Flux line lattice symmetries in the borocarbide superconductor LuNi2B2C

We compare the results of small angle neutron scattering on the flux line lattice (FLL) obtained in the borocarbide superconductor LuNi₂B₂C with the applied field along the c- and a-axes. For H‖c the temperature dependence of the FLL structural phase transition from square to hexagonal symmetry was investigated. Above 10 K the transition onset field. H ₂(T), rises sharply, bending away from H _c2(T) in contradiction to theoretical predictions of the two merging. For H‖a a first order FLL reorientation transition is observed at H _tr=3–3.5 kOe. Below H _tr the FLL nearest neighbor direction is parallel to the b-axis, and above H _tr to the c-axis. This transition cannot be explained using nonlocal corrections to the London model.     

Simulated microstructure-sensitive extreme value probabilities for high cycle fatigue of duplex Ti-6Al-4V

A newly developed microstructure-sensitive extreme value probabilistic framework to characterize the performance/variability for damage evolution processes is exercised to compare the driving forces for fatigue crack formation (nucleation and early growth) at room temperature for four different microstructure variants of a duplex Ti-6Al-4V alloy. The aforementioned probabilistic framework links certain extreme value fatigue response parameters with microstructure attributes at fatigue critical sites through the use of marked correlation functions. By applying this framework to study the driving forces for fatigue crack formation in these microstructure variants of Ti-6Al-4V, these microstructures can be ranked in terms of relative high cycle fatigue (HCF) performance and the correlated microstructure attributes that have the most influence on the predicted fatigue response can be identified. Nonlocal fatigue indicator parameters (FIPs) based on the cyclic plastic strain averaged over domains on the length scale of the microstructure attributes (e.g., grains, phases) are used to estimate the driving force(s) for fatigue crack formation at the grain scale. By simulating multiple statistical volume elements (SVEs) using crystal plasticity constitutive relations, extreme value distributions of the predicted driving forces for fatigue crack formation are estimated using these FIPs. This strategy of using multiple SVEs contrasts with simulation based on a single representative volume element (RVE), which is often untenably large when considering extreme value responses. The simulations demonstrate that microstructures with smaller relative primary α grain sizes and lower volume fractions of the primary α grains tend to exhibit less variability and smaller magnitudes of the driving forces for fatigue crack formation. The extreme value FIPs are predicted to most likely occur at clusters of primary α grains oriented for easy basal slip. Additionally, surrounding grains/phases with soft orientation shed load to less favorably oriented primary α grains, producing extreme value FIPs.     

Metal-mediated tandem coassembly of collagen peptides into banded microstructures

The ability to recapitulate the features of natural collagen at the micro- and nanoscale with novel biopolymers has the potential to lead to improved biomaterials. Herein we describe stimuli-responsive collagen-based peptides (IdaCol and HisCol) that together form higher order assemblies in the presence of added metal ions. SEM and TEM imaging of these assemblies revealed microscale petal-like and intertwined fiber morphologies, each with periodic banding on the nanometer scale. The observed banding is consistent with tandem coassembly of alternating IdaCol and HisCol triple helical blocks that may laterally associate either in or out of register to form higher order structures, and mimics the banding found in natural collagen fibers.     

Preparation of phosphinic acids: Michael additions of phosphonous acids/esters to conjugated systems.

A very mild and facile method for the preparation of phosphinic acids via Michael addition of phosphonous acids as well as esters, through an intermediate silyl alkyl phosphonite, to activated conjugated systems is described.     

Mild Arbuzov reactions of phosphonous acids

A very mild and simple method for the preparation of phosphinic acids from phosphonous acids through the intermediacy of silylalkyl phosphonites is described.     

Direct use of unassigned resonances in NMR structure calculations with proxy residues

We present a method that significantly enhances the robustness of (automated) NMR structure determination by allowing the NOE data corresponding to unassigned NMR resonances to be used directly in the calculations. The unassigned resonances are represented by additional atoms or groups of atoms that have no interaction with the regular protein atoms except through distance restraints. These so-called "proxy" residues can be used to generate NOE-based distance restraints in a similar fashion as for the assigned part of the protein. If sufficient NOE information is available, the restraints are expected to place the proxies at positions close to the correct atoms for the unassigned resonance, which can facilitate subsequent assignment. Convergence can be further improved by supplying additional information about the possible identities of the unassigned resonances. We have implemented this approach in the widely used automated assignment and structure calculation protocols ARIA and CANDID. We find that it significantly increases the robustness of structure calculations with regard to missing assignments and yields structures of higher quality. Our approach is still able to find correctly folded structures with up to 30% randomly missing resonance assignments, and even when only backbone and beta resonances are present! This should be of significant value to NMR-based structural proteomics initiatives.     

Dynamics of Ligand Binding to a Rigid Glycosidase**

The single-domain GH11 glycosidase from Bacillus circulans (BCX) is involved in the degradation of hemicellulose, which is one of the most abundant renewable biomaterials in nature. We demonstrate that BCX in solution undergoes minimal structural changes during turnover. NMR spectroscopy results show that the rigid protein matrix provides a frame for fast substrate binding in multiple conformations, accompanied by slow conversion, which is attributed to an enzyme-induced substrate distortion. A model is proposed in which the rigid enzyme takes advantage of substrate flexibility to induce a conformation that facilitates the acyl formation step of the hydrolysis reaction.     

Evidence for resonance and absorption effects in positron-atom differential elastic scattering

This review focuses on recent positron-atom elastic differential cross section (DCS) measurements which reveal evidence that interference effects may be occurring between the elastic and inelastic scattering channels. These effects appear as (1) absorption effects which are observable in relative elastic DCSs by the washing out of structure in the DCS versus angle as the positron energy is increased above the positronium formation threshold, and (2) a new type of resonance-like structures at intermediate energies (well above the normal inelastic thresholds) that have been observed in absolute elastic DCS measurements when plotted at a fixed scattering angle versus energy. A discussion is provided of possibly relevant information on positron-atom scattering that also indicates that coupling is occurring between various scattering channels.