Johannes Möller

The Effect of Ionic Strength, Temperature, and Pressure on the Interaction Potential of Dense Protein Solutions: From Nonlinear Pressure Response to Protein Crystallization

Understanding the intermolecular interaction potential, V(r), of proteins under the influence of temperature, pressure, and salt concentration is essential for understanding protein aggregation, crystallization, and protein phase behavior in general. Here, we report small-angle x-ray scattering studies on dense lysozyme solutions of high ionic strength as a function of temperature and pressure. We show that the interaction potential changes in a nonlinear fashion over a wide range of temperatures, salt, and protein concentrations. Neither temperature nor protein and salt concentration lead to marked changes in the pressure dependence of V(r), indicating that changes of the water structure dominate the pressure dependence of the intermolecular forces. Furthermore, by analysis of the temperature, pressure, and ionic strength dependence of the normalized second virial coefficient, b2, we show that the interaction can be fine-tuned by pressure, which can be used to optimize b2 values for controlled protein crystallization.

Gradual destruction of magnetism in the superconducting family NaFe1−xCoxAs

The interplay and coexistence of superconducting, magnetic and structural order parameters in NaFe{1-x}Co{x}As has been studied using SQUID magnetometry, muon-spin rotation and synchrotron x-ray powder diffraction. Substituting Fe by Co weakens the ordered magnetic state through both a suppression of T_N and a reduction in the size of the ordered moment. Upon further substitution of Fe by Co the high sensitivity of the muon as a local magnetic probe reveals a magnetically disordered phase, in which the size of the moment continues to decrease and falls to zero around the same point at which the magnetically-driven structural distortion is no longer resolvable. Both magnetism and the structural distortion are weakened as the robust superconducting state is established.

Evolution Of Magnetic Interactions In A Pressure-Induced Jahn-Teller Driven Magnetic Dimensionality Switch

We present the results of high-field magnetization and muon-spin relaxation measurements on the coordination polymer CuF 2 (H 2 O) 2 (pyrazine) in pressures up to 22.5 kbar. We observe a transition from a quasi-two-dimensional to a quasi-one-dimensional antiferromagnetic phase at 9.1 kbar, driven by a rotation of the Jahn-Teller axis. Long-range antiferromagnetic ordering is seen in both regimes, as well as a phase separation in the critical pressure region. The magnetic dimensionality switching as pressure is increased is accompanied by a halving of the primary magnetic exchange energy J and a fivefold decrease in the ordering temperature T N . J decreases gradually with pressure in the two-dimensional phase, and then increases in the one-dimensional regime. We relate both effects to the changes in the crystal structure with applied pressure.

Anisotropic local modification of crystal field levels in Pr-based pyrochlores : a muon-induced effect modeled using density functional theory.

Although muon spin relaxation is commonly used to probe local magnetic order, spin freezing, and spin dynamics, we identify an experimental situation in which the measured response is dominated by an effect resulting from the muon-induced local distortion rather than the intrinsic behavior of the host compound. We demonstrate this effect in some quantum spin ice candidate materials Pr(2)B(2)O(7) (B=Sn, Zr, Hf), where we detect a static distribution of magnetic moments that appears to grow on cooling. Using density functional theory we show how this effect can be explained via a hyperfine enhancement arising from a splitting of the non-Kramers doublet ground states on Pr ions close to the muon, which itself causes a highly anisotropic distortion field. We provide a quantitative relationship between this effect and the measured temperature dependence of the muon relaxation and discuss the relevance of these observations to muon experiments in other magnetic materials.

X-ray reflectivity measurements of liquid/solid interfaces under high hydrostatic pressure conditions

A high-pressure cell for in situ X-ray reflectivity measurements of liquid/solid interfaces at hydrostatic pressures up to 500 MPa (5 kbar), a pressure regime that is particularly important for the study of protein unfolding, is presented. The original set-up of this hydrostatic high-pressure cell is discussed and its unique properties are demonstrated by the investigation of pressure-induced adsorption of the protein lysozyme onto hydrophobic silicon wafers. The presented results emphasize the enormous potential of X-ray reflectivity studies under high hydrostatic pressure conditions for the in situ investigation of adsorption phenomena in biological systems.

