Predicting polycyclic aromatic hydrocarbon formation with an automatically generated mechanism for acetylene pyrolysis

Using Reaction Mechanism Generator (RMG), we have automatically constructed a detailed mechanism for acetylene pyrolysis, which predicts formation of polycyclic aromatic hydrocarbons (PAHs) up to pyrene. To improve the data available for formation pathways from naphthalene to pyrene, new high‐pressure limit reaction rate coefficients and species thermochemistry were calculated using a combination of electronic structure data from the literature and new quantum calculations. Pressure‐dependent kinetics for the CH potential energy surface calculated by Zádor et al. were incorporated to ensure accurate pathways for acetylene initiation reactions. After adding these new data into the RMG database, a pressure‐dependent mechanism was generated in a single RMG simulation which captures chemistry from C to C. In general, the RMG‐generated model accurately predicts major species profiles in comparison to plug‐flow reactor data from the literature. The primary shortcoming of the model is that formation of anthracene, phenanthrene, and pyrene are underpredicted, and PAHs beyond pyrene are not captured. Reaction path analysis was performed for the RMG model to identify key pathways. Notable conclusions include the importance of accounting for the acetone impurity in acetylene in accurately predicting formation of odd‐carbon species, the remarkably low contribution of acetylene dimerization to vinylacetylene or diacetylene, and the dominance of the hydrogen abstraction CH addition (HACA) mechanism in the formation pathways to all PAH species in the model. This work demonstrates the improved ability of RMG to model PAH formation, while highlighting the need for more kinetics data for elementary reaction pathways to larger PAHs.     

Activity-Directed Synthesis of Inhibitors of the p53/hDM2 Protein–Protein Interaction

Protein–protein interactions (PPIs) provide a rich source of potential targets for drug discovery and biomedical science research. However, the identification of structural-diverse starting points for discovery of PPI inhibitors remains a significant challenge. Activity-directed synthesis (ADS), a function-driven discovery approach, was harnessed in the discovery of the p53/hDM2 PPI. Over two rounds of ADS, 346 microscale reactions were performed, with prioritisation on the basis of the activity of the resulting product mixtures. Four distinct and novel series of PPI inhibitors were discovered that, through biophysical characterisation, were shown to have promising ligand efficiencies. It was thus shown that ADS can facilitate ligand discovery for a target that does not have a defined small-molecule binding site, and can provide distinctive starting points for the discovery of PPI inhibitors.     

Scaling law analysis of electrohydrodynamics and dielectrophoresis for isomotive dielectrophoresis microfluidic devices

Isomotive dielectrophoresis (isoDEP) is a unique DEP geometrical configuration where the gradient of the field-squared () is constant. IsoDEP analyzes polarizable particles based on their magnitude and direction of translation. Particle translation is a function of the polarizability of both the particles and suspending medium, the particles’ size and shape, and the frequency of the electric field. However, other electrokinetics act on the particles simultaneously, including electrothermal hydrodynamics. Hence, to maximize the DEP force relative to over electrokinetic forces, design parameters such as microchannel geometry, fabrication materials, and applied electric field must be properly tuned. In this work, scaling law analyses were developed to derive design rules, relative to particle diameter, to reduce unwanted electrothermal hydrodynamics relative to DEP-induced particle translation. For a particle suspended in 10 mS/m media, if the channel width and height are below ten particle diameters, the electrothermal-driven flow is reduced by ∼500 times compared to a channel that is 250 particles diameters in width and height. Replacing glass with silicon as the device's underlying substrate for an insulative-based isoDEP reduces the electrothermal induced flow approximately 20 times less.     

Nickel‐Catalyzed Amination of Aryl Chlorides with Ammonia or Ammonium Salts

The nickel‐catalyzed amination of aryl chlorides to form primary arylamines occurs with ammonia or ammonium sulfate and a well‐defined single‐component nickel(0) precatalyst containing a Josiphos ligand and an η²‐bound benzonitrile ligand. This system also catalyzes the coupling of aryl chlorides with gaseous amines in the form of their hydrochloride salts.     

A linear theory of straight elastic rods

This paper is based on the work of Green & Laws who have given a general thermodynamical theory of rods which is valid for any material. Here, starting with the general non-linear theory of elastic rods, we derive a linear theory allowing for thermal effects. The resulting free energy as a quadratic function of kinematic variables is restricted by certain symmetry conditions. The basic equations then separate into four groups, two for flexure, one for torsion and one for extension of the rod with temperature effects occurring only in the latter group. Wave propagation along an infinite rod is considered. There are two wave speeds for each type of flexure, two for torsion and three for isothermal extension and all wave speeds depend on the wave length.     

Composite and filament models for the mechanical behaviour of elastomeric materials

In this work we present a composite model, which combines the approach of Poisson's function with the filament theory and requires three material parameters. We also suggest the form for a strain-energy function that approximates the constitutive equations of the composite model. Furthermore, a simple asymptotic analysis allows us to reduce the number of material constants to only two, thus, forming a new filament model. The predictive capability of the two models to reproduce the mechanical behaviour of elastomeric materials in deformation experiments is evaluated against the extensive data of Kawabata et al. (Macromolecules 14 (1981) 154). The models give excellent agreement in not only uniaxial and equibiaxial but also non-equibiaxial extension. Although being rather more simplistic in comparison with some successful network models involving non-Gaussian chain statistics, the two models conform much more closely to the classical experimental data of Treloar (Trans. Faraday Soc. 40 (1944) 59).     

A comparison of quasi-static uniaxial-strain and hugoniot tests for quartz-phenolic composite

The purpose of this paper is to show that, within experimental uncertainty, the change in volume with stress obtained by quasi-static uniaxial-strain tests matches that obtained by hugoniot experiments over the same pressure range for quartz phenolic. The result of these tests shows that comparing the data by both techniques is meaningful. In addition, the use of the relatively simple and inexpensive quasi-static uniaxial-strain test (strain rates of 10^?4/sec) may provide designers and materials engineers a method for rapid surveying of materials for their hugoniot properties.     

Parameterization of the in-water motions of falling cylinders using high-speed video

A methodology to observe the motions of large cylinders falling freely at large (~10⁶) Reynolds numbers using a stereometric, high-speed video technique is presented. Parameter variation in length, weight, center of mass, and nose shape combined with changes in release height and initial inclination angle were used to estimate the influence of net drag forces on six cylinder bodies. Cylinders with coincident centers of volume and mass typically assumed body orientations with the major axis aligned normal to the path of descent indicating that buoyancy forces and turbulent drag balanced the inertia of the body and displaced water. Displacement of the center of mass resulted in more vertical orientations and more complex motions. Abrupt changes in position, orientation, and velocity were also observed when air-dropped cylinders separated from a trapped cloud of bubbles signifying the onset of less predictable behaviors.