RESUMO
We present an in situ X-ray reflectivity study of the adsorption behavior of the protein lysozyme on titanium oxide layers under variation of different thermodynamic parameters, such as temperature, hydrostatic pressure, and pH value. Moreover, by varying the layer thickness of the titanium oxide layer on a silicon wafer, changes in the adsorption behavior of lysozyme were studied. In total, we determined less adsorption on titanium oxide compared with silicon dioxide, while increasing the titanium oxide layer thickness causes stronger adsorption. Furthermore, the variation of temperature from 20 to 80 °C yields an increase in the amount of adsorbed lysozyme at the interface. Additional measurements with variation of the pH value of the system in a region between pH 2 and 12 show that the surface charge of both protein and titanium oxide has a crucial role in the adsorption process. Further pressure-dependent experiments between 50 and 5000 bar show a reduction of the amount of adsorbed lysozyme with increasing pressure.
Assuntos
Muramidase/metabolismo , Titânio/química , Água/química , Adsorção , Concentração de Íons de Hidrogênio , Muramidase/química , Propriedades de Superfície , Temperatura , TermodinâmicaRESUMO
An X-ray reflectivity study on the adsorption behavior of human apolipoprotein A1 (apoA1) at hydrophilic and hydrophobic interfaces is presented. It is shown that the protein interacts via electrostatic and hydrophobic interactions with the interfaces, resulting in the absorption of the protein. pH dependent measurements at the solid/liquid interface between silicon dioxide and aqueous protein solution show that in a small pH range between pH 4 and 6, adsorption is increased due to electrostatic attraction. Here, the native shape of the protein seems to be conserved. In contrast, the adsorption at the liquid/gas interface is mainly driven by hydrophobic effects, presumably by extending the hydrophobic regions of the amphipathic helices, and results in a conformational change of the protein during adsorption. However, the addition of differently charged membrane-forming lipids at the liquid/gas interface illustrates the ability of apoA1 to include lipids, resulting in a depletion of the lipids from the interface.
Assuntos
Apolipoproteína A-I/química , Proteínas/química , Dióxido de Silício/química , Água/química , Ar , Humanos , Concentração de Íons de Hidrogênio , Interações Hidrofóbicas e Hidrofílicas , Eletricidade Estática , Tensão SuperficialRESUMO
Iron-bearing carbonates are candidate phases for carbon storage in the deep Earth and may play an important role for the Earth's carbon cycle. To elucidate the properties of carbonates at conditions of the deep Earth, we investigated the pressure driven magnetic high spin to low spin transition of synthetic siderite FeCO3 and magnesiosiderite (Mg0.74Fe0.26)CO3 single crystals for pressures up to 57 GPa using diamond anvil cells and x-ray Raman scattering spectroscopy to directly probe the iron 3d electron configuration. An extremely sharp transition for siderite single crystal occurs at a notably low pressure of 40.4 ± 0.1 GPa with a transition width of 0.7 GPa when using the very soft pressure medium helium. In contrast, we observe a broadening of the transition width to 4.4 GPa for siderite with a surprising additional shift of the transition pressure to 44.3 ± 0.4 GPa when argon is used as pressure medium. The difference is assigned to larger pressure gradients in case of argon. For magnesiosiderite loaded with argon, the transition occurs at 44.8 ± 0.8 GPa showing similar width as siderite. Hence, no compositional effect on the spin transition pressure is observed. The spectra measured within the spin crossover regime indicate coexistence of regions of pure high- and low-spin configuration within the single crystal.
RESUMO
We present a study of the local atomic environment of the oxygen atoms in the aqueous solutions of NaOH and HCl under simultaneous high-temperature and high-pressure conditions. Experimental nonresonant X-ray Raman scattering core-level spectra at the oxygen K-edge show systematic changes as a function of temperature and pressure. These systematic changes are distinct for the two different solutes and are described well by calculations within the Bethe-Salpeter formalism for snapshots from ab initio molecular dynamics simulations. The agreement between experimental and simulation results allows us to use the computations for a detailed fingerprinting analysis in an effort to elucidate the local atomic structure and hydrogen-bonding topology in these relevant solutions. We observe that both electrolytes, especially NaOH, enhance hydrogen bonding and tetrahedrality in the water structure at supercritical conditions, in particular in the vicinity of the hydration shells. This effect is accompanied with the association of the HCl and NaOH molecules at elevated temperatures.
RESUMO
We present an X-ray Compton scattering study on aqueous trimethylamine N-oxide (TMAO) and guanidine hydrochloride solutions (GdnHCl) as a function of temperature. Independent from the concentration of the solvent, Compton profiles almost resemble results for liquid water as a function of temperature. However, the number of hydrogen bonds per water molecule extracted from the Compton profiles suggests a decrease of hydrogen bonds with rising temperature for all studied samples, and the differences between water and the solutions are weak. Nevertheless, the data indicate a reduced bond weakening with rising TMAO concentration up to 5 M of 7.2% compared to 8% for pure water. In contrast, the addition of GdnHCl appears to behave differently for concentrations up to 3.1 M with a weaker impact on the temperature response of the hydrogen bond structure.
RESUMO
Using a combination of high resolution X-ray powder diffraction and X-ray Raman scattering spectroscopy at the B K- and Ca L2,3-edges, we analyzed the reaction products of Ca(BH4)2 after annealing at 350 °C and 400 °C under vacuum conditions. We observed the formation of nanocrystalline/amorphous CaB6 mainly and found only small contributions from amorphous B for annealing times larger than 2 h. For short annealing times of 0.5 h at 400 °C we observed neither CaB12H12 nor CaB6. The results indicate a reaction pathway in which Ca(BH4)2 decomposes to B and CaH2 and finally reacts to form CaB6. These findings confirm the potential of using Ca(BH4)2 as a hydrogen storage medium and imply the desired cycling capabilities for achieving high-density hydrogen storage materials.
RESUMO
We studied the structure and energetics of supercooled water by means of X-ray Raman and Compton scattering. Under supercooled conditions down to 255 K, the oxygen K-edge measured by X-ray Raman scattering suggests an increase of tetrahedral order similar to the conventional temperature effect observed in non-supercooled water. Compton profile differences indicate contributions beyond the theoretically predicted temperature effect and provide a deeper insight into local structural changes. These contributions suggest a decrease of the electron mean kinetic energy by 3.3 ± 0.7 kJ (mol K)(-1) that cannot be modeled within established water models. Our surprising results emphasize the need for water models that capture in detail the intramolecular structural changes and quantum effects to explain this complex liquid.