| 1. |
- Bjelčić, Monika, et al.
(författare)
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Anaerobic fixed-target serial crystallography using sandwiched silicon nitride membranes
- 2023
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Ingår i: Acta Crystallographica Section D: Structural Biology. - 2059-7983. ; 79:Pt 11, s. 1018-1025
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Tidskriftsartikel (refereegranskat)abstract
- In recent years, the emergence of serial crystallography, initially pioneered at X-ray free-electron lasers (XFELs), has sparked a growing interest in collecting macromolecular crystallographic data at room temperature. Various fixed-target serial crystallography techniques have been developed, ranging from commercially available chips to in-house designs implemented at different synchrotron facilities. Nevertheless, there is currently no commercially available chip (known to the authors) specifically designed for the direct handling of oxygen-sensitive samples. This study presents a methodology employing silicon nitride chips arranged in a 'sandwich' configuration, enabling reliable room-temperature data collection from oxygen-sensitive samples. The method involves the utilization of a custom-made 3D-printed assembling tool and a MX sample holder. To validate the effectiveness of the proposed method, deoxyhemoglobin and methemoglobin samples were investigated using the BioMAX X-ray macromolecular crystallography beamline, the Balder X-ray absorption spectroscopy beamline and UV-Vis absorption spectroscopy.
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| 2. |
- Łyczko, Krzysztof, et al.
(författare)
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Striking stability of a mixed-valence thallium(III)-thallium(I) complex in some solvents
- 2023
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Ingår i: Journal of Molecular Liquids. - 0167-7322. ; 385
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Tidskriftsartikel (refereegranskat)abstract
- At the dissolution of solid anhydrous thallium(III) trifluoromethanesulfonate, Tl(CF3SO3)3, or thallium(III) trifluoroacetate, Tl(CF3COO)3, in dimethylsulfoxide (dmso) or N,N,N’,N’-tetramethylurea (tmu), intensely red-colored complexes are formed. This red thallium complex is stable for years in dmso, while it is reduced fairly rapidly to thallium(I) in tmu with a half-life time of an hour. At the dissolution of Tl(CF3SO3)3 in N,N-dimethylpropyleneurea (dmpu) an immediate reduction to thallium(I) takes place. A stable colorless aqueous thallium(III) solution is obtained at the dissolution in acidic water. Stable dmso solutions and solid dmso solvates of thallium(III) perchlorate, nitrate and trifluormethanesulfonate can be prepared by adding dmso to concentrated acidic aqueous thallium(III) solutions. These experimental observations conclude that the pure solids Tl(CF3SO3)3 and Tl(CF3COO)3 play an essential role in the formation of the red-colored thallium complexes. 205Tl NMR data show that the red thallium complex contains equal amounts of thallium(III) and thallium(I). The structure of the red thallium complex in dmso, as determined by EXAFS, has Tl–O bond distances of 2.216(3) and 2.80(2) Å, which are in very close agreement with the bond distances obtained in the pure dmso solvates of the thallium(III) and thallium(I) ions, respectively, and a Tl···Tl distance of 3.49(1) Å bridged by oxygen atoms. From the EXAFS data it is impossible to distinguish if dmso molecules and/or trifluoromethanesulfonate ions act as bridges. DFT calculations could eliminate some structures due to the irrelevant structural parameters or the energetics of the proposed reactions.
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| 3. |
- Vajda, Vivi, et al.
(författare)
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Changes in Fe-redox and Fe-species across the end-Permian ‘Dead Zone’ in the Sydney Basin, Australia (252.10 ± 0.06 Ma): Evidence from X-ray absorption spectroscopy
- 2023
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Ingår i: Evolving Earth. - : Elsevier. - 2950-1172. ; 1
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Tidskriftsartikel (refereegranskat)abstract
- The end-Permian mass extinction event is traceable across several non-marine basins in Australia. In the Sydney Basin, the lithological succession is characterized by a change from coal seams to mudstones and sandstones, recording a major environmental change following the disappearance of the Permian vegetation. A few millimeter-thick iron-rich ‘rusty’ layer occurs between the uppermost Permian coal seam and the mudstone, a layer that extends laterally across the basin and which has also been documented from coeval successions in Antarctica. This layer is overlain by the <1.5-m-thick Frazer Beach Member, whose basal 10-cm-thick microbreccia bed comprises 99% kaolinite and quartz, and is dated as 252.10 ± 0.06 Ma. The Frazer Beach Member corresponds to the so-called end-Permian ‘Dead Zone’ lacking fossil pollen and leaves. This distinctive member was deposited directly following the extinction of the Permian peat-forming forests.Here we identify, through X-ray absorption spectroscopy, a drastic redox shift across the extinction interval with increasing amount of reduced Fe-species followed by highly oxidized Fe-species, most resembling Fe(III) complexed with organic matter. Values subsequently normalise in younger samples through the ‘Dead Zone’, attaining only slightly higher redox-levels than before the event. The organically complexed Fe-species in the event bed is consistent with the standard Suwannee River fulvic acid, an acid Fe-complex with iron bound to organic matter, whereas the samples above and below the extinction layer yield spectra predominantly resembling magnetite (Fe3O4) mineral phase. We consider that the iron redox fluctuation marking the extinction interval is related to significant environmental changes with accumulation of organic matter following the mass extinction. The highly reduced iron in the extinction layer may relate to methane release from bacterial degradation, or emissions from clathrates. The presence of fulvic acid in the distinct iron-rich extinction layer indicates that an abrupt onset of the process of degradation of plant matter, lipids and calcium hydroxide (CaOH) took place, resulting in this ‘Death layer’. This was followed by millions of years of erosive conditions before new, complex vegetation could establish.
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