Navier–Stokes simulations in gappy PIV data

Velocity measurements conducted with particle image velocimetry (PIV) often exhibit regions where the flow motion cannot be evaluated. The principal reasons for this are the absence of seeding particles or limited optical access for illumination or imaging. Additional causes can be laser light reflections and unwanted out-of-focus effects. As a consequence, the velocity field measured with PIV contains regions where no velocity information is available, that is gaps. This work investigates the suitability of using the unsteady incompressible Navier–Stokes equations to obtain accurate estimates of the local transient velocity field in small gaps; the present approach applies to time-resolved two-dimensional experiments of incompressible flows. The numerics are based on a finite volume discretization with partitioned time-stepping to solve the governing equations. The measured velocity distribution at the gap boundary is taken as time-varying boundary condition, and an approximate initial condition inside the gap is obtained via low-order spatial interpolation of the velocity at the boundaries. The influence of this I.C. is seen to diminish over time, as information is convected through the gap. Due to the form of the equations, no initial or boundary conditions on the pressure are required. The approach is evaluated by a time-resolved experiment where the true solution is known a priori. The results are compared with a boundary interpolation approach. Finally, an application of the technique to an experiment with a gap of complex shape is presented.     

Halogenation of 2-Hydroxynicotinic Acid

A convenient method to prepare 5-halo-2-hydroxy-nicotinic acid is described.     

Evidence for the Chain‐Growth Synthesis of Statistical π‐Conjugated Donor–Acceptor Copolymers

The synthesis of a series of dithienosilole–benzotriazole donor–acceptor statistical copolymers with various donor–acceptor ratios is reported, prepared by Kumada catalyst‐transfer polymerization. Statistical copolymer structure is verified by ¹H NMR and optical absorption spectroscopy, and supported by density functional theory (DFT) calculations. The copolymers exhibit a single optical absorption band that lies between dithienosilole and benzotriazole homopolymers, which shifts with varying donor–acceptor content. A chain extension experiment using a partially consumed benzotriazole solution as a macroinitiator followed by addition of dithienosilole leads to the synthesis of a statistical dithienosilole–benzotriazole block copolymer from a pure benzotriazole block, demonstrating that both chain extension and simultaneous monomer incorporation are possible using this methodology.

     

THE SYNTHESIS OF 1,3,2-DIOXAPHOSPHOLENES. EVIDENCE FOR AN ARYLOXYPHOSPHINIDENE INTERMEDIATE

Abstract

The reaction of 2,6-di-t-butyl-4-methylphenylphosphorodichloridite with α-diketones in the presence of magnesium metal affords modest yields of 1,3,2-dioxaphospholenes. This may be the first evidence for the existence of the monocoordinate aryloxyphosphinidene intermediate, ROP.     

Cardiac glycosides: 5. Stereoselective syntheses of digitoxigenin α-D, β-D, α-L,and β-L-glucosides

As part of a continuing study of cardiac g1ycos1des,^1,2 stereoselective syntheses of the four possible glucosides of digitoxigenin were developed via the thermodynamically produced tetra-O-benzyl-D- and L-glucosyl α-trichloroacetaimidates 2α and 11α, and the kinetically produced β-trichloroacetaimidates 2β and 11β. A 58%:19% isolated yield ratio of α-D and β-D benzyl protected glycosides 6 and 3 could be obtained in 30 minutes reaction at ?10°. Halide ion catalysis with a 2:1 excess of tetra-O-benzyl-α-D-glucopyranosyl bromide for 14 days in methylene chloride at room temperature gave a 39%:11% ratio of 6 and 3, along with 43% of recovered digitoxigenin. Debenzylation of the D-glucosides required milder conditions (20% Pd/C, atmospheric pressure, 45 min-1 hr) than the L-glucosides (40% Pd/C, 2 hr) but yields were typically 80% for both groups.     

Computational study of turbulent laminar patterns in couette flow

Turbulent-laminar patterns near transition are simulated in plane Couette flow using an extension of the minimal-flow-unit methodology. Computational domains are of minimal size in two directions but large in the third. The long direction can be tilted at any prescribed angle to the streamwise direction. Three types of patterned states are found and studied: periodic, localized, and intermittent. These correspond closely to observations in large-aspect-ratio experiments.     

Alpha,omega-bis(thioacetyl)oligophenylenevinylene chromophores from thioanisol precursors

The selective cleavage of arylmethyl thioethers provides a convenient protocol for the synthesis of all-E isomers of alpha, omega-bis(thioacetyl)oligophenyenevinylene molecules (OPVs). The S-methyl group is tolerant of Wittig-type and Heck-type reactions for forming OPV structures and can be converted to the S-acetyl group by treatment with sodium thiomethoxide and acetyl chloride. The thermal conditions of the deprotection/reprotection step concurrently isomerize the conjugated chromophore to the all-E isomer, regardless of the stereochemistry of the starting olefins. This approach is demonstrated for a variety of linear and [2.2]paracyclophane containing OPVs, which have been characterized by electrochemical and spectroscopic techniques. Additionally, these S-acetyl-terminated OPVs self-assemble on gold surfaces. Monolayers containing these molecules were characterized by water contact angle measurements, ellipsometry, and X-ray photoelectron spectroscopy.     

Feasibility of probing boundary morphology of structured materials by 2D NMR q-space imaging

It is well known that one-dimensional (1D) q-space imaging allows retrieval of structural information at cellular resolution. Here we demonstrate by simulation that boundary morphology of structured materials can be derived from 2D q-space mapping. Based on a finite-difference model for restricted diffusion, 2D q-space maps obtained from water diffusion inside apertures at various levels of asperity were simulated. The results indicate that the observed ring patterns (diffraction minima) reveal the boundary profiles of the apertures but become blurred in the case of significant variation in aperture size. For uniform size distribution of apertures, a quantitative measure of surface roughness can be established by means of spatial autocorrelation analysis. The results suggest that 2D q-space imaging may allow probing of the boundary morphology of structured materials and possibly biological cells.     

Agent-based and multi-agent simulations: coming of age or in search of an identity?

The promise of agent-based for explicating properties of social systems has not yet been fully realized. Agent models sometimes provide only a veneer of, rather than substantive engagement with, social behavior. The problem will be illustrated with Axelrod’s model for evolution of ethnocentrism (a biological model) versus Schelling’s model for spatial segregation based on preferences (a cultural model). The examples show the need to incorporate both the biological and cultural basis for behavior through a schema that includes behavior based on cultural/cognitive processing of information and behavior based on biological/cognitive processing of information. An example of an agent-based model that implements decision making in this manner is discussed. The model accounts for heterogeneity in behavior outcomes and leads to two main predictions: (1) small scale, hunter-gatherer societies in resource scarce environments will have stable adaptations less affected by variation in resource abundance in comparison to groups in resource rich regions where inter-group conflict is more likely and (2) the relationship between community size, population size and administrative complexity will have two distinct patterns, one for patrilineally organized societies and the other for matrilineally organized societies. Both predictions have been verified empirically.