Genetic studies of disorders of calcium crystal deposition

In summary, although many factors are likely to be involved in regulating calcification and ossification processes, studies of the causation of articular chondrocalcinosis and disorders of spinal ossification, such as DISH and OPLL, implicate control over inorganic pyrophosphate levels as being one of the most important factors in their aetiopathogenesis. The findings of these studies may prove relevant to other rheumatic diseases in which ectopic ossification occurs, such as AS.

Crystal structures and hydrogen bonding in the morpholinium salts of four phenoxyacetic acid analogues

The anhydrous salts morpholinium (tetrahydro-2-H-1,4-oxazine) phenxyacetate, C4H10NO+ C8H7O3- (I), (4-fluorophenoxy)acetate, C4H10NO+ C8H6FO3- (II) and isomeric morpholinium (3,5-dichlorophenoxy)acetate (3,5-D) (III) and morpholinium (2,4-dichlorophenoxy)acetate (2,4-D), C4H10NO+ C8H5Cl2O3- (IV), have been determined and their hydrogen-bonded structures are described. In the crystals of (I), (III) and (IV), one of the the aminium H atoms is involved in a three-centre asymmetric cation-anion N-H...O,O' R2/1(4) hydrogen-bonding interaction with the two carboxyl O-atom acceptors of the anion. With the structure of (II), the primary N---H...O interaction is linear. In the structures of (I), (II) and (III), the second N-H...O(carboxyl) hydrogen bond generates one-dimensional chain structures extending in all cases along [100]. With (IV), the ion pairs are linked though inversion-related N-H...O hydrogen bonds [graph set R2/4(8)], giving a cyclic heterotetrameric structure.

Crystal structure of morpholin-4-ium cinnamate

In the anhydrous salt formed from the reaction of morpholine with cinnamic acid, C4H10NO+ C9H7O2-, the acid side chain in the trans-cinnamate anion is significantly rotated out of the benzene plane [C-C-C-C torsion angle = 158.54(17)deg. In the crystal, one of the the aminium H atoms is involved in a asymmetric three-centre cation-anion N-H...(O,O') R2/1(4) hydrogen-bonding interaction with the two carboxyl O-atom acceptors of the anion. The second aminium H atom forms an inter-species N-H...O(carboxyl) hydrogen bond, generating a one-dimensional chain structure extending along [100]. Chains are linked by C-H...O interactions forming a supramolecular layer parallel to (01-1).

Crystal engineering in two dimensions: An approach to molecular nanopatterning

We describe a surprising cooperative adsorption process observed by scanning tunneling microscopy (STM) at the liquid−solid interface. The process involves the association of a threefold hydrogen-bonding unit, trimesic acid (TMA), with straight-chain aliphatic alcohols of varying length (from C7 to C30), which coadsorb on highly oriented pyrolytic graphite (HOPG) to form linear patterns. In certain cases, the known TMA “flower pattern” can coexist temporarily with the linear TMA−alcohol patterns, but it eventually disappears. Time-lapsed STM imaging shows that the evolution of the flower pattern is a classical ripening phenomenon. The periodicity of the linear TMA−alcohol patterns can be modulated by choosing alcohols with appropriate chain lengths, and the precise structure of the patterns depends on the parity of the carbon count in the alkyl chain. Interactions that lead to this odd−even effect are analyzed in detail. The molecular components of the patterns are achiral, yet their association by hydrogen bonding leads to the formation of enantiomeric domains on the surface. The interrelation of these domains and the observation of superperiodic structures (moiré patterns) are rationalized by considering interactions with the underlying graphite surface and within the two-dimensional crystal of the adsorbed molecules. Comparison of the observed two-dimensional structures with the three-dimensional crystal structures of TMA−alcohol complexes determined by X-ray crystallography helps reveal the mechanism of molecular association in these two-component systems.

