Computer Tomograph Measurements in Shear and Gravity Particle Flows

The paper reports the recent results obtained on the applicability of cross-sectional digital imaging method to study particle flow characteristics in 3D particle beds forced to move by gravity or shear. X-ray CT imaging technique is widely used in medical diagnostics and, during the last decades, its spatial and temporal resolution has been improved significantly. In this study, an attempt was made to use this technique for engineering purposes. Two experimental set-ups with different types of particle flows were investigated using Siemens Somatom Plus type CT equipment. A series of trials were carried out in a small model hopper with flat bottom and almost cylindrical side wall slightly deviating from verticality. Non steady-state flow was studied during the outflow of particulate material from this vessel, through a central hole at the bottom. Further investigation was fulfilled in a modified Cuette-type shearing device to study steady-state shear flow. This equipment consisted of an almost cylindrical vessel identical to that used for gravity flow measurements, and a smaller inner cylinder rotating within this vessel concentrically, around its vertical axis. The surface of the inner cylinder was notched vertically, i.e. perpendicularly to the direction of rotation to increase wall friction between the particles and the cylinder. Almost spherical sucrose granules, also used for gravity flow measurements, were filled into the gap between the rotating cylinder and the outer wall of the equipment. Movement of particles took place due to shear, generated within the particle bed. By using X-ray CT technique, cross-sectional digital images were obtained in every two seconds for both types of particle flows. For this, the cross-sectional variation of the local Hounsfield density values were measured in a matrix of 0.1x0.1x2.0 mm space elements. It was proved that the applied non-invasive crosssectional imaging technique was suitable to distinguish the stationary and moving particle regions, and by this, to estimate the location of the boundary zone between them

Joint neutron/X-ray crystal structure of a mechanistically relevant complex of perdeuterated urate oxidase and simulations provide insight into the hydration step of catalysis

Cofactor-independent urate oxidase (UOX) is an ~137 kDa tetrameric enzyme essential for uric acid (UA) catabolism in many organisms. UA is first oxidized by O2 to dehydroisourate (DHU) via a peroxo intermediate. DHU then undergoes hydration to 5-hydroxyisourate (5HIU). At different stages of the reaction both catalytic O2 and water occupy the 'peroxo hole' above the organic substrate. Here, high-resolution neutron/X-ray crystallographic analysis at room temperature has been integrated with molecular dynamics simulations to investigate the hydration step of the reaction. The joint neutron/X-ray structure of perdeuterated Aspergillus flavus UOX in complex with its 8-azaxanthine (8AZA) inhibitor shows that the catalytic water molecule (W1) is present in the peroxo hole as neutral H2O, oriented at 45° with respect to the ligand. It is stabilized by Thr57 and Asn254 on different UOX protomers as well as by an O-H∙ ∙ ∙π interaction with 8AZA. The active site Lys10-Thr57 dyad features a charged Lys10-NH3+ side chain engaged in a strong hydrogen bond with Thr57OG1, while the Thr57OG1-HG1 bond is rotationally dynamic and oriented toward the π system of the ligand, on average. Our analysis offers support for a mechanism in which W1 performs a nucleophilic attack on DHUC5 with Thr57HG1 central to a Lys10-assisted proton-relay system. Room-temperature crystallography and simulations also reveal conformational heterogeneity for Asn254 that modulates W1 stability in the peroxo hole. This is proposed to be an active mechanism to facilitate W1/O2 exchange during catalysis

Mechanistic study of an immobilized molecular electrocatalyst by in situ gap-plasmon-assisted spectro-electrochemistry

Immobilised first-row transition metal complexes are potential low-cost electrocatalysts for selective CO2 conversion to produce renewable fuels. Mechanistic understanding of their function is vital for the development of next-generation catalysts, though poor surface sensitivity of many techniques makes this challenging. Here, a nickel bis(terpyridine) complex is introduced as a CO2 reduction electrocatalyst in a unique electrode geometry, sandwiched by thiol anchoring moieties between two gold surfaces. Gap-plasmon-assisted surface-enhanced Raman scattering spectroscopy coupled with density functional theory calculations reveals the nature of the anchoring group plays a pivotal role in the catalytic mechanism by eliminating ligand loss. Our in-situ spectro-electrochemical measurement enables the detection of as few as 8 molecules undergoing redox transformations in the individual gold-sandwiched nanocavities, together with the calibration of electrical fields via vibrational Stark effects. This advance allows rapid exploration of non-resonant redox reactions at the few-molecule level and provides scope for future mechanistic studies of single-molecules

