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The kinetics of hydrogen reduction of magnetite was investigated in different magnetic fields. The magnetic moment measurements in situ were used for the control of the reaction. A strong difference in the magnetic properties of the reaction results was obtained for applied strong and weak magnetic fields. The X-ray diffraction and Mössbauer spectra of the reduced samples confirmed their different composition. The mechanism of the magnetic field effect is discussed., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In the present paper, Mössbauer spectroscopic studies of dry biomass samples of the cyanobacterium Arthrospira platensis (formerly known as Spirulina platensis) were performed with regard to metabolic iron accumulation. 57 Fe Mössbauer parameters of iron in the biomass correspond to ferrihydrite. Spectra of iron hydroxides in A. platensis biomass differ from those of iron complexes with ethylenediaminetetraacetic acid injected to Zarrouk culture medium. The limit of saturation of A. platensis trichomes with iron in the form of ferrihydrite was found to be 5 μg/ml (0.09 μmol/ml) Fe in the culture medium. Conglomerates precipitated in the medium at higher iron concentrations also contain ferrihydrite but the ratio of the crystal lattice forms is different from that in the biomass., (Copyright © 2018 Elsevier GmbH. All rights reserved.)

In the emission ( 57 Co) variant of Mössbauer spectroscopy (EMS), the 57 Co radionuclide (with a half-life of 9months) is used that undergoes a nuclear decay 57 Co→ 57 Fe via electron capture followed by the emission of a γ-quantum, the energy of which is modified by the chemical state and the close coordination environment of the parent 57 Co atom. While EMS has been used largely in materials science and nuclear chemistry, its high sensitivity can also be of great advantage in revealing fine structural features and for speciation analysis of biological complexes, whenever the 57 Co 2+ cation can be used directly as the coordinating metal or as a substitute for native cobalt or other metal ions. As such EMS applications are yet rare, in order to reliably interpret emission spectra of sophisticated 57 Co 2+ -doped biosystems, model EMS studies of simple cobalt biocomplexes are necessary. In this work, EMS spectroscopic data are analysed and discussed for 57 Co 2+ complexes with a range of small biomolecules of different structures, including 4-n-hexylresorcinol, homoserine lactone and a few amino acids (spectra measured in rapidly frozen dilute aqueous solutions or in the dried state at T=80K). The EMS data obtained are discussed with regard to the available literature data related to the coordination modes of the biocomplexes under study., (Copyright © 2016. Published by Elsevier B.V.)

In biosciences and biotechnology, the expanding application of physicochemical approaches using modern instrumental techniques is an efficient strategy to obtain valuable and often unique information at the molecular level. In this work, we applied a combination of vibrational (Fourier transform infrared (FTIR), FT-Raman) spectroscopic techniques, useful in overall structural and compositional analysis of bacterial cells of the rhizobacterium Azospirillum brasilense, with 57Co emission Mössbauer spectroscopy (EMS) used for sensitive monitoring of metal binding and further transformations in live bacterial cells. The information obtained, together with ICP-MS analyses for metals taken up by the bacteria, is useful in analysing the impact of the environmental conditions (heavy metal stress) on the bacterial metabolism and some differences in the heavy metal stress-induced behaviour of non-endophytic (Sp7) and facultatively endophytic (Sp245) strains. The results show that, while both strains Sp7 and Sp245 take up noticeable and comparable amounts of heavy metals from the medium (0.12 and 0.13 mg Co, 0.48 and 0.44 mg Cu or 4.2 and 2.1 mg Zn per gram of dry biomass, respectively, at a metal concentration of 0.2 mM in the medium), their metabolic responses differ essentially. Whereas for strain Sp7 the FTIR measurements showed significant accumulation of polyhydroxyalkanoates as storage materials involved in stress endurance, strain Sp245 did not show any major changes in cellular composition. Nevertheless, EMS measurements showed rapid binding of cobalt(II) by live bacterial cells (chemically similar to metal binding by dead bacteria) and its further transformation in the live cells within an hour.