Performance modulation of α-MnO2 nanowires by crystal facet engineering

Modulation of material physical and chemical properties through selective surface engineering is currently one of the most active research fields, aimed at optimizing functional performance for applications. The activity of exposed crystal planes determines the catalytic, sensory, photocatalytic, and electrochemical behavior of a material. In the research on nanomagnets, it opens up new perspectives in the fields of nanoelectronics, spintronics, and quantum computation. Herein, we demonstrate controllable magnetic modulation of α-MnO 2 nanowires, which displayed surface ferromagnetism or antiferromagnetism, depending on the exposed plane. First-principles density functional theory calculations confirm that both Mn- and O-terminated α-MnO2(1 1 0) surfaces exhibit ferromagnetic ordering. The investigation of surface-controlled magnetic particles will lead to significant progress in our fundamental understanding of functional aspects of magnetism on the nanoscale, facilitating rational design of nanomagnets. Moreover, we approved that the facet engineering pave the way on designing semiconductors possessing unique properties for novel energy applications, owing to that the bandgap and the electronic transport of the semiconductor can be tailored via exposed surface modulations.

Mechanical properties and damage tolerance of Y2SiO5

Y2SiO5 has potential applications as functional-structural ceramic and environmental/thermal barrier coating material. As an important grain-boundary phase in the sintered Si3N4, it also influences the mechanical and dielectric performances of the host material. In this paper, we present the mechanical properties of Y2SiO5 including elastic moduli, hardness, strength and fracture toughness, and try to understand the mechanical features from the viewpoint of crystal structure. Y2SiO5 has low shear modulus, low hardness, as well as high capacity for dispersing mechanical damage energy and for resisting crack penetration. Particularly, it can be machined by cemented carbides tools. The crystal structure characteristics of Y2SiO5 suggest the low-energy weakly bonded atomic planes crossed only by the easily breaking Y-O bonds as well as the rotatable rigid SiO4 tetrahedra are the origins of low shear deformation, good damage tolerance and good machinability of this material. TEM observations also demonstrate that the mechanical damage energy was dispersed in the form of the micro-cleavages, stacking faults and twins along these weakly bonded atomic planes, which allows the "microscale-plasticity" for Y2SiO5.

Synergistic crystal facet engineering and structural control of WO3 films exhibiting unprecedented photoelectrochemical performance

WO3 nanoplate arrays with (002) oriented facets grown on fluorine doped SnO2 (FTO) glass substrates are tailored by tuning the precursor solution via a facile hydrothermal method. A 2-step hydrothermal method leads to the preferential growth of WO3 film with enriched (002) facets, which exhibits extraordinary photoelectrochemical (PEC) performance with a remarkable photocurrent density of 3.7 mA cm–2 at 1.23 V vs. revisable hydrogen electrode (RHE) under AM 1.5 G illumination without the use of any cocatalyst, corresponding to ~93% of the theoretical photocurrent of WO3. Density functional theory (DFT) calculations together with experimental studies reveal that the enhanced photocatalytic activity and better photo-stability of the WO3 films are attributed to the synergistic effect of highly reactive (002) facet and nanoplate structure which facilitates the photo–induced charge carrier separation and suppresses the formation of peroxo-species. Without the use of oxygen evolution cocatalysts, the excellent PEC performance, demonstrated in this work, by simply tuning crystal facets and nanostructure of pristine WO3 films may open up new opportunities in designing high performance photoanodes for PEC water splitting.

Characterisation of head-hardened rail steel in terms of cyclic plasticity response and microstructure for improved material modelling

Stress- and strain-controlled tests of heat treated high-strength rail steel (Australian Standard AS1085.1) have been performed in order to improve the characterisation of the said material׳s ratcheting and fatigue wear behaviour. The hardness of the rail head material has also been studied and it has been found that hardness reduces considerably below four-millimetres from the rail top surface. Historically, researchers have used test coupons with circular cross-sections to conduct cyclic load tests. Such test coupons, typically five-millimetres in gauge diameter and ten‐millimetres in grip diameter, are usually taken from the rail head sample. When there is considerable variation of material properties over the cross-section it becomes likely that localised properties of the rail material will be missed. In another case from the literature, disks 47 mm in diameter for a twin-disk rolling contact test machine were obtained directly from the rail sample and used to validate ratcheting and rolling contact fatigue wear models. The question arises: How accurate are such tests, especially when large material property gradients exist? In this research paper, the effects of rail sampling location on the ratcheting behaviour of AS1085.1 rail steel were investigated using rectangular-shaped specimens obtained at four different depths to observe their respective cyclic plasticity behaviour. The microstructural features of the test coupons were also analysed, especially the pearlite inter-lamellar spacing which showed strong correlation with both hardness and cyclic plasticity behaviour of the material. This work ultimately provides new data and testing methodology to aid the selection of valid parameters for material constitutive models to better understand rail surface ratcheting and wear.