scholarly journals Vanadium K-edge X-ray-absorption spectroscopy of the functioning and thionine-oxidized forms of the VFe-protein of the vanadium nitrogenase from Azotobacter chroococcum

1989 ◽  
Vol 258 (3) ◽  
pp. 733-737 ◽  
Author(s):  
J M Arber ◽  
B R Dobson ◽  
R R Eady ◽  
S S Hasnain ◽  
C D Garner ◽  
...  
Keyword(s):  
Absorption Spectra ◽  
Absorption Spectroscopy ◽  
Azotobacter Chroococcum ◽  
Vanadium Atom ◽  
Oxidation States ◽  
Edge Structure ◽  
X Ray ◽  
Vanadium Nitrogenase ◽  
Enzyme Turnover ◽  
X Ray Absorption

Vanadium K-edge X-ray-absorption spectra were collected for samples of thionine-oxidized, super-reduced (during enzyme turnover) and dithionite-reduced VFe-protein of the vanadium nitrogenase of Azotobacter chroococcum (Acl*). Both the e.x.a.f.s and the x.a.n.e.s. (X-ray-absorption near-edge structure) are consistent with the vanadium being present as part of a VFeS cluster; the environment of the vanadium is not changed significantly in different oxidation states of the protein. The vanadium atom is bound to three oxygen (or nitrogen), three sulphur and three iron atoms at 0.215(3), 0.231(3) and 0.275(3) nm respectively.

scholarly journals A compact furnace for in situ X-ray absorption spectroscopy: design, fabrication and study of cationic oxidation states in Pr6O11 and NiO

2021 ◽  
Vol 28 (2) ◽  
pp. 455-460
Author(s):  
Suchinda Sattayaporn ◽  
Somboonsup Rodporn ◽  
Pinit Kidkhunthod ◽  
Narong Chanlek ◽  
Chutarat Yonchai ◽  
...  
Keyword(s):  
Oxidation State ◽  
Absorption Spectroscopy ◽  
Heating Temperature ◽  
Reduction Process ◽  
Oxidation States ◽  
Quartz Tube ◽  
Edge Structure ◽  
X Ray ◽  
X Ray Absorption

A well designed compact furnace has been designed for in situ X-ray absorption spectroscopy (XAS). It enables various heat ramps from 300 K to 1473 K. The furnace consists of heaters, a quartz tube, a circulated refrigerator and a power controller. It can generate ohmic heating via an induction process with tantalum filaments. The maximum heating rate exceeds 20 K min−1. A quartz tube with gas feedthroughs allows the mixing of gases and adjustment of the flow rate. The use of this compact furnace allows in situ XAS investigations to be carried out in transmission or fluorescence modes under controlled temperature and atmosphere. Moreover, the furnace is compact, light and well compatible to XAS. The furnace was used to study cationic oxidation states in Pr6O11 and NiO compounds under elevated temperature and reduced atmosphere using the in situ X-ray absorption near-edge structure (XANES) technique at beamline 5.2 SUT-NANOTEC-SLRI of the Synchrotron Light Research Institute, Thailand. At room temperature, Pr6O11 contains a mixture of Pr3+ and Pr4+ cations, resulting in an average oxidation state of +3.67. In situ XANES spectra of Pr (L 3-edge) show that the oxidation state of Pr4+ cations was totally reduced to +3.00 at 1273 K under H2 atmosphere. Considering NiO, Ni2+ species were present under ambient conditions. At 573 K, the reduction process of Ni2+ occurred. The Ni0/Ni2+ ratio increased linearly with respect to the heating temperature. Finally, the reduction process of Ni2+ was completely finished at 770 K.

Manganese speciation in soils using X-ray absorption spectroscopy

2020 ◽  
Author(s):  
Teresa Zahoransky ◽  
Christian Mikutta
Keyword(s):  
Absorption Spectroscopy ◽  
Chemical Reactivity ◽  
Mixed Valence ◽  
Oxidation States ◽  
Plant Residues ◽  
Edge Structure ◽  
Coordination Environment ◽  
X Ray ◽  
Local Coordination ◽  
X Ray Absorption

