Hydrophosphinylation of Styrenes Catalysed by Well‐Defined s‐Block Bimetallics

Advancing the applications of s-block heterobimetallic complexes in catalysis, we report the use of potassium magnesiate (PMDETA)2K2Mg(CH2SiMe3)4 [PMDETA=N,N,N’,N’,N’’-pentamethyldiethylenetriamine] for the catalytic hydrophosphinylation of styrenes under mild conditions. Exploiting chemical cooperation, this bimetallic approach offers greater catalytic activity and chemoselectivity than the single-metal components KCH2SiMe3 and Mg(CH2SiMe3)2. Stoichiometric studies between (PMDETA)2K2Mg(CH2SiMe3)4 and Ph2P(O)H help to elucidate the constitution of the active catalytic species, and illustrate the influence of donors on the potassium cation coordination, and how this may impact catalytic activity. Mechanistic investigations support that the rate determining step is the insertion of the olefinic substrate

Traveling Wave Fronts and Localized Traveling Wave Convection in Binary Fluid Mixtures

Nonlinear fronts between spatially extended traveling wave convection (TW) and quiescent fluid and spatially localized traveling waves (LTWs) are investigated in quantitative detail in the bistable regime of binary fluid mixtures heated from below. A finite-difference method is used to solve the full hydrodynamic field equations in a vertical cross section of the layer perpendicular to the convection roll axes. Results are presented for ethanol-water parameters with several strongly negative separation ratios where TW solutions bifurcate subcritically. Fronts and LTWs are compared with each other and similarities and differences are elucidated. Phase propagation out of the quiescent fluid into the convective structure entails a unique selection of the latter while fronts and interfaces where the phase moves into the quiescent state behave differently. Interpretations of various experimental observations are suggested.Comment: 46 pages, 11 figures. Accepted for publication in Phys. Rev.

Convection in nanofluids with a particle-concentration-dependent thermal conductivity

Thermal convection in nanofluids is investigated by means of a continuum model for binary-fluid mixtures, with a thermal conductivity depending on the local concentration of colloidal particles. The applied temperature difference between the upper and the lower boundary leads via the Soret effect to a variation of the colloid concentration and therefore to a spatially varying heat conductivity. An increasing difference between the heat conductivity of the mixture near the colder and the warmer boundary results in a shift of the onset of convection to higher values of the Rayleigh number for positive values of the separation ratio psi>0 and to smaller values in the range psi<0. Beyond some critical difference of the thermal conductivity between the two boundaries, we find an oscillatory onset of convection not only for psi<0, but also within a finite range of psi>0. This range can be extended by increasing the difference in the thermal conductivity and it is bounded by two codimension-2 bifurcations.Comment: 13 pages, 11 figures; submitted to Physical Review

Multiple frequencies of synchronization in classical and quantum networks

Complex systems consisting of vector or matrix oscillators can synchronize to a common state characterized by a frequency matrix with distinct eigenvalues, leading to multiple frequencies of synchronization. In quantum networked systems the synchronized state is a linear combination of states corresponding to different energy levels. Suitable symmetry-breaking network interactions, however, allow only one or more such frequencies to appear. A specific example in three dimensions, where all trajectories lie on the 2-sphere, is a model of interacting spin-1 quantum angular momentum states, where synchronization to a nontrivial frequency occurs despite the presence of zero-frequency modes of oscillation.Skye M. Platten, M. A. Lohe, and Peter J. Mora

Sustainable green chemical synthesis of discrete, well-dispersed silver nanoparticles with bacteriostatic properties from carrot extracts aided by polyvinylpyrrolidone

Large amounts of food products are disposed of around the world because they are below market standards. In Australia, low value, non-marketable carrots (Daucus carota) are ploughed into farmlands as green manure or are treated as waste. In recent years significant research interest has focused on developing waste valorisation strategies using new green chemistry-based sustainable processes. More importantly, strategies that also provide solutions for emerging challenges like the rising reports of resistance of bacteria to existing microbes are favourable. This study explored a facile synthesis process to reduce aqueous silver ions in aqueous carrot extracts to form silver nanoparticles that may have antibacterial properties. The synthesis process produced particles with surface plasmon resonance peaks typical of crystalline silver. The silver nanoparticles produced from pure carrot extracts were spherical and pseudo-spherical, 2 to 25 nm wide. However, with polyvinylpyrrolidone, much wider (10-50 nm), well-dispersed silver nanoparticles of various shapes including spherical, polygonal, rod-like and triangular types were produced. Several biomolecules which may act as reducing and capping agents for the process were identified; they included ascorbic, gallic and chlorogenic acids. The Ag nanoparticles produced significant zones of inhibition against the gram-negative E. coli and gram-positive S. epidermidis, indicating they had bacteriostatic properties. The study demonstrates that producing Ag nanoparticles with antibiotic properties from carrots is a good valorisation strategy because other uses for rejected carrot produce such as application as green manure may not be interrupted

