Reaction mechanisms of carbon dioxide methanation

Constant increase of carbon dioxide emissions from anthropogenic activities leads to the search of options for its recycling and utilization. Although recycled CO₂ utilization as a raw material for the production of chemicals and propellants can be challenging, it is the most sustainable way to mitigate its emissions. Among the most promising applications of CO₂ is its catalytic fixation with hydrogen via the methanation reaction to methane. CO₂ methanation, depending on the used catalyst and overall reaction conditions, can proceed through different mechanism or pathways. A literature review on the methanation reaction mechanism shows that CO₂ can be converted to methane either by direct methanation or through the formation of a CO intermediate. This article analyses the proposed reaction mechanisms of CO₂ methanation.     

Electrical conductivity imaging via contactless measurements

A new imaging modality is introduced to image electrical conductivity of biological tissues via contactless measurements. This modality uses magnetic excitation to induce currents inside the body and measures the magnetic fields of the induced currents. In this study, the mathematical basis of the methodology is analyzed and numerical models are developed to simulate the imaging system. The induced currents are expressed using the A-phi formulation of the electric field where A is the magnetic vector potential and phi is the scalar potential function. It is assumed that A describes the primary magnetic vector potential that exists in the absence of the body. This assumption considerably simplifies the solution of the secondary magnetic fields caused by induced currents. In order to solve phi for objects of arbitrary conductivity distribution a three-dimensional (3-D) finite-element method (FEM) formulation is employed. A specific 7 x 7-coil system is assumed nearby the upper surface of a 10 x 10 x 5-cm conductive body. A sensitivity matrix, which relates the perturbation in measurements to the conductivity perturbations, is calculated. Singular-value decomposition of the sensitivity matrix shows various characteristics of the imaging system. Images are reconstructed using 500 voxels in the image domain, with truncated pseudoinverse. The noise level is assumed to produce a representative signal-to-noise ratio (SNR) of 80 dB. It is observed that it is possible to identify voxel perturbations (of volume 1 cm3) at 2 cm depth. However, resolution gradually decreases for deeper conductivity perturbations.     

A Radical Process towards the Development of Transition‐Metal‐Free Aromatic Carbon?Carbon Bond‐Forming Reactions

Transition‐metal‐free cross‐coupling reactions have been a hot topic in recent years. With the aid of a radical initiator, a number of unactivated arene C? H bonds can be directly arylated/functionalized by using aryl halides through homolytic aromatic substitution. Commercially available or specially designed promoters (e.g. diamines, diols, and amino alcohols) have been used to make this synthetically attractive method viable. This protocol offers an inexpensive, yet efficient route to aromatic C? C bond formations since transition metal catalysts and impurities can be avoided by using this reaction system. In this article, we focus on the significance of the reaction conditions (e.g. bases and promoters), which allow this type of reaction to proceed smoothly. Substrate scope limitations and challenges, as well as mechanistic discussion are also included.     

GPU-accelerated atom and dynamic bond visualization using hyperballs: a unified algorithm for balls, sticks, and hyperboloids

Ray casting on graphics processing units (GPUs) opens new possibilities for molecular visualization. We describe the implementation and calculation of diverse molecular representations such as licorice, ball-and-stick, space-filling van der Waals spheres, and approximated solvent-accessible surfaces using GPUs. We introduce HyperBalls, an improved ball-and-stick representation replacing tubes, linking the atom spheres by hyperboloids that can smoothly connect them. This type of depiction is particularly useful to represent dynamic phenomena, such as the evolution of noncovalent bonds. It is furthermore well suited to represent coarse-grained models and spring networks. All these representations can be defined by a single general algebraic equation that is adapted for the ray-casting technique and is well suited for execution on the GPU. Using GPU capabilities, this implementation can routinely, accurately, and interactively render molecules ranging from a few atoms up to huge macromolecular assemblies with more than 500,000 particles. In simple cases, based only on spheres, we have been able to display up to two million atoms smoothly.     