<p>Being one of Earth´s most redox-active elements, manganese participates in a great variety of environmental processes and is recognized as a key player controlling carbon turnover and oxidative transformation of organic and inorganic pollutants in soils. Moreover, Mn(III), Mn(IV) or mixed-valence Mn(III/IV) oxides and (oxy)hydroxides are highly effective sorbents for metal pollutants and nutrients in soils. Chemical reactivity, mobility, and bioavailability of Mn depend crucially on its speciation (chemical form). Yet, speciation studies on soil Mn are scarce. Therefore, we employed Mn K-edge (6,539 eV) X-ray absorption spectroscopy (XAS) to determine the oxidation states and local coordination environment (<5 Å) of Mn in oxic bulk soils (Cambisols, Luvisols, Stagnosol) from various field sites in Germany. Our XAS analyses cover 23 soil L, O, A, B, and C horizons exhibiting total Mn concentrations of between 200 and 2,300 mg/kg. For comparison, we also analyze a suite of 31 Mn reference compounds, including Mn carbonate, phosphate, oxides and (oxy)hydroxides, silicates, organic Mn compounds as well as clay and hydroxide minerals with adsorbed Mn(II). X-ray absorption near-edge structure (XANES) spectra are evaluated for the oxidation states of soil Mn using linear combination fit (LCF) analysis. In addition, the average local coordination environment of Mn in the soil samples is assessed by shell-fitting of extended X-ray absorption fine structure (EXAFS) spectra. Based on our XAS results, we will test the following hypotheses: (1) Soil L/O horizons comprise predominantly organically complexed Mn(II) and Mn(III), dominated by the former Mn species; (2) soil A horizons are dominated by Mn(III/IV) in Mn(III/IV)-oxide structures owing to high microbial activity, release of Mn(II) from primary silicates and/or plant residues, and its subsequent (a)biotic oxidation and precipitation as Mn(III/IV) oxides; (3) soil B horizons of different genesis differ in their bulk Mn speciation; Bt horizons of Luvisols are dominated by Mn(II) associated with phyllosilicates, whereas the Stagnosol Bg horizon is dominated by layer-type Mn(III/IV) oxides. In summary, our study will provide first comprehensive data on bulk Mn speciation in three major European soil types. This knowledge is a prerequisite for a better understanding of the biogeochemical Mn cycle in soils.</p>

Automatic oxidation threshold recognition of XAFS data using supervised machine learning

2019 ◽  
Vol 4 (5) ◽  
pp. 1014-1018 ◽  
Author(s):  
Itsuki Miyazato ◽  
Lauren Takahashi ◽  
Keisuke Takahashi
Keyword(s):  
Machine Learning ◽  
Absorption Spectroscopy ◽  
Supervised Machine Learning ◽  
Oxidation States ◽  
Edge Structure ◽  
X Ray ◽  
X Ray Absorption

Oxidation states of materials are characterized by the X-ray absorption near edge structure (XANES) region in X-ray absorption spectroscopy (XAS).

X-ray absorption spectroscopy and density functional analysis of the Fe3+ distribution profile on Al sites in a chrysoberyl crystal, BeAl2O4:Fe3+

2016 ◽  
Vol 49 (2) ◽  
pp. 385-388 ◽  
Author(s):  
Kanokwan Kanchiang ◽  
Atipong Bootchanont ◽  
Janyaporn Witthayarat ◽  
Sittichain Pramchu ◽  
Panjawan Thanasuthipitak ◽  
...  
Keyword(s):  
Optical Properties ◽  
Absorption Spectroscopy ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Distribution Profile ◽  
Laser Applications ◽  
Edge Structure ◽  
X Ray ◽  
Site Distribution ◽  
X Ray Absorption

Chrysoberyl is one of the most interesting minerals for laser applications, widely used for medical purposes, as it exhibits higher laser performance than other materials. Although its utilization has been vastly expanded, the location of transition metal impurities, especially the iron that is responsible for chrysoberyl's special optical properties, is not completely understood. The full understanding and control of these optical properties necessitates knowledge of the precise location of the transition metals inside the structure. Therefore, synchrotron X-ray absorption spectroscopy (XAS), a local structural probe sensitive to the different local geometries, was employed in this work to determine the site occupation of the Fe3+ cation in the chrysoberyl structure. An Fe K-edge X-ray absorption near-edge structure (XANES) simulation was performed in combination with density functional theory calculations of Fe3+ cations located at different locations in the chrysoberyl structure. The simulated spectra were then qualitatively compared with the measured XANES features. The comparison indicates that Fe3+ is substituted on the two different Al2+ octahedral sites with the proportion 60% on the inversion site and 40% on the reflection site. The accurate site distribution of Fe3+ obtained from this work provides useful information on the doping process for improving the efficiency of chrysoberyl as a solid-state laser material.

scholarly journals Probing the variability in oxidation states of magnetite nanoparticles by single-particle spectroscopy

2018 ◽  
Vol 6 (4) ◽  
pp. 875-882 ◽  
Author(s):  
A. Fraile Rodríguez ◽  
C. Moya ◽  
M. Escoda-Torroella ◽  
A. Romero ◽  
A. Labarta ◽  
...  
Keyword(s):  
Oxidation State ◽  
Absorption Spectroscopy ◽  
Magnetite Nanoparticles ◽  
Single Particle ◽  
Cation Distribution ◽  
Oxidation States ◽  
Magnetic Response ◽  
X Ray ◽  
Single Particle Spectroscopy ◽  
X Ray Absorption

Single-particle X-ray absorption spectroscopy reveals that the oxidation state and cation distribution of individual magnetite nanoparticles may be largely heterogeneous even when the macroscopic structural and magnetic response of the ensembles is uniform.