Influence of HF2- geometry on magnetic interactions elucidated from polymorphs of the metal-organic framework [Ni(HF2)(pyz)2]PF6 (pyz = pyrazine).

A tetragonal polymorph of [Ni(HF(2))(pyz)(2)]PF(6) (designated β) is isomorphic to its SbF(6)-congener at 295 K and features linear Ni-FHF-Ni pillars. Enhancements in the spin exchange (J(FHF) = 7.7 K), Néel temperature (T(N) = 7 K), and critical field (B(c) = 24 T) were found relative to monoclinic α-PF(6). DFT reveals that the HF(2)(-) bridges are significantly better mediators of magnetic exchange than pyz (J(pyz)), where J(FHF) ≈ 3J(pyz), thus leading to quasi-1D behavior. Spin density resides on all atoms of the HF(2)(-) bridge whereas N-donor atoms of the pyz ring bear most of the density.

Multi-speckle X-ray photon correlation spectroscopy in the ultra-small-angle X-ray scattering range

The feasibility for multi-speckle XPCS measurements in the ultra-low-angle range is demonstrated. The performance of the setup is illustrated by means of colloidal dynamics.

Intermolecular interactions in highly concentrated protein solutions upon compression and the role of the solvent

The influence of high hydrostatic pressure on the structure and protein-protein interaction potential of highly concentrated lysozyme solutions up to about 370 mg ml(-1) was studied and analyzed using small-angle X-ray scattering in combination with a liquid-state theoretical approach. In the concentration region below 200 mg ml(-1), the interaction parameters of lysozyme solutions are affected by pressure in a nonlinear way, which is probably due to significant changes in the structural properties of bulk water, i.e., due to a solvent-mediated effect. Conversely, for higher concentrated protein solutions, where hydration layers below ∼4 water molecules are reached, the interaction potential turns rather insensitive to compression. The onset of transient (dynamic) clustering is envisaged in this concentration range. Our results also show that pressure suppresses protein nucleation, aggregation and finally crystallization in supersaturated condensed protein solutions. These findings are of importance for controlling and fine-tuning protein crystallization. Moreover, these results are also important for understanding the high stability of highly concentrated protein solutions (as they occur intracellularly) in organisms thriving under hydrostatic pressure conditions such as in the deep sea, where pressures up to the kbar-level are reached.

[Ni(HF2)(3-Clpy)4]BF4 (py = pyridine): evidence for spin exchange along strongly distorted F···H···F- bridges in a one-dimensional polymeric chain.

[Ni(HF(2))(3-Clpy)(4)]BF(4) (py = pyridine) is a simple one-dimensional (1D) coordination polymer composed of compressed NiN(4)F(2) octahedra that form chains with bridging HF(2)(-) ligands. In spite of significant distortion of the HF(2)(-) bridge, a quasi-1D antiferromagnetic (AFM) behavior was observed with J(FHF) = 4.86 K.

Weak magnetic transitions in pyrochlore Bi2Ir2O7

Muon spin relaxation measurements on Bi 2 Ir 2 O 7 show that it undergoes a bulk magnetic transition at 1.84(3) K. This is accompanied by increases in the muon spin relaxation rate and the amplitude of the nonrelaxing part of the signal. The magnetic field experienced by muons is estimated to be 0.7 mT at low temperature, around two orders of magnitude smaller than that in other pyrochlore iridates. These results suggest that the low-temperature state represents static magnetism of exceptionally small magnetic moments, ∼ 0.01μ B /Ir. The relaxation rate increases further below 0.23(4) K, coincident with an upturn in the specific heat, suggesting the existence of a second low-temperature magnetic transition.