Why Do Protein Crystals Grown With the Aid of Porous Materials Show Better Diffraction Quality?

Well-diffracting protein crystals are indispensable for X-ray diffraction analysis, which is still the most powerful method for structure-function studies of biomolecules. A promising approach to growing such crystals is by using porous nucleation-inducing materials. However, while protein crystal nucleation in pores has been thoroughly considered, little attention has been paid to the subsequent growth of the crystals. Although the nucleation stage is decisive, it is the subsequent growth of the crystals outside the pore that determines their diffraction quality. The molecular-scale mechanism of growth of protein crystals in and outside pores is here considered theoretically. Due to the metastable conditions, the crystals that emerge from the pores grow slowly, which is a prerequisite for better diffraction. This expectation has been corroborated by experiments carried out with several types of porous material, such as Bioglass (“Naomi’s Nucleant”), Buckypaper, porous gold and porous silicon. Protein crystals grown with the aid of Bioglass and Buckypaper yielded significantly better diffraction quality compared with crystals grown conventionally. In all cases, visually superior crystals are usually obtained. We furthermore conclude that heterogeneous nucleation of a crystal outside the pore is an exceptional case. Rather, the protein crystals nucleating inside the pores continue growing outside them.

Structure of GaN grown from vapour phase on a seeded layer of gallium melt formed on a boron nitride ceramic substrate

In this study, two empirical models for the growth of millimetre–thick GaN material with either highly ordered textured or polycrystalline structure on a ceramic substrate by Hydride Vapour Phase Epitaxy (HVPE) are considered. It is suggested that the specific type of the structure of GaN is determined at the nucleation stage and depends on the character of the wetting of the surface of the substrate by the liquid gallium melt.

Effect of Graphene on Ice Polymorph

Recently, ice with the stacking disorder structure, consisting of random sequences of cubic ice (Ic) and hexagonal ice (Ih) layers, is reported to be more stable than pure Ih/Ic. While, due to a much lower free energy barrier of heterogeneous nucleation, in practice, the freezing process of water is usually controlled by heterogeneous nucleation which is triggered by an external medium. Herein, molecular dynamic simulations were carried out to explore the polymorph dependence of ice on the lattice structure of substrates. It turns out that, during the nucleation stage, the polymorph of ice nuclei can be severely altered by the graphene substrate, on which the Ih was found to occupy an absolute majority in new-formed ice. This can be attributed to the structure similarity between graphene and basal face of Ih. Besides the nucleation stage, our results suggest that the substrate can not affect the polymorph of ice which is far from the graphene surface. The polymorph selectivity of graphene to Ih will diminish with the growth of ice layer.

Stabilization of Calcium Oxalate Precursors during the Pre- and Post-Nucleation Stages with Poly(acrylic acid)

In this work, calcium oxalate (CaOx) precursors were stabilized by poly(acrylic acid) (PAA) as an additive under in vitro crystallization assays involving the formation of pre-nucleation clusters of CaOx via a non-classical crystallization (NCC) pathway. The in vitro crystallization of CaOx was carried out in the presence of 10, 50 and 100 mg/L PAA by using automatic calcium potentiometric titration experiments at a constant pH of 6.7 at 20 °C. The results confirmed the successful stabilization of amorphous calcium oxalate II and III (ACOII and ACO III) nanoparticles formed after PNC in the presence of PAA and suggest the participation and stabilization of polymer-induced liquid-precursor (PILP) in the presence of PAA. We demonstrated that PAA stabilizes CaOx precursors with size in the range of 20–400 nm. PAA additive plays a key role in the in vitro crystallization of CaOx stabilizing multi-ion complexes in the pre-nucleation stage, thereby delaying the nucleation of ACO nanoparticles. Indeed, PAA additive favors the formation of more hydrated and soluble phase of ACO nanoparticles that are bound by electrostatic interactions to carboxylic acid groups of PAA during the post-nucleation stage. These findings may help to a better understanding of the pathological mineralization resulting in urolithiasis in mammals.

Reproducible Orientation Relationships Developed from Phase Transformations—Role of Interfaces

The orientation relationship (OR) between phases related by a phase transformation is often reproducible. This study interprets and predicts the reproducible ORs with a two-stage approach. The initial OR formed at the nucleation stage tends to allow a periodic structure of a preferred state to form in the interface. A matching correspondence of either a one-to-one or n-to-m nature can be specified in the periodic structure. An initial OR will become the final reproducible OR if there is no misfit. Otherwise, a reproducible OR developed at the growth stage tends to permit a singular dislocation structure to form in an interface where the preferred state must be sustained locally. The actual change in the OR is subject to the given material system and the phase-transformation condition. Various singular dislocation structures and their constraints on the ORs are analyzed, with thermodynamics and kinetics applied conceptually. The resulting ORs can be specified by following one or more Δg parallelism rules. A set of workable steps is provided to facilitate the interpretation of observed reproducible ORs. Some unsolved problems are identified, which call for further studies that can quantitatively combine the thermodynamics, kinetics and crystallography of phase transformations.

Patterns of Fracture Initiation in Metallic Materials with a Heterogeneous Structure under Dynamic Cyclic Loading

The process of nucleation of fatigue defects in metal alloys with different structural morphology is considered. A physical model was built, calculation expressions were presented, a numerical experiment was performed to determine the moment of nucleation of the critical-size defect in Fe-based alloys during high-speed droplet impacts. The physical model is based on the theory of dislocations. It is shown that the determining factor in the process of wear nucleation under dynamic cyclic loading has a structural factor. Depending on the structure and properties of the material, as well as on the nature of the loads, the critical fatigue defect develops in the form of cracks, pores or microcraters. Comparative data of calculations and bench tests for droplet impingement erosion were presented. The contribution of the nucleation stage during the incubation period of erosive wear of the materials studied was evaluated. Due to the fact that rigorous instrumental methods for determining the duration of the nucleation stage are absent, the usage of the proposed analytical model is recommended for this purpose.

Analysis of the initial stage of fatigue wear in heterostructure materials under contact cyclic loading

Introduction. The process of formation of fatigue defects in metal alloys with different structural morphology is considered. The work objective is to develop a computational tool for determining the moment of the defect nucleation under cyclic loading.Materials and Methods. A physical model is built, calculation expressions are presented. The physical model is based on the theory of dislocations. It is shown that a structure factor is particularly important in the process of fracture nucleus origination under dynamic cyclic loading. Depending on the structure and properties of the material, as well as on the nature of the loads, the critical fatigue defect develops in the form of cracks, pores or micro-crater wear.Research Results. A numerical experiment was performed to determine the moment of nucleation of the critical-size defect in iron-base alloys under the drop hypervelocity impacts. Comparative data of calculations and bench tests for droplet impingement erosion of steels and alloys with the structure of ferrite, austenite, sorbitol and martensite are presented. The efficiency of the nucleation stage during the incubation period of erosive wear of the materials studied was evaluated.Discussion and Conclusions. There are no strict instrumental methods for determining the duration of the nucleation stage; therefore, it is recommended to use the proposed analytical model. In addition, the work performed gave a significant application result, i.e. it showed that the focused design of the material structure can significantly increase the wear resistance.

The role of pre-nucleation clusters in the crystallization of gold nanoparticles

The gold nanoparticle nucleation stage identified by XAS is accompanied in SAXS by an abrupt shrinkage of the size of molecular pre-nucleation clusters into gold nuclei, which is interpreted as a non-classical nucleation mechanism.