Assignment of the oxidation states of Zr and Co in a highly reactive heterobimetallic Zr/Co complex using X-ray absorption spectroscopy (XANES)

2014 ◽  
Vol 43 (37) ◽  
pp. 13852 ◽  
Author(s):  
Jeremy P. Krogman ◽  
James R. Gallagher ◽  
Guanghui Zhang ◽  
Adam S. Hock ◽  
Jeffrey T. Miller ◽  
...  
Keyword(s):  
Absorption Spectroscopy ◽  
Oxidation States ◽  
X Ray ◽  
X Ray Absorption

Oxygen Reduction Effect on T’-Pr2-xCexCuO4 Nanopowders in the Underdoped Regime Studied by X-Ray Absorption near Edge Structure

2018 ◽  
Vol 936 ◽  
pp. 93-97 ◽  
Author(s):  
Irfanita Resky ◽  
Putu Eka Dharma Putra ◽  
Triono Bambang ◽  
Saiyasombat Chatree ◽  
Kamonsuangkasem Krongthong ◽  
...  
Keyword(s):  
Oxidation State ◽  
Oxidation States ◽  
Edge Structure ◽  
X Ray ◽  
Reduction Annealing ◽  
Gas Atmosphere ◽  
Reduction Effect ◽  
Ar Gas ◽  
X Ray Absorption ◽  
Cu Ions

This research is aimed to examine oxidation state of Copper (Cu) in both as-synthesized and reduced T’-Pr2-xCexCuO4 (T’-PCCO) with x = 0, 0.10, and 0.15 using Cu K-edge x-ray absorption near edge structure (XANES). The T‘-PCCO nanopowders were successfully synthesized by the chemically dissolved method with HNO3 as a dissolving agent continued by calcination at 1000°C for 15 h. The reduced T’-PCCO nanopowders were obtained by reduction annealing process at 700°C for 5 h under Ar gas atmosphere. The analyses of XANES spectra show that oxidation states of the Cu ions in all of the T'-PCCO nanopowders have values between +1 and +2. This indicates the existence of electron doping in the CuO2 planes, even in the undoped T’-structure. It is found that the oxidation states of the Cu ions change after reduction annealing depending on the existence of apical oxygen in the T'-structure. Based on the XANES analyses, it is revealed that the change of oxidation state is influenced by the presence of both electron and hole carriers in the two-carrier model of T’-structure.

scholarly journals Solution X-Ray Absorption Spectroscopy (XAS) for Analysis of Catalytically Active Species in Reactions with Ethylene by Homogeneous (Imido)vanadium(V) Complexes—Al Cocatalyst Systems

Catalysts ◽  
2019 ◽  
Vol 9 (12) ◽  
pp. 1016 ◽  
Author(s):  
Kotohiro Nomura
Keyword(s):  
Active Species ◽  
Oxidation States ◽  
Donor Ligands ◽  
Ethylene Dimerization ◽  
Edge Structure ◽  
Donor Ligand ◽  
X Ray ◽  
Catalytically Active ◽  
Type V ◽  
X Ray Absorption

Solution V K-edge XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) analysis of vanadium(V) complexes containing both imido ligands and anionic ancillary donor ligands (L) of type, V(NR)(L)X2 (R = Ar, Ad (1-adamantyl); Ar = 2,6-Me2C6H3; X = Cl, Me, L = 2-(ArNCH2)C5H4N, OAr, WCA-NHC, and 2-(2’-benzimidazolyl)pyridine; WCA-NHC = anionic NHCs containing weak coordinating B(C6F5)3), which catalyze ethylene dimerization and/or polymerization in the presence of Al cocatalysts, has been explored. Different catalytically actives species with different oxidation states were formed depending upon the Al cocatalyst (MAO, Me2AlCl, AliBu3, etc.) and the anionic ancillary donor ligand employed. The method is useful for obtainment of the direct information of the active species (oxidation state, basic framework around the centered metal) in solution, and for better understanding in catalysis mechanism and organometallic as well as coordination chemistry.

X-ray absorption spectroscopy studies for the determination of adsorption binding modes of selenium oxoanions onto iron and manganese based nanomaterials

2012 ◽  
Vol 1480 ◽  
Author(s):  
Christina M. Gonzalez ◽  
Jason G. Parsons ◽  
Jeffrey Hernandez ◽  
Jorge L. Gardea-Torresdey
Keyword(s):  
Absorption Spectroscopy ◽  
Binding Modes ◽  
Edge Structure ◽  
X Ray ◽  
Microwave Assisted ◽  
Spectroscopy Studies ◽  
X Ray Absorption ◽  
Binding Mechanisms ◽  
Iron And Manganese

ABSTRACTIncreasing concentrations of selenium oxoanions in the environment are placing many animals at risk for reproduction failure and deformities. The understanding of binding mechanisms of selenium oxoanions to iron and manganese based oxide minerals could lead to enhanced understanding of selenium mobility in the environment. In this study, the binding mechanisms of selenium oxoanions, selenite and selenate, to non microwave-assisted and microwave-assisted synthetic Fe3O4, Mn3O4, and MnFe2O4 nanomaterials were investigated through the use of X-ray absorption spectroscopy. The X-ray absorption near-edge structure (XANES) spectroscopy studies revealed the oxidation state of selenite and selenate remains the same after binding occurs to all nanomaterials in pH 2, 4, or 6 environments. The binding modes of selenite and selenate were determined to be bidentate binuclear through use of Extended x-ray absorption fine structure (EXAFS) and were independent of nanomaterials, synthetic technique, and pH.

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