Strong structuring arising from weak cooperative O-H···π and C-H···O hydrogen bonding in benzene-methanol solution

Weak hydrogen bonds, such as O-H···π and C-H···O, are thought to direct biochemical assembly, molecular recognition, and chemical selectivity but are seldom observed in solution. We have used neutron diffraction combined with H/D isotopic substitution to obtain a detailed spatial and orientational picture of the structure of benzene-methanol mixtures. Our analysis reveals that methanol fully solvates and surrounds each benzene molecule. The expected O-H···π interaction is highly localised and directional, with the methanol hydroxyl bond aligned normal to the aromatic plane and the hydrogen at a distance of 2.30 Å from the ring centroid. Simultaneously, the tendency of methanol to form chain and cyclic motifs in the bulk liquid is manifest in a highly templated solvation structure in the plane of the ring. The methanol molecules surround the benzene so that the O-H bonds are coplanar with the aromatic ring while the oxygens interact with C-H groups through simultaneous bifurcated hydrogen bonds. This demonstrates that weak hydrogen bonding can modulate existing stronger interactions to give rise to highly ordered cooperative structural motifs that persist in the liquid phase

A Counterexample Regarding Labelled Well-Quasi-Ordering

Korpelainen, Lozin, and Razgon conjectured that a hereditary property of graphs which is well-quasi-ordered by the induced subgraph order and defined by only finitely many minimal forbidden induced subgraphs is labelled well-quasi-ordered, a notion stronger than that of n-well-quasi-order introduced by Pouzet in the 1970s. We present a counterexample to this conjecture. In fact, we exhibit a hereditary property of graphs which is well-quasi-ordered by the induced subgraph order and defined by finitely many minimal forbidden induced subgraphs yet is not 2-well-quasi-ordered. This counterexample is based on the widdershins spiral, which has received some study in the area of permutation patterns

New Polynomial Cases of the Weighted Efficient Domination Problem

Let G be a finite undirected graph. A vertex dominates itself and all its neighbors in G. A vertex set D is an efficient dominating set (e.d. for short) of G if every vertex of G is dominated by exactly one vertex of D. The Efficient Domination (ED) problem, which asks for the existence of an e.d. in G, is known to be NP-complete even for very restricted graph classes. In particular, the ED problem remains NP-complete for 2P3-free graphs and thus for P7-free graphs. We show that the weighted version of the problem (abbreviated WED) is solvable in polynomial time on various subclasses of 2P3-free and P7-free graphs, including (P2+P4)-free graphs, P5-free graphs and other classes. Furthermore, we show that a minimum weight e.d. consisting only of vertices of degree at most 2 (if one exists) can be found in polynomial time. This contrasts with our NP-completeness result for the ED problem on planar bipartite graphs with maximum degree 3

Pathogen Sensing Pathways in Human Embryonic Stem Cell Derived-Endothelial Cells: Role of NOD1 Receptors.

Human embryonic stem cell-derived endothelial cells (hESC-EC), as well as other stem cell derived endothelial cells, have a range of applications in cardiovascular research and disease treatment. Endothelial cells sense Gram-negative bacteria via the pattern recognition receptors (PRR) Toll-like receptor (TLR)-4 and nucleotide-binding oligomerisation domain-containing protein (NOD)-1. These pathways are important in terms of sensing infection, but TLR4 is also associated with vascular inflammation and atherosclerosis. Here, we have compared TLR4 and NOD1 responses in hESC-EC with those of endothelial cells derived from other stem cells and with human umbilical vein endothelial cells (HUVEC). HUVEC, endothelial cells derived from blood progenitors (blood outgrowth endothelial cells; BOEC), and from induced pluripotent stem cells all displayed both a TLR4 and NOD1 response. However, hESC-EC had no TLR4 function, but did have functional NOD1 receptors. In vivo conditioning in nude rats did not confer TLR4 expression in hESC-EC. Despite having no TLR4 function, hESC-EC sensed Gram-negative bacteria, a response that was found to be mediated by NOD1 and the associated RIP2 signalling pathways. Thus, hESC-EC are TLR4 deficient but respond to bacteria via NOD1. This data suggests that hESC-EC may be protected from unwanted TLR4-mediated vascular inflammation, thus offering a potential therapeutic advantage