UV lasers has demonstrated that the peak in quantum yield and rate both occur at wavelengths some 50 nm red shifted from the maxima observed in the UV spectra. A detailed explanation for these findings using time-dependent DFT calculations is presented, and the implications for a previously adopted mechanism are discussed. 相似文献
143.
Irreversible electrowetting on thin fluoropolymer films 总被引:1,自引:0,他引:1
Berry S Kedzierski J Abedian B 《Langmuir : the ACS journal of surfaces and colloids》2007,23(24):12429-12435
A study was conducted to investigate electrowetting reversibility associated with repeated voltage actuations for an aqueous droplet situated on a silicon dioxide insulator coated with an amorphous fluoropolymer film ranging in thickness from 20 to 80 nm. The experimental results indicate that irreversible trapped charge may occur at the aqueous-solid interface, giving rise to contact angle relaxation. The accumulation of trapped charge was found to be related to the applied electric field intensity and the breakdown strength of the fluoropolymer. On the basis of the data, an empirical model was developed to estimate the amount of trapped charge in the fluoropolymer as well as the voltage threshold for the onset of irreversible electrowetting. 相似文献
144.
Robert E. Berry Elaine M. Armstrong Roy L. Beddoes David Collison S. Nigar Ertok Madeleine Helliwell C. David Garner 《Angewandte Chemie (International ed. in English)》1999,38(6):795-797
Fly agaric accumulate vanadium in the form of amavadin, whose structure has been elucidated (see picture for the crystal structure). Amavadin contains one VIV center coordinated to two (S,S)-hidpa3− ligands (H3hidpa=2,2′-(hydroxyimino)dipropionic acid) through one η2-NO− group and two unidentate carboxylato groups from each ligand. The arrangement of the two η2-NO− groups leads to a chiral vanadium center, which has been characterized in both the Λ and Δ forms. The carboxylato groups of the amavadin anions bind cations, for example, Ca2+ ions, and/or become involved in hydrogen bonding. 相似文献
145.
Numerical approximation of the five-equation two-phase flow of Kapila et al. [A.K. Kapila, R. Menikoff, J.B. Bdzil, S.F. Son, D.S. Stewart, Two-phase modeling of deflagration-to-detonation transition in granular materials: reduced equations, Physics of Fluids 13(10) (2001) 3002–3024] is examined. This model has shown excellent capabilities for the numerical resolution of interfaces separating compressible fluids as well as wave propagation in compressible mixtures [A. Murrone, H. Guillard, A five equation reduced model for compressible two phase flow problems, Journal of Computational Physics 202(2) (2005) 664–698; R. Abgrall, V. Perrier, Asymptotic expansion of a multiscale numerical scheme for compressible multiphase flows, SIAM Journal of Multiscale and Modeling and Simulation (5) (2006) 84–115; F. Petitpas, E. Franquet, R. Saurel, O. Le Metayer, A relaxation-projection method for compressible flows. Part II. The artificial heat exchange for multiphase shocks, Journal of Computational Physics 225(2) (2007) 2214–2248]. However, its numerical approximation poses some serious difficulties. Among them, the non-monotonic behavior of the sound speed causes inaccuracies in wave’s transmission across interfaces. Moreover, volume fraction variation across acoustic waves results in difficulties for the Riemann problem resolution, and in particular for the derivation of approximate solvers. Volume fraction positivity in the presence of shocks or strong expansion waves is another issue resulting in lack of robustness. To circumvent these difficulties, the pressure equilibrium assumption is relaxed and a pressure non-equilibrium model is developed. It results in a single velocity, non-conservative hyperbolic model with two energy equations involving relaxation terms. It fulfills the equation of state and energy conservation on both sides of interfaces and guarantees correct transmission of shocks across them. This formulation considerably simplifies numerical resolution. Following a strategy developed previously for another flow model [R. Saurel, R. Abgrall, A multiphase Godunov method for multifluid and multiphase flows, Journal of Computational Physics 150 (1999) 425–467], the hyperbolic part is first solved without relaxation terms with a simple, fast and robust algorithm, valid for unstructured meshes. Second, stiff relaxation terms are solved with a Newton method that also guarantees positivity and robustness. The algorithm and model are compared to exact solutions of the Euler equations as well as solutions of the five-equation model under extreme flow conditions, for interface computation and cavitating flows involving dynamics appearance of interfaces. In order to deal with correct dynamic of shock waves propagating through multiphase mixtures, the artificial heat exchange method of Petitpas et al. [F. Petitpas, E. Franquet, R. Saurel, O. Le Metayer, A relaxation-projection method for compressible flows. Part II. The artificial heat exchange for multiphase shocks, Journal of Computational Physics 225(2) (2007) 2214–2248] is adapted to the present formulation. 相似文献
146.
