Experimental validation of polyhedral discrete element model

The flow of polyhedral granular particles in a small 3D slice hopper is studied experimentally and computationally by applying the discrete element method (DEM). A high speed camera was used to obtain the experimental results. The experimental packing structure, flow behaviour, arching and discharging in the hopper are analysed and compared with the DEM results for three hopper half angles. Reasonable agreement is shown on the static packing, flow behaviour and hopper discharge rates. The critical orifice length at which flow ceases to be smooth is investigated and arching of the material around the orifice is demonstrated experimentally and computationally. Spherical particles of nearly identical volume and density to the average of the polyhedral particles are also tested and compared to the polyhedra. The DEM is shown to be reasonably adept at modelling the interactions between polyhedral particles in a system in which there are very many possible particle geometrical interactions. Further work should consider the cohesion between the particles and the particle and the wall. Simulations of a greater number of particles in different hopper geometries should also be explored.     

The design of biplanar,shielded, minimum energy,or minimum power pulsed B0 coils

By extending the formalism previously developed for the design of unshielded, biplanar gradient coils, shielded biplanarB ₀ coils optimized for homogeneity and either minimum energy or minimum power may be designed. We present results from an integrated approach to shielded biplanar coil design, the results of which are also applicable to gradient coils, enabling the design of shielded coils with a concomitant decrease in total inductance of the coil. Length constraints are also included in the integrated minimization procedure. Results from a preliminary design indicate that high-homogeneity, low-impedance, well-shielded coils result from this design approach.     

Reduced indentation recovery temperature at the surface of a crosslinked epoxy coating in humid conditions

Relaxation of surface defects shows that the surface of a crosslinked epoxy system, under normal laboratory conditions, apparently has a softening transition temperature that is approximately 20°C lower than calorimetric measures of T _g in the bulk. Physical aging data here confirms that this transition does resemble a glass transition. This observation is significant for properties that are determined by the surface of a coating. When ambient humidity is such that an epoxy may absorb significant quantities of moisture, it is plasticized, reducing its T _g. When the relaxation of nanoindentations was measured in a humid environment, the value of this softening surface transition temperature was further reduced by 10°C. Thus, the surface properties of a polymer coating, such as wear, durability, friction, will depend not only on the ambient temperature, but also on whether the environment is humid. This is very important when such a coating responds to an environment that changes, e.g., natural weather.     

Water as a Promoter of the Complete Oxidation of Volatile Organic Compounds over Uranium Oxide Catalysts

The effect of water addition on the complete oxidation of benzene and propane VOCs by uranium oxide catalysts has been investigated. Benzene oxidation was studied using a silica supported U₃O₈ catalyst. Complete oxidation is promoted by the addition of 2.6% water compared with the reactivity when no water is added to the reactant feed. Increasing the water concentration to 12.1% resulted in a suppression of oxidation activity. Investigation of propane oxidation using U₃O₈ shows a dramatic promotion of activity. Propane conversion was ca. 50% at 600 °C without added water, whilst it increased to 100% at 400 °C with the addition of 2.6% water. A comparison of oxidation activity has been made with Mn₂O₃, an oxide recognised for complete oxidation. In contrast to the U₃O₈ catalysts the addition of 2.6% water suppresses the activity of Mn₂O₃. In situ powder X-ray diffraction studies showed that the bulk U₃O₈ structure was stable under all the reaction conditions. The origin of the increased activity is not clear but may be due to modification of the catalyst surface and the contribution from new reaction pathways such as steam reforming.     

The development of a high throughput reactor for the catalytic screening of three phase reactions

The design and utilisation of a reactor for the optimisation of multiple heterogeneous catalytic reactions in liquid phase is described. With the ability to screen up to 25 samples simultaneously at a maximum pressure of 50 bar, the reactor is one of the first to be designed specifically for what is termed stage II, the optimisation phase, of catalytic high throughput experimentation (HTE). Experiments demonstrating the reliability and reproducibility of the reactor are described, including the use of the reactor to study the catalytic hydrogenation of crotonaldehyde (CrAld) over bimetallic samples based on a commercial 5 wt.% Pt on activated carbon catalyst. Modification of the mono-metallic Pt sample by the impregnation of aqueous metal salts and various pre-treatments, resulted in 140 bimetallic catalysts that were used in the hydrogenation study. The changes observed in both selectivity and reactivity of the modified catalysts are described and show, by way of example, how the speed of catalyst screening can be increased by at least an order of magnitude.     