Interaction of cobalt(II) at micromolar concentrations with live cells of the plant-growth-promoting rhizobacterium Azospirillum brasilense (strain Sp245) and further transformations of the metal cation were monitored using 57Co emission Mössbauer spectroscopy (EMS). Cell suspensions of the bacterial culture (2.4 x 10(8) cells ml(-1)) were doped with radioactive 57CoCl2 (1 mCi; final concentration 2 x 10(-6) M 57Co2+), kept under physiological conditions for various periods of time (from 2 min up to 1 hour) and then rapidly frozen in liquid nitrogen. Analysis of emission Mössbauer spectra of the frozen aqueous suspensions of the bacterial cell samples shows that the primary absorption of cobalt(II) at micromolar concentrations by the bacterial cells is rapid and virtually complete, giving at least two major forms of cobalt(II) species bound to the cells. Within an hour, the metal is involved in further metabolic transformations reflected by changes occurring in the spectra. The Mössbauer parameters calculated from the EMS data by statistical treatment were different for suspensions of live and dead (thermally killed) bacterial cells that had been in contact with 57Co2+ for 1 h, as well as for the cell-free culture medium containing the same concentration of 57Co2+. Chemical after-effects of the nuclear transition (57Co --> 5 7Fe), which provide additional information on the chemical environment of metal ions, are also considered. The data presented demonstrate that EMS is a valuable tool for monitoring the chemical state of cobalt species in biological matter providing information at the atomic level in the course of its uptake and/or metabolic transformations.

CD spectroscopic study of the secondary structure of partly adenylylated glutamine synthetase (GS) of the bacterium Azospirillum brasilense showed both the native and cation-free (EDTA-treated) enzyme to be highly structured (58 and 49% as alpha-helices, 10 and 20% as beta-structure, respectively). Mg(2+), Mn(2+), or Co(2+), when added to the native GS, had little effect on its CD spectrum, whereas their effects on the cation-free GS were more pronounced. Emission ((57)Co) Mössbauer spectroscopic (EMS) study of (57)Co(2+)-doped cation-free GS in frozen solution and in the dried state gave similar spectra and Mössbauer parameters for the corresponding spectral components, reflecting the ability of the Co(2+)-enzyme complex to retain its properties upon drying. The EMS data show that (a) A. brasilense GS has 2 cation-binding sites per active center and (b) one site has a higher affinity to Co(2+) than the other, in line with the data on other bacterial GSs., (Copyright 2004 Wiley Periodicals, Inc. Biopolymers, 2004)

57Co emission Mössbauer spectroscopy (EMS) allows the chemical state of cobalt, as influenced by its coordination environment, to be monitored in biological samples at its physiological (trace) concentrations. To draw attention to EMS as a valuable tool for speciation of cobalt in biocomplexes, the process of cobalt(II) metabolism in cells of the plant growth-promoting rhizobacterium Azospirillum brasilense Sp245 was investigated using EMS of 57CoII-doped bacterial cells. EMS measurements also showed 57CoII-activated glutamine synthetase (GS, a key enzyme of nitrogen metabolism, isolated from this bacterium) to have two different cobalt(II) forms at its active sites, in agreement with data available on other bacterial GSs. Chemical after-effects following electron capture by the nucleus of the parent 57CoII during the 57Co-->57Fe transition, which contribute to the formation of a stabilised daughter 57FeIII component along with the nucleogenic 57FeII forms, are also briefly considered.

Recent attention has been given to a reexamination of results from the early Viking missions to Mars that suggested the presence of one or more strong oxidants in Martian soil. Since Fe is one of the main constituents of the Martian surface and Fe(VI) is known to be a highly reactive, strong oxidant, we have made XANES and EXAFS measurements of Fe(II), Fe(III), Fe(IV), and Fe(VI) in solid and solution forms. Results from these studies indicate a preedge XANES feature from Fe(VI) samples similar to that commonly seen from Cr(VI) samples. Results of first shell analysis indicate a linear relationship between the Fe-O bondlength and Fe valence state.