A Glycosylated Cationic Block Poly(β‐peptide) Reverses Intrinsic Antibiotic Resistance in All ESKAPE Gram‐Negative Bacteria

Carbapenem‐resistant Gram‐negative bacteria (GNB) are heading the list of pathogens for which antibiotics are the most critically needed. Many antibiotics are either unable to penetrate the outer‐membrane or are excluded by efflux mechanisms. Here, we report a cationic block β‐peptide (PAS8‐b‐PDM12) that reverses intrinsic antibiotic resistance in GNB by two distinct mechanisms of action. PAS8‐b‐PDM12 does not only compromise the integrity of the bacterial outer‐membrane, it also deactivates efflux pump systems by dissipating the transmembrane electrochemical potential. As a result, PAS8‐b‐PDM12 sensitizes carbapenem‐ and colistin‐resistant GNB to multiple antibiotics in vitro and in vivo. The β‐peptide allows the perfect alternation of cationic versus hydrophobic side chains, representing a significant improvement over previous antimicrobial α‐peptides sensitizing agents. Together, our results indicate that it is technically possible for a single adjuvant to reverse innate antibiotic resistance in all pathogenic GNB of the ESKAPE group, including those resistant to last resort antibiotics.     

Symmetry-Based Indexing of Image Databases

The use of shape as a cue for indexing into pictorial databases has been traditionally based on global invariant statistics and deformable templates, on the one hand, and local edge correlation on the other. This paper proposes an intermediate approach based on a characterization of the symmetry in edge maps. The use of symmetry matching as a joint correlation measure between pairs of edge elements further constrains the comparison of edge maps. In addition, a natural organization of groups of symmetry into a hierarchy leads to a graph-based representation of relational structure of components of shape that allows for deformations by changing attributes of this relational graph. A graduated assignment graph matching algorithm is used to match symmetry structure in images to stored prototypes or sketches. The results of matching sketches and grey-scale images against a small database consisting of a variety of fish, planes, tools, etc., are promising.     

Analysis of open-loop tanlock carrier recovery for BPSK

An approximate analysis valid for high SNR, is presented for the probability density function of the phase tracking error of the open-loop carrier recovery structure for BPSK proposed by Kam (see ibid., vol. 30, no. 23, p. 1923-4). The result is verified by computer simulations, and enables the evaluation of error probability of the tanlock structure     

Transported PDF Modelling of a High Velocity Bluff-Body Stabilised Flame (HM2) Using Detailed Chemistry

A transported probability density function (PDF) approach closed at the joint scalar level was used to model a bluff body stabilised turbulent diffusion flame (HM2) investigated experimentally by Masri and co-workers. The current effort extends a previous study of HM1 (Re?=?15,800) to a flame with a higher degree of local extinction (Re?=?23,900). The impact of an algebraic model that accounts for local Damköhler number effects on the time-scale ratio of scalar to mechanical turbulence is also evaluated along with the impact of improved thermochemistry. The computations have been performed using a hybrid Monte Carlo/finite volume algorithm and a systematically reduced H/C/N/O mechanism featuring 300 reactions, 20 solved and 28 steady-state species. The joint scalar PDF equations were solved using moving particles in a Lagrangian framework and the velocity field was closed at the second moment level. The redistribution terms were modelled using the Generalized Langevin model of Haworth and Pope. Results show that scalar fields are reproduced with encouraging accuracy and that the revised time scale model improves agreement with experimental data. A high sensitivity to the NO chemistry was observed and encouraging agreement was obtained for the first two moments following adoption of updated reaction rates proposed in an earlier study.     

Nonmigratory internal plasticization of poly(vinyl chloride) via pendant triazoles bearing alkyl or polyether esters

Branched and linear nonmigratory internal plasticizers attached to PVC by a pendant triazole linkage were synthesized and investigated. Copper-free azide-alkyne thermal cycloaddition was employed to covalently bind triazole-based phthalate mimics to PVC. To systematically investigate the effect of plasticizer structure on glass transition temperature, several architectural motifs were explored. Free volume theory was considered when designing many of these internal plasticizers: hexyl-tethers were utilized to generate additional space between the triazole-phthalate mimic and the polymer backbone. Miscibility of these triazole-plasticizers in PVC is important: variation of the ester moieties on the triazole possessing alkyl and/or poly(ethylene oxide) chains produced a wide range of glass transition temperatures (T_g): from anti-plasticizing 96 °C, to highly efficient plasticized materials exhibiting T_g values as low as −42 °C. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2397–2411