Photocatalytic degradation of contaminants of concern with composite NF-TiO2 films under visible and solar light

This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO2) for the removal of contaminants of concern (COCs) in wastewater under visible and solar light. Monodisperse anatase TiO2 nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO2 by direct incorporation into the sol-gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high resolution-transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO2-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO2 + monodisperse TiO2 (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO2-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO2-P25. Using NF-TiO2 layer-by-layer with monodisperse TiO2 (50 nm) under the solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5·10-3 min-1 for caffeine, 12.5 and 9.0·10-3 min-1 for carbamazepine, and 10.9 and 5.8·10-3 min-1 for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO2-based films compared to the direct addition of nanoparticles into the sol

Influence of through-flow on linear pattern formation properties in binary mixture convection

We investigate how a horizontal plane Poiseuille shear flow changes linear convection properties in binary fluid layers heated from below. The full linear field equations are solved with a shooting method for realistic top and bottom boundary conditions. Through-flow induced changes of the bifurcation thresholds (stability boundaries) for different types of convective solutions are deter- mined in the control parameter space spanned by Rayleigh number, Soret coupling (positive as well as negative), and through-flow Reynolds number. We elucidate the through-flow induced lifting of the Hopf symmetry degeneracy of left and right traveling waves in mixtures with negative Soret coupling. Finally we determine with a saddle point analysis of the complex dispersion relation of the field equations over the complex wave number plane the borders between absolute and convective instabilities for different types of perturbations in comparison with the appropriate Ginzburg-Landau amplitude equation approximation. PACS:47.20.-k,47.20.Bp, 47.15.-x,47.54.+rComment: 19 pages, 15 Postscript figure

Bistability of Slow and Fast Traveling Waves in Fluid Mixtures

The appearence of a new type of fast nonlinear traveling wave states in binary fluid convection with increasing Soret effect is elucidated and the parameter range of their bistability with the common slower ones is evaluated numerically. The bifurcation behavior and the significantly different spatiotemporal properties of the different wave states - e.g. frequency, flow structure, and concentration distribution - are determined and related to each other and to a convenient measure of their nonlinearity. This allows to derive a limit for the applicability of small amplitude expansions. Additionally an universal scaling behavior of frequencies and mixing properties is found. PACS: 47.20.-k, 47.10.+g, 47.20.KyComment: 4 pages including 5 Postscript figure

Best friends: children use mutual gaze to identify friendships in others

This study examined children’s ability to use mutual eye gaze as a cue to friendships in others. In Experiment 1, following a discussion about friendship, 4-, 5-, and 6-year-olds were shown animations in which three cartoon children looked at one another, and were told that one target character had a best friend. Although all age groups accurately detected the mutual gaze between the target and another character, only 5- and 6-year-olds used this cue to infer friendship. Experiment 2 replicated the effect with 5- and 6-year-olds when the target character was not explicitly identified. Finally, in Experiment 3, where the attribution of friendship could only be based on synchronized mutual gaze, 6-year-olds made this attribution, while 4- and 5-year-olds did not. Children occasionally referred to mutual eye gaze when asked to justify their responses in Experiments 2 and 3, but it was only by the age of 6 that reference to these cues correlated with the use of mutual gaze in judgements of affiliation. Although younger children detected mutual gaze, it was not until 6 years of age that children reliably detected and justified mutual gaze as a cue to friendship

Influence of boundaries on pattern selection in through-flow

The problem of pattern selection in absolutely unstable open flow systems is investigated by considering the example of Rayleigh-B\'{e}nard convection. The spatiotemporal structure of convection rolls propagating downstream in an externally imposed flow is determined for six different inlet/outlet boundary conditions. Results are obtained by numerical simulations of the Navier-Stokes equations and by comparison with the corresponding Ginzburg-Landau amplitude equation. A unique selection process is observed being a function of the control parameters and the boundary conditions but independent of the history and the system length. The problem can be formulated in terms of a nonlinear eigen/boundary value problem where the frequency of the propagating pattern is the eigenvalue. PACS: 47.54.+r, 47.20.Bp, 47.27.Te, 47.20.KyComment: 8 pages, 5 Postscript figures, Physica D 97, 253-263 (1996