Interrelated Mechanism by Which the Methide Quinone Celastrol,Obtained from the Roots of Tripterygium wilfordii,Inhibits Main Protease 3CLpro of COVID-19 and Acts as Superoxide Radical Scavenger

We describe the potential anti coronavirus disease 2019 (COVID-19) action of the methide quinone inhibitor, celastrol. The related methide quinone dexamethasone is, so far, among COVID-19 medications perhaps the most effective drug for patients with severe symptoms. We observe a parallel redox biology behavior between the antioxidant action of celastrol when scavenging the superoxide radical, and the adduct formation of celastrol with the main COVID-19 protease. The related molecular mechanism is envisioned using molecular mechanics and dynamics calculations. It proposes a covalent bond between the S(Cys145) amino acid thiolate and the celastrol A ring, assisted by proton transfers by His164 and His41 amino acids, and a π interaction from Met49 to the celastrol B ring. Specifically, celastrol possesses two moieties that are able to independently scavenge the superoxide radical: the carboxylic framework located at ring E, and the methide-quinone ring A. The latter captures the superoxide electron, releasing molecular oxygen, and is the feature of interest that correlates with the mechanism of COVID-19 inhibition. This unusual scavenging of the superoxide radical is described using density functional theory (DFT) methods, and is supported experimentally by cyclic voltammetry and X-ray diffraction.     

Pressureless sintering of β-SiAlON ceramic compositions using fluorine and oxide additive system

SiAlONs are silicon aluminium oxynitride ceramic materials with a range of technically important applications, from cutting tools to specialised refractories and the properties of SiAlONs can be tailored for specific purposes. In this study, different β-SiAlON compositions were prepared using fluoride (MgF₂ as fluorine source plus Y₂O₃) and oxide (MgO plus Y₂O₃). These compositions were pressureless sintered under nitrogen atmosphere in the range of 1450–1750 °C for 0.5–2.5 h for comparison of densification behaviour and mechanical properties. Densities of samples were measured and analyses of result products were carried out using SEM and XRD. The F-doped sintered β-SiAlON ceramics showed better densities and less pore micrographs especially at lower temperatures compared with the fluorine free samples. Full densifications were achieved for β-SiAlON ceramics with fluoride addition at 1700 °C for 60 min. Consequently, fluorine addition to additive system has a good effect on mechanical properties and densification behaviour.     

Collaborative test of determination of iodine value in fish oils. 1. Reaction time and carbon tetrachloride or cyclohexane as solvents

Twenty-two laboratories participated in a collaborative test to determine the iodine value (IV) of eight samples of fish oil (four with IV<150, four with IV>150) with either carbon tetrachloride (AOCS Official Method Cd 1–25) or cyclohexane (AOCS Recommended Practice Cd 1b-87) as solvent and either 1 or 2 h of reaction time. Laboratories received coded duplicate samples (hidden duplicates) and carried out duplicate determinations on each oil by each solvent-time combination (open duplicates). Replacing carbon tetrachloride with cyclohexane resulted in a lower IV (P<0.001). The decrease averaged 1.6 IV units for low-IV oils and 3.8 IV units for high-IV oils; this difference in response of 2.2 IV units between low- and high-IV oils was significant (P<0.001). Increasing the reaction time had a relatively small effect (0.34±0.18). There was no interaction of reaction time with solvent or oil type. Cyclohexane caused emulsions, which made it difficult to titrate residual iodine and thus increased the variability of the determination. The repeatability standard deviations (s _r ), based on hidden duplicates, for 1-h reaction time with carbon tetrachloride and cyclohexane were 2.17 and 3.35, respectively. The corresponding reproducibility standard deviations were 2.73 and 4.53.     

An FTIR/ATR in situ study of sorption and transport in corrosion protective organic coatings: Paper 2. The effects of temperature and isotopic dilution

A detailed temperature variation (18–50 °C) FTIR/ATR study of sorption and desorption of water into a series of cured epoxy resins has been reported. For higher temperatures (35–50 °C) the data were modelled with a single Fickian diffusion equation, giving an increased D as the temperature increased and an activation energy (E_A) in the 55–60 kJ mol⁻¹ region. At lower temperatures (18–35 °C)—well-below the T_g—a two-stage sorption equation was needed and the apparent E_A was negative. This is probably associated with changes in water clustering among the distributed ‘voids’ in the glassy polymer associated with chain relaxation at extended times. The use of D₂O as a penetrant allowed diffusion coefficient measurements for highly dense epoxy matrices, where FTIR/ATR cannot detect the ν(OH) band of water over and above the residual polymer–OH groups (in the dry state). The data for the D₂O studies were notably influenced by isotopic exchange; which was found to be a diffusion controlled process, even in a polymer matrix.     

Chemical Biology Towards Precision Medicine

Organic chemistry is primed to fill a much-needed gap in our understanding of human biology and disease on the one hand and our ability to treat disease effectively on the other. The key challenge is to discover compounds having the novel mechanisms of action demanded by these new patient-derived insights.