A simple isothermal model for homogeneous-heterogeneous reactions in boundary-layer flow. I Equal diffusivities

A simple model for homogeneous-heterogeneous reactions in stagnation-point boundary-layer flow is constructed in which the homogeneous (bulk) reaction is assumed to be given by isothermal cubic autocatalator kinetics and the heterogeneous (surface) reaction by first order kinetics. The possible steady states of this system are analysed in detail in the case when the diffusion coefficients of both reactant and autocatalyst are equal. Hysteresis bifurcations leading to multiple solutions are found. The temporal stability of these steady states is then discussed.     

Zur Strömung viskoser Flüssigkeiten durch gewellte Rohre

Zusammenfassung Die Strömung zäher nicht-newtonscher Flüssigkeiten durch gewellte kreisförmige Rohre unter Wirkung eines axialen Druckgefälles wurde theoretisch und experimentell untersucht. Das besondere Interesse galt dabei der durch die Wellung veränderten Druck-Durchsatz-Charakteristik. Die theoretischen Betrachtungen beziehen sich auf den Grenzfall hinreichend langer Wellen, wo sich der Querschnitt des Flüssigkeitsfadens in Strömungsrichtung nur langsam ändert und sowohl die Trägheit als auch die Elastizität der Flüssigkeit eine untergeordnete Rolle spielen. In dieser Näherung konnte der Durchsatz in Abhängigkeit vom Druckgefälle und den nichtlinearen Fließeigenschaften der Flüssigkeit für beliebige Wellenamplituden analytisch bestimmt werden. Die theoretischen Ergebnisse sind in Einklang mit experimentellen Befunden.

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The flow of a non-Newtonian fluid driven by an axial pressure gradient through a corrugated pipe of circular cross-section is analysed theoretically and realized experimentally. Particular attention is directed toward the pressure-discharge characteristics of the pipe which change due to the corrugation. A theory is developed for the limiting case of corrugations with long wave-length, where the cross-section of the pipe varies gradually in the flow direction and the effects of inertia and elasticity of the fluid are of minor importance. Within such a long-wave approximation the flow rate, in dependence on the applied pressure drop and on the non-linear viscous properties of the fluid, is determined analytically for arbitrary wave amplitudes. The theoretical results are in agreement with experimental findings.

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Efficient complexation of pyrrole-bridged dizinc(II) bisporphyrin with fluorescent probe pyrene: synthesis, structure, and photoinduced singlet-singlet energy transfer

A diethylpyrrole‐bridged dizinc(II) bisporphyrin (Zn₂DEP) is reported that encapsulates fluorescent probe pyrene molecules through strong π–π interactions, which can relay information about the chemical environment in the interior of the host–guest supramolecular assembly. X‐ray structures of both Zn₂DEP and the encapsulated pyrene complex are reported, which provides a rare opportunity to investigate the structural changes upon guest binding. A comparative structural analysis demonstrated the exceptional ability of this bisporphyrin platform to open its binding pocket for pyrene encapsulation by a vertical displacement of more than 2.45 Å, although both Zn₂DEP and the pyrene complex have nearly parallel porphyrin ring orientations. The ¹H NMR spectrum of the encapsulated pyrene complex in solution shows the upfield shifts of the pyrene protons due to a strong ring current effect, which demonstrates the retention of the solid‐state structure in solution. To further assess the extent to which pyrene guests remain encapsulated in solution, a known fluorescence quencher, dimethylaniline, was added to the host–guest assembly, which shows no exciplex formation for days in nonpolar solvents. Thus, the assembly also retained the structural integrity in solution for a long time. The association constant (K_asso) for such a complexation process in solution was observed to be 1.78×10⁵ M ^?2 for 1:2 binding. Steady‐state fluorescence and lifetime studies indicate significant photoinduced singlet–singlet energy transformation from the excited state of pyrene to zinc bisporphyrin.     

