Search results for "extended X-ray absorption fine structure"

The complementary structural studies of the double metal cyanide type catalysts for the ring opening polymerization of the oxiranes

2016

Przeprowadzono badania strukturalne katalizatorów dimetalocyjankowych (DMC) z dwoma rodzajami ligandów organicznych. Zaproponowano wyjaśnienie etapów przebiegu krzywych otrzymanych metodą analizy termograwimetrycznej i różnicowej kalorymetrii skaningowej (TG/DSC) badanych katalizatorów. Wykazano obecność kilku stopni związania ligandów w kompleksach DMC. Na podstawie wyników badań z wykorzystaniem absorpcji rentgenowskiej (XAS) stwierdzono, że centrum aktywne katalizatora stanowi atom cynku. W bezpośrednim sąsiedztwie atomów Zn wykryto obecność atomów Cl, natomiast w najbliższych sferach koordynacyjnych atomu Zn nie wykryto atomów tlenu.

The active center of superoxide dismutase from Propionibacterium shermanii

1996

A self-consistent description of the EPR spectra and of the Mossbauer spectra of the natural superoxide dismutase from Propionibacterium shermanii with ferric iron as an active centre is presented. The spectra were measured at pH 6.5, 7.8 and 9.4. The theoretical approach is based on the use of the complete crystal field Hamiltonian for the high-spin ferric complexes with due regard for the terms of the fourth power of the electronic spin. It is shown that a SOD molecule can exist in two conformations. The low-pH conformation has predominantly trigonal symmetry, while the high-pH conformation has the symmetry close to the «extreme rhombic». This interpretation is in full agreement with EXAF…

Uranyl sorption onto birnessite: A surface complexation modeling and EXAFS study

2014

This work investigates the mechanism of the uranyl interaction with birnessite, one of the most common layer-type MnO2 mineral at the Earth's surface, by coupling macroscopic (surface complexation experiments) and microscopic (EXAFS measurements) approaches. The sorption of uranyl on synthetic hexagonal birnessite, the low-pH birnessite form, was studied under various conditions of pH (3–6), electrolyte backgrounds (0.1 M NaClO4, NaNO3 and Na2CO3), and solid/liquid ratios (from 0.27 to 4.5 g/L). Sorption isotherms exhibit a complex form indicative of at least two types of sorption sites. EXAFS data reveal the presence of two equatorial O shells at ca. 2.32 Å and 2.46 Å for all the samples, …

Low-Molecular-Weight Organic Acid Complexation Affects Antimony(III) Adsorption by Granular Ferric Hydroxide.

2019

Antimony(III) mobility in natural aquatic environments is generally enhanced by dissolved organic matter. Tartaric acid is often used to form complexes with and stabilize dissolved Sb(III) in adsorption studies. However, competition between such low-molecular-weight organic acid complexation and adsorption of Sb(III) has received little attention, which prompted us to measure Sb(III) adsorption by iron oxyhydroxide adsorbents commonly used in water treatment plants. Sb K-edge X-ray absorption fine structure (EXAFS) spectra gave Sb–O and Sb–Fe distances and coordinations compatible with a bidentate binuclear inner-sphere complex with trigonal Sb(O,OH)3 polyhedra sharing corners with Fe(O,OH)…

Plutonium(III) complexation by humic substances studied by X-ray absorption fine structure spectroscopy

2006

Abstract We determined structural parameters for the near-neighbor surrounding of plutonium(III) in complexes with humic and fulvic acids at pH 1 and for the purpose of comparison also for the plutonium(III) aquo ion by means of X-ray absorption fine structure (XAFS) spectroscopy. It could be shown that in the complexes with humic substances as well as in the plutonium(III) aquo ion sample the trivalent oxidation state of plutonium was stable within the time of the experiment. In the humate and fulvate complexes, the plutonium(III) is surrounded by about eight oxygen atoms with an average Pu–O distance of 2.48 ± 0.02 A. The structural parameters determined for plutonium(III)–humate and –ful…

Structural characterization of frozen n-heptane solutions of metal-containing reverse micelles

2007

The microstructure of temperature-quenched solutions of reverse micelles formed by sodium, cobalt, ytterbium, and cobalt/ytterbium bis(2-ethylhexyl)sulfosuccinate in n-heptane has been investigated by SAXS and EXAFS. Some changes in the X-ray absorption spectra with respect to the same systems at room temperature have been observed. The analysis of the SAXS spectra leads to the hypothesis that at 77 K the closed spherical structure of reverse micelles is retained and that during the temperature quench they undergo a clustering process involving the transition from a quite random dispersion to the formation of more or less large clusters of strongly packed reverse micelles. This behavior is …

Local Environment of Co2+ Ions in β″-Alumina Crystals

1992

Structural characterization of U(VI) surface complexes on kaolinite in the presence of humic acid using EXAFS spectroscopy.

2007

To determine the influence of humic acid (HA), pH, and presence of atmospheric CO2 on the sorption of U(VI) onto kaolinite, the structure of the surface complexes was studied by U L III-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The best fits to the experimental EXAFS data were obtained by including two uranium coordination shells with two axial (O ax) and five equatorial (O eq) oxygen atoms at 1.77+/-0.02 and 2.34+/-0.02 A, respectively, and two coordination shells with one Al/Si atom each at 3.1 and 3.3 A. As in the case of the binary system U(VI)-kaolinite, uranium forms inner-sphere surface complexes by edge sharing with aluminum octahedra and/or silicon tetrahe…

Temperature and pH Dependence of Gd-DOTA and Gd-DTPA Complexes Dissociation Studied by EXAFS

1997

The Gd L3-edge of Gd(DTPA) 2- and Gd(DOTA) - complexes, in crystalline state and aqueous solutions presenting various pH (0.15-8) at different temperatures (25-90 °C), are investigated by XAFS experiments. For the Gd(DTPA) 2- . complexes we observe a strong pH (0.15-1.5) dependence of XAFS signals. On the other hand, the XAFS signals of Gd(DOTA) - complexes exhibit a light pH (1-1.5) dependence and for pH<1 we observe a ligand decomposition. Conceming both complexes, we note just a light temperature dependence. To obtain information about the short and medium range order (up to 5 A), multiple scattering calculation is performed. For the first coordination shell, we apply multi-shell fitting…

Complexation of Uranium by Cells and S-Layer Sheets of Bacillus sphaericus JG-A12

2005

ABSTRACT Bacillus sphaericus JG-A12 is a natural isolate recovered from a uranium mining waste pile near the town of Johanngeorgenstadt in Saxony, Germany. The cells of this strain are enveloped by a highly ordered crystalline proteinaceous surface layer (S-layer) possessing an ability to bind uranium and other heavy metals. Purified and recrystallized S-layer proteins were shown to be phosphorylated by phosphoprotein-specific staining, inductive coupled plasma mass spectrometry analysis, and a colorimetric method. We used extended X-ray absorption fine-structure (EXAFS) spectroscopy to determine the structural parameters of the uranium complexes formed by purified and recrystallized S-laye…