| 1. |
- Purgel, Mihály, et al.
(författare)
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Glyphosate complexation to aluminium(III). An equilibrium and structural study in solution using potentiometry, multinuclear NMR, ATR-FTIR, ESI-MS and DFT calculations
- 2009
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Ingår i: Journal of Inorganic Biochemistry. - : Elsevier. - 0162-0134 .- 1873-3344. ; 103:11, s. 1426-1438
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Tidskriftsartikel (refereegranskat)abstract
- The stoichiometries and stability constants of a series of Al(3+)-N-phosponomethyl glycine (PMG/H(3)L) complexes have been determined in acidic aqueous solution using a combination of precise potentiometric titration data, quantitative (27)Al and (31)P NMR spectra, ATR-FTIR spectrum and ESI-MS measurements (0.6M NaCl, 25 degrees C). Besides the mononuclear AlH(2)L(2+), Al(H(2)L)(HL), Al(HL)(2)(-) and Al(HL)L(2-), dimeric Al(2)(HL)L(+) and trinuclear Al(3)H(5)L(4)(2+) complexes have been postulated. (1)H and (31)P NMR data show that different isomers co-exist in solution and the isomerization reactions are slow on the (31)P NMR time scale. The geometries of monomeric and dimeric complexes likely double hydroxo bridged and double phosphonate bridged isomers have been optimized using DFT ab initio calculations starting from rational structural proposals. Energy calculations using the PCM solvation method also support the co-existence of isomers in solutions.
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| 2. |
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| 3. |
- Andersson, Ingegärd, et al.
(författare)
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Speciation in the aqueous H+/H2VO4–/H2O2/phosphate system
- 2005
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Ingår i: DALTON TRANSACTIONS. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; 22, s. 3658-66
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Tidskriftsartikel (refereegranskat)abstract
- The speciation in the aqueous H+/H2VO4- /phosphate (dihydrogen phosphate, P) and H+/H2VO4/H2O2/P systems has been determined in the physiological medium of 0.150 M Na(Cl) at 25 degrees C. A combination of multinuclear NMR integral and chemical shift (Bruker AMX500) as well as potentiometric data (glass electrode) have been collected and treated simultaneously by the computer program LAKE. The pK(a)-values for phosphoric acid have been determined by potentiometric and P-31 NMR chemical shift data, and have been found to be 1.85 +/- 0.02, 6.69 +/- 0.02 and 11.58 +/- 0.07. The errors given are 3 sigma. Altogether nine vanadate phosphate species have been found in the ternary H+/H2VO4-/P- system in the PH region 1-11, with the following compositions: VP, VP2 and V14P. Equilibrium is very slow in acidic solutions, requiring more than 3 months for the formation of V14P species. On the other hand, less than 15 min are needed for equilibration at neutral and alkaline pH. In the H+/H2VO4-/H2O2/P- system, four new species have been found in addition to all binary and ternary complexes. They are of VXP and VX2P compositions, where X denotes the peroxo ligand. V-51 and P-31 NMR chemical shifts, compositions and formation constants are given, and equilibrium conditions are illustrated in distribution diagrams as well as the fit of the model to the experimental data. Biological and medical relevance of the species is also discussed and physiological conditions are modelled.
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| 4. |
- Banyai, Istvan, et al.
(författare)
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Simple O-17 NMR method for studying electron self-exchange reaction between UO22+ and U4+ aqua ions in acidic solution
- 2016
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Ingår i: Magnetic Resonance in Chemistry. - : WILEY-BLACKWELL. - 0749-1581 .- 1097-458X. ; 54:6, s. 444-450
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Tidskriftsartikel (refereegranskat)abstract
- O-17 NMR spectroscopy is proven to be suitable and convenient method for studying the electron exchange by following the decrease of O-17-enrichment in (UOO2+)-O-17 ion in the presence of U4+ ion in aqueous solution. The reactions have been performed at room temperature using I=5MClO(4)(-) ionic medium in acidic solutions in order to determine the kinetics of electron exchange between the U4+ and UO22+ aqua ions. The rate equation is given as R = a[H+](-2) + R, where R is an acid independent parallel path. R depends on the concentration of the uranium species according to the following empirical rate equation: R = k(1)[UO2+](1/2)[U4+](1/2) + k(2)[UO2+](3/2)[U4+](1/2). The mechanism of the inverse H+ concentration-dependent path is interpreted as equilibrium formation of reactive UO2+ species from UO22+ and U4+ aqua ions and its electron exchange with UO22+. The determined rate constant of this reaction path is in agreement with the rate constant of UO22+-UO2+, one electron exchange step calculated by Marcus theory, match the range given experimentally of it in an early study. Our value lies in the same order of magnitude as the recently calculated ones by quantum chemical methods. The acid independent part is attributed to the formation of less hydrolyzed U(V) species, i.e. UO3+, which loses enrichment mainly by electron exchange with UO22+ ions. One can also conclude that O-17 NMR spectroscopy, or in general NMR spectroscopy with careful kinetic analysis, is a powerful tool for studying isotope exchange reactions without the use of sophisticated separation processes. Copyright (C) 2015 John Wiley amp; Sons, Ltd.