Catalytic dioxygen activation by Co(II) complexes employing a coordinatively versatile ligand scaffold

The ligand bis(2-isobutyrylamidophenyl)amine has been prepared and used to stabilize both mononuclear and dinuclear cobalt(II) complexes. The nuclearity of the cobalt product is regulated by the deprotonation state of the ligand. Both complexes catalytically oxidize triphenylphosphine to triphenylphosphine oxide in the presence of O(2).     

Thermal analyses of organic powders made from precipitation polymerization of triallyl monomers

Organic solids have been prepared from radical-initiated activation of solutions composed of tetradecane and triallyl trimesate (TAM) monomer or triallyl phosphate (TAP) monomer using a recently developed variation of precipitation polymerization methods. The powders, which comprise fused aggregates, are shown to be rich in monomer (83–88 wt% TAM or 86–92 wt% TAP), and are believed to be formed by a combination of hydrocarbon addition and allyl group oligomerization. TAM-g-tetradecane primary particles are on the order of 500 nm in diameter, while TAP-g-tetradecane particles are on the order of 100–200 nm diameter. These products are thermochemically assessed using a combination of differential scanning calorimetry, thermogravimetry and pyrolysis combustion flow calorimetry. The phosphorus-containing TAP-g-tetradecane shows exothermic activity around 230 °C, likely due to thermal decomposition of the trialkyl phosphate moiety, and may find use in advanced materials applications.     

The Relationship Between VHI Scores and Specific Acoustic Measures of Mildly Disordered Voice Production

This study was designed to examine the relationship between the Voice Handicap Index (VHI) and acoustic measures of voice samples common in clinical practice. Fifty participants, 38 women and 12 men, ranging in age from 19 to 80 years, with a mean age of 49 years, served as participants. Of these 50 participants, 17 participants could be included in the acoustic analysis of voice based on measures of error calculated with the TF32 software. All participants completed the VHI and provided voice samples including three trials of the sustained vowel /A/ at a comfortable loudness level as well as a connected speech sample consisting of the Zoo Passage. Acoustic measures were made with TF32 and Cool Edit software and included fundamental frequency, jitter %, shimmer %, signal-to-noise ratio, mean root-mean-square intensity, fundamental frequency standard deviation, aphonic periods, and breath groups. Results indicate that these measures were not predictive of overall VHI score, and no cohesive or predictable pattern was identified when comparing individual measures with overall VHI or with each subscale item. Likely contributions to this lack of correlation and subsequent clinical implications are discussed, as well as the direction for further research.     

Heat transfer for laminar flow through parallel porous disks of different permeability

The problem of temperature distribution and heat transfer for laminar flow through two parallel porous disks of different permeability, has been investigated when the flow is entirely due to injection and/or suction at the two disks. Viscous dissipation terms have been included in the energy equation and the injection and/or suction velocities at the two disks are assumed to be small. The boundaries are kept at constant temperatures. The variation of temperature and Nusselt numbers at the two disks has been graphically depicted for various values of the injection and suction velocities.     

Biocompatibility of gold nanoparticles and their endocytotic fate inside the cellular compartment: a microscopic overview

Macrophages are one of the principal immune effector cells that play essential roles as secretory, phagocytic, and antigen-presenting cells in the immune system. In this study, we address the issue of cytotoxicity and immunogenic effects of gold nanoparticles on RAW264.7 macrophage cells. The cytotoxicity of gold nanoparticles has been correlated with a detailed study of their endocytotic uptake using various microscopy tools such as atomic force microscopy (AFM), confocal-laser-scanning microscopy (CFLSM), and transmission electron microscopy (TEM). Our findings suggest that Au(0) nanoparticles are not cytotoxic, reduce the production of reactive oxygen and nitrite species, and do not elicit secretion of proinflammatory cytokines TNF-alpha and IL1-beta, making them suitable candidates for nanomedicine. AFM measurements suggest that gold nanoparticles are internalized inside the cell via a mechanism involving pinocytosis, while CFLSM and TEM studies indicate their internalization in lysosomal bodies arranged in perinuclear fashion. Our studies thus underline the noncytotoxic, nonimmunogenic, and biocompatible properties of gold nanoparticles with the potential for application in nanoimmunology, nanomedicine, and nanobiotechnology.