The 2,2′-bipyrimidine (bpm) adducts of the β-diketonate complexes of Eu(III), Sm(III), or Yb(III) with 2,2′,6,6′-tetramethyl-2,4-heptanedione (tmhd) resulted in the formation of dinuclear species. The synthesis and X-ray structure of these three new dinuclear lanthanide complexes are found to be similar. Each lanthanide ion is eight coordinate, bound to six O-atoms from the β-diketonates and 2N atoms from the bridging bpm ligand. They exhibit Ln–Ln distances (Sm(III): 6.935 Å, Eu(III): 6.901 Å, Yb(III): 6.679 Å) and Ln–ligand distances that are consistent with the decrease in radii across the lanthanide series. Absorption spectra of the complexes are dominated by ligand absorptions. Both the solution and solid state emission spectra of the complexes resemble ordinary monomeric lanthanide species, indicating independent ions in the dinuclear species. Cyclic voltammetry of all the complexes appear almost identical with discernable ligand centered redox reactions. The complex with Eu(III) ions, having the lowest possible lanthanide redox potential, was not found to display a signal corresponding to metal reduction. 相似文献
147.
H. El Shinawi J.F. Marco F.J. Berry C. Greaves 《Journal of solid state chemistry》2009,182(8):2261-2268
The M4+-containing K2NiF4-type phases La0.8Sr1.2Co0.5Fe0.5O4 and La0.8Sr1.2Co0.5Mn0.5O4 have been synthesized by a sol–gel procedure and characterized by X-ray powder diffraction, thermal analysis, neutron powder diffraction and Mössbauer spectroscopy. Oxide ion vacancies are created in these materials via reduction of M4+ to M3+ and of Co3+ to Co2+. The vacancies are confined to the equatorial planes of the K2NiF4-type structure. A partial reduction of Mn3+ to Mn2+ also occurs to achieve the oxygen stoichiometry in La0.8Sr1.2Co0.5Mn0.5O3.6. La0.8Sr1.2Co0.5Fe0.5O3.65 contains Co2+ and Fe3+ ions which interact antiferromagnetically and result in noncollinear magnetic order consistent with the tetragonal symmetry. Competing ferromagnetic and antiferromagnetic interactions in La0.8Sr1.2Co0.5Fe0.5O4, La0.8Sr1.2Co0.5Mn0.5O4 and La0.8Sr1.2Co0.5Mn0.5O3.6 induce spin glass properties in these phases. 相似文献
148.
149.
Garner DK Vaughan MD Hwang HJ Savelieff MG Berry SM Honek JF Lu Y 《Journal of the American Chemical Society》2006,128(49):15608-15617
The conserved axial ligand methionine 121 from Pseudomonas aeruginosa azurin (Az) has been replaced by isostructural unnatural amino acid analogues, oxomethionine (OxM), difluoromethionine (DFM), trifluoromethionine (TFM), selenomethionine (SeM), and norleucine (Nle) using expressed protein ligation. The replacements resulted in < 6 nm shifts in the S(Cys)-Cu charge transfer (CT) band in the electronic absorption spectra and < 8 gauss changes in the copper hyperfine coupling constants (AII) in the X-band electron paramagnetic resonance spectra, suggesting that isostructural replacement of Met resulted in minimal structural perturbation of the copper center. The slight blue shifts of the CT band follow the trend of stronger electronegativity of the ligands. This trend is supported by 19F NMR studies of the fluorinated methionine analogues. However, the order of AII differs, suggesting additional factors influencing AII. In contrast to the small changes in the UV-vis and EPR spectra, a large variation of > 227 mV in reduction potential was observed for the series of variants reported here. Additionally, a linear correlation was established between the reduction potentials and hydrophobicity of the variants. Extension of this analysis to other type 1 copper-containing proteins reveals a linear correlation between change in hydrophobicity and change in reduction potential, independent of the protein scaffold, experimental conditions, measurement techniques, and steric modifications. This analysis has also revealed for the first time high and low potential states for type 1 centers, and the difference may be attributable to destabilization of the protein fold by disruption of hydrophobic or hydrogen bonding interactions that stabilize the type 1 center. 相似文献
150.
Acoustic imaging aims at localization and characterization of sound sources using microphone arrays. In this paper a new regularization method for acoustic imaging by inverse approach is proposed. The method first relies on the singular value decomposition of the plant matrix and on the projection of the measured data on the corresponding singular vectors. In place of regularization using classical methods such as truncated singular value decomposition and Tikhonov regularization, the proposed method involves the direct definition of the filter factors on the basis of a thresholding operation, defined from the estimated measurement noise. The thresholding operation is achieved using modified filter functions. The originality of the approach is to propose the definition of a filter factor which provides more damping to the singular components dominated by noise than that given by the Tikhonov filter. This has the advantage of potentially simplifying the selection of the best regularization amount in inverse problems. Theoretical results show that this method is comparatively more accurate than Tikhonov regularization and truncated singular value decomposition. 相似文献