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| 5. |
- Hazay, Máté, et al.
(författare)
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Engineering optimization of decompressive craniectomy based on finite element simulations
- 2020
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Ingår i: Acta of bioengineering and biomechanics. - : Wroclaw University of Technology. - 1509-409X .- 1509-409X. ; 22:4, s. 109-122
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Tidskriftsartikel (refereegranskat)abstract
- Purpose: The optimal execution of decompressive craniectomy in terms of the size and location of the skull opening is not straightforward. Our main goals are twofold: (1) constructing a design optimization method which can be applied to determine optimal skull opening for individual patient-specific cases and (2) performing a large-scale parametric optimization study to give some guidance in general about the optimal skull opening in case of oedematous brain tissue.Methods: A large number of virtual experiments performed by finite element simulations were applied to determine tendencies of tissue behaviour during surgery. The multiobjective optimization is performed by Goal Programming and Physical Programming methods.Results: Our results show that the postoperative pressure has an approximately linear dependence on the preoperative pressure and the skull opening area, while the damaged brain volume could have a more complex nonlinear dependence on the input data. Based on the averaged results of the parametric optimization study, the optimal skull opening has been determined in the function of the preoperative pressure and the relative importance of the pressure reduction. These results show that the optimal size of the unilateral skull opening is usually between 130-180 cm² and these openings are more beneficial than the currently analysed bifrontal openings.Conclusions: The optimal skull opening is patient-specific and depends on several input data. The presented methodology can be applied to optimize surgery based on these input parameters for different injury types. Based on the results of large-scale parametric study generally applicable approximate results have been provided.
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| 6. |
- Jones, Geraint H., et al.
(författare)
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The Comet Interceptor Mission
- 2024
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Ingår i: Space Science Reviews. - : Springer Nature. - 0038-6308 .- 1572-9672. ; 220:1
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Tidskriftsartikel (refereegranskat)abstract
- Here we describe the novel, multi-point Comet Interceptor mission. It is dedicated to the exploration of a little-processed long-period comet, possibly entering the inner Solar System for the first time, or to encounter an interstellar object originating at another star. The objectives of the mission are to address the following questions: What are the surface composition, shape, morphology, and structure of the target object? What is the composition of the gas and dust in the coma, its connection to the nucleus, and the nature of its interaction with the solar wind? The mission was proposed to the European Space Agency in 2018, and formally adopted by the agency in June 2022, for launch in 2029 together with the Ariel mission. Comet Interceptor will take advantage of the opportunity presented by ESA’s F-Class call for fast, flexible, low-cost missions to which it was proposed. The call required a launch to a halo orbit around the Sun-Earth L2 point. The mission can take advantage of this placement to wait for the discovery of a suitable comet reachable with its minimum Δ V capability of 600 ms − 1 . Comet Interceptor will be unique in encountering and studying, at a nominal closest approach distance of 1000 km, a comet that represents a near-pristine sample of material from the formation of the Solar System. It will also add a capability that no previous cometary mission has had, which is to deploy two sub-probes – B1, provided by the Japanese space agency, JAXA, and B2 – that will follow different trajectories through the coma. While the main probe passes at a nominal 1000 km distance, probes B1 and B2 will follow different chords through the coma at distances of 850 km and 400 km, respectively. The result will be unique, simultaneous, spatially resolved information of the 3-dimensional properties of the target comet and its interaction with the space environment. We present the mission’s science background leading to these objectives, as well as an overview of the scientific instruments, mission design, and schedule.
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| 7. |
- 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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| 8. |
- Molnár, Anna, et al.
