Role of microscopic phase separation in gelation of aqueous gelatin solutions.

Using a unique home-made cell for four-contact impedance spectroscopy of conductive liquid samples, we establish the existence of two low frequency conductivity relaxations in aqueous solutions of gelatin, in both liquid and gel states. A comparison with diffusion measurements using pulsed field gradient NMR, and circular dichroism spectroscopy, shows that the faster relaxation process is due to gelatin macromolecule self-diffusion. This single molecule diffusion is mostly insensitive to the macroscopic state of the sample, implying that we have a clear separation of gelatin molecules into a free and network-bound phase. Scaling relationships for the self-diffusion indicate that the gelation process is not a percolative phenomenon, but is caused by aggregation of triple helices into a system-spanning fibre network.

Solid-state NMR/NQR and first-principles study of two niobium halide cluster compounds.

Two hexanuclear niobium halide cluster compounds with a [Nb6X12](2+) (X=Cl, Br) diamagnetic cluster core, have been studied by a combination of experimental solid-state NMR/NQR techniques and PAW/GIPAW calculations. For niobium sites the NMR parameters were determined by using variable Bo field static broadband NMR measurements and additional NQR measurements. It was found that they possess large positive chemical shifts, contrary to majority of niobium compounds studied so far by solid-state NMR, but in accordance with chemical shifts of (95)Mo nuclei in structurally related compounds containing [Mo6Br8](4+) cluster cores. Experimentally determined δiso((93)Nb) values are in the range from 2,400 to 3,000 ppm. A detailed analysis of geometrical relations between computed electric field gradient (EFG) and chemical shift (CS) tensors with respect to structural features of cluster units was carried out. These tensors on niobium sites are almost axially symmetric with parallel orientation of the largest EFG and the smallest CS principal axes (Vzz and δ33) coinciding with the molecular four-fold axis of the [Nb6X12](2+) unit. Bridging halogen sites are characterized by large asymmetry of EFG and CS tensors, the largest EFG principal axis (Vzz) is perpendicular to the X-Nb bonds, while intermediate EFG principal axis (Vyy) and the largest CS principal axis (δ11) are oriented in the radial direction with respect to the center of the cluster unit. For more symmetrical bromide compound the PAW predictions for EFG parameters are in better correspondence with the NMR/NQR measurements than in the less symmetrical chlorine compound. Theoretically predicted NMR parameters of bridging halogen sites were checked by (79/81)Br NQR and (35)Cl solid-state NMR measurements.

Cooperative mercury motion in the ionic conductor Cu2HgI4.

We present the observation of glasslike dynamic correlations of mobile mercury ions in the ionic conductor Cu2HgI4, detected in both NMR and nonlinear conductivity experiments. The results show that dynamic cooperativity appears in systems seemingly unrelated to glassy and soft arrested materials. A simple kinetic two-component model is proposed, which seems to provide a good description of the cooperative ionic dynamics.

Emergence of superconductivity in the cuprates via a universal percolation process.

A pivotal step toward understanding unconventional superconductors would be to decipher how superconductivity emerges from the unusual normal state. In the cuprates, traces of superconducting pairing appear above the macroscopic transition temperature Tc, yet extensive investigation has led to disparate conclusions. The main difficulty has been to separate superconducting contributions from complex normal-state behaviour. Here we avoid this problem by measuring nonlinear conductivity, an observable that is zero in the normal state. We uncover for several representative cuprates that the nonlinear conductivity vanishes exponentially above Tc, both with temperature and magnetic field, and exhibits temperature-scaling characterized by a universal scale Ξ0. Attempts to model the response with standard Ginzburg-Landau theory are systematically unsuccessful. Instead, our findings are captured by a simple percolation model that also explains other properties of the cuprates. We thus resolve a long-standing conundrum by showing that the superconducting precursor in the cuprates is strongly affected by intrinsic inhomogeneity.

Determination of the hyperfine magnetic field in magnetic carbon-based materials: DFT calculations and NMR experiments.

The prospect of carbon-based magnetic materials is of immense fundamental and practical importance, and information on atomic-scale features is required for a better understanding of the mechanisms leading to carbon magnetism. Here we report the first direct detection of the microscopic magnetic field produced at (13)C nuclei in a ferromagnetic carbon material by zero-field nuclear magnetic resonance (NMR). Electronic structure calculations carried out in nanosized model systems with different classes of structural defects show a similar range of magnetic field values (18-21 T) for all investigated systems, in agreement with the NMR experiments. Our results are strong evidence of the intrinsic nature of defect-induced magnetism in magnetic carbons and establish the magnitude of the hyperfine magnetic field created in the neighbourhood of the defects that lead to magnetic order in these materials.

Contactless measurement of nonlinear conductivity in the radio-frequency range.

We have developed a system for contactless measurement of nonlinear conductivity in the radio-frequency band, and over a wide temperature range. A non-resonant circuit is used to electrically excite the sample, and the induced signal is detected by a resonant circuit whose natural frequency matches higher harmonics of the excitation. A simple modification of the probe allows non-resonant detection suitable for stronger signals. Two measurement procedures are proposed that allow significant excitation power variation, up to 150 W. The apparatus has been validated through the measurement of the nonlinear response at the superconducting transition of a high-Tc superconductor, and the nematic transition of an iron pnictide.