How carbo-benzenes fit molecules in their inner core as do biologic ion carriers?

Structural Chemistry - The present computational study complements experimental efforts to describe and characterize carbo-benzene derivatives as paradigms of aromatic carbo-mers. A long-lasting...     

No more conventional reference electrode: Transition time for determining chloride ion concentration

Ion selective electrodes (ISE) are used extensively for the potentiometric determination of ion concentrations in electrolytes. However, the inherent drift in these measurements and the requirement of a stable reference electrode restrict the feasibility of this method for long-term in-situ applications. This work presents a chronopotentiometric approach to minimize drift and avoid the use of a conventional reference electrode for measuring chloride ion concentration. An anodic current pulse is applied to a Ag/AgCl working electrode which initiates a faradaic reaction that depletes the chloride ions near the electrode surface. The rate of change in potential at the Ag/AgCl electrode, due to chloride ion depletion, reaches an inflection point once the chloride ions deplete completely near the electrode surface. The moment of the inflection point, also known as the transition time, is a function of the chloride ion concentration and is described by the Sand equation. It is shown that the square root of the transition time is linearly proportional to the chloride ion concentration. Drift in the response over two weeks is negligible: 59 μM/day when measuring 1 mM of Cl⁻ ions using a 10 A m⁻² current pulse. The transition time at a specific ion concentration can be tuned by the applied current pulse, e.g., in a solution containing 5 mM chloride ions, the transition times with current pulses of 10 and 20 A m⁻² are 1.56 and 0.25 s, respectively. The moment of inflection determines the response, and thus is independent of the absolute potential of reference electrode. Therefore, any metal wire can act as a pseudo-reference electrode, enabling this approach for long-term and integrated-sensor applications such as measurement inside concrete structures.     

Spin adducts of group IVB organometallic radicals with Thioketones. an esr study

The radical adducts resulting from the reaction between group IVB organometallic radicals MR₃ (M = Si, Ge, Sn; R = alkyl or aryl) and a number of thioketones of the chromone and flavone series have been investigated by ESR spectroscopy. The spectral parameters obtained for these species have been compared with those of similar adducts of the corresponding ketones. Both classes of radicals adopt an orthogonal conformation, and the differences between the former and the latter paramagnetic species can be accounted for by the different electronegativity of oxygen and sulphur. the effects of substitution of the heterocyclic oxygen with a sulphur or selenium atom on the spin density distribution are likewise explained. INDO calculations have been carried out on the model systems CH₂XSiH₃ (X = O, S).     

Natural Low-Frequency Riblets

A turbulent flow at modest Reynolds numbers (26,000–32,000, as defined in the text) over flat erodible sandy beds was investigated. The beds were composed of sand grains of uniform size with a diameter smaller than the viscous sublayer of the flow. When a modest sand transport (1.2 × 10-3–8.5 × 10-3 g/s·cm) was present, the near-wall coherent structures of the flow produced a bed form with a streaky longitudinal pattern. This pattern had a lateral spacing of about 100 viscous units and had less drag than a flat wall.The mechanism causing the drag reduction is due to a low-frequency riblet pattern which allows the flow to sustain higher wall shear stresses without additional erosion. That means during the riblet regime the sediment transport remains quasi-constant.The formation of the sand streaks as well as the drag reducing mechanism are discussed.     

An analytical interface reconstruction algorithm in the PLIC‐VOF method for 2D polygonal unstructured meshes

Piecewise linear interface calculation (PLIC) schemes have been extensively employed in the volume‐of‐fluid (VOF) method for interface capturing in numerical simulations of multiphase flows. Polygonal unstructured meshes are often adopted because of their geometric flexibility and superiority in gradient calculation. An analytical interface reconstruction algorithm in the PLIC‐VOF method for arbitrary convex polygonal cells has been proposed in this study. The line interface at a given orientation within a polygonal cell is located by an analytical technique. It has been tested successfully for four different geometric shapes that are common in polygonal meshes. The computational efficiency of the present algorithm has been compared with several published schemes in the literature. The proposed algorithm has been shown to yield higher accuracy with reduction in computational complexity. A numerical simulation of a dam‐breaking problem has been performed using the proposed analytical PLIC technique on polygonal meshes. The results are in good agreement with experimental data available in the literature, which serves as a demonstration of its performance in a real multiphase flow.