(författare)
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Untargeted metabolomic analyses support the main phylogenetic groups of the common plant-associated Alternaria fungi isolated from grapevine (Vitis vinifera)
- 2023
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Ingår i: Scientific Reports. - : Nature Publishing Group. - 2045-2322. ; 13:1
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Tidskriftsartikel (refereegranskat)abstract
- Alternaria, a cosmopolitan fungal genus is a dominant member of the grapevine (Vitis vinifera) microbiome. Several Alternaria species are known to produce a variety of secondary metabolites, which are particularly relevant to plant protection and food safety in field crops. According to previous findings, the majority of Alternaria species inhabiting grapevine belong to Alternaria sect. Alternaria. However, the phylogenetic diversity and secondary metabolite production of the distinct Alternaria species has remained unclear. In this study, our aim was to examine the genetic and metabolic diversity of endophytic Alternaria isolates associated with the above-ground tissues of the grapevine. Altogether, 270 Alternaria isolates were collected from asymptomatic leaves and grape clusters of different grapevine varieties in the Eger wine region of Hungary. After analyses of the nuclear ribosomal DNA internal transcribed spacer (ITS) and RNA polymerase second largest subunit (rpb2) sequences, 170 isolates were chosen for further analyses. Sequences of the Alternaria major allergen gene (Alt a 1), endopolygalacturonase (endoPG), OPA10-2, and KOG1058 were also included in the phylogenetic analyses. Identification of secondary metabolites and metabolite profiling of the isolates were performed using high-performance liquid chromatography (HPLC)–high-resolution tandem mass spectrometry (HR-MS/MS). The multilocus phylogeny results revealed two distinct groups in grapevine, namely A. alternata and the A. arborescens species complex (AASC). Eight main metabolites were identified in all collected Alternaria isolates, regardless of their affiliation to the species and lineages. Multivariate analyses of untargeted metabolites found no clear separations; however, a partial least squares-discriminant analysis model was able to successfully discriminate between the metabolic datasets from isolates belonging to the AASC and A. alternata. By conducting univariate analysis based on the discriminant ability of the metabolites, we also identified several features exhibiting large and significant variation between A. alternata and the AASC. The separation of these groups may suggest functional differences, which may also play a role in the functioning of the plant microbiome.
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| 9. |
- Pajola, Maurizio, et al.
(författare)
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The southern hemisphere of 67P/Churyumov-Gerasimenko : Analysis of the preperihelion size-frequency distribution of boulders >= 7m
- 2016
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Ingår i: Astronomy and Astrophysics. - : EDP Sciences. - 0004-6361 .- 1432-0746. ; 592
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Tidskriftsartikel (refereegranskat)abstract
- Aims. We calculate the size-frequency distribution of the boulders on the southern hemisphere of comet 67P Churyumov-Gerasimenko (67P), which was in shadow before the end of April 2015. We compare the new results with those derived from the northern hemisphere and equatorial regions of 67P, highlighting the possible physical processes that lead to these boulder size distributions. Methods. We used images acquired by the OSIRIS Narrow Angle Camera (NAC) on 2 May 2015 at a distance of 125 km from the nucleus. The scale of this dataset is 2.3 m/px; the high resolution of the images, coupled with the favorable observation phase angle of 62 degrees, provided the possibility to unambiguously identify boulders >= 7 m on the surface of 67P and to manually extract them with the software ArcGIS. We derived the size-frequency distribution of the illuminated southern hemisphere. Results. We found a power-law index of -3.6 +/- 0.2 for the boulders on the southern hemisphere with a diameter range of 7-35 m. The power-law index is equal to the one previously found on northern and equatorial regions of 67P, suggesting that similar boulder formation processes occur in both hemispheres. The power-law index is related to gravitational events triggered by sublimation and/or thermal fracturing causing regressive erosion. In addition, the presence of a larger number of boulders per km(2) in the southern hemisphere, which is a factor of 3 higher with respect to the northern hemisphere, suggests that the southernmost terrains of 67P are affected by a stronger thermal fracturing and sublimating activity, hence possibly causing larger regressive erosion and gravitational events.
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| 10. |
- Pettersson, Lage, et al.
(författare)
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17O NMR Study of Aqueous Peroxoisopolymolybdates at lower peroxide/Mo ratios.
- 2003
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Ingår i: Dalton Trans. ; :1, s. 146-152
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Tidskriftsartikel (refereegranskat)abstract
- Aqueous peroxomolybdates have been studied using 17O NMR together with equilibrium measurements and calculations, over a wide range of conditions. Ten peroxo species are identified, mostly in more than one state of protonation. Some are already known in the solid state, or from equilibrium analysis, but structural information is also obtained for MoO3(HO2)− and the new or previously tentative species Mo2O5(O2)22−, HpMo7O23(O2)2p−6 and HpMo7O23(O2)p−6 (p = 0–2). Sites of protonation are identified, as are 17O resonances from both bidentate and monodentate peroxide. Several oxygen exchange processes are also seen, including a probable dimer–tetramer exchange.
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