Mean flow and turbulence statistics over groups of urban-like cubical obstacles

Direct numerical simulations of turbulent flow over regular arrays of urban-like, cubical obstacles are reported. Results are analysed in terms of a formal spatial averaging procedure to enable interpretation of the flow within the arrays as a canopy flow, and of the flow above as a rough wall boundary layer. Spatial averages of the mean velocity, turbulent stresses and pressure drag are computed. The statistics compare very well with data from wind-tunnel experiments. Within the arrays the time-averaged flow structure gives rise to significant 'dispersive stress' whereas above the Reynolds stress dominates. The mean flow structure and turbulence statistics depend significantly on the layout of the cubes. Unsteady effects are important, especially in the lower canopy layer where turbulent fluctuations dominate over the mean flow.

The quasi-nondispersive regimes of long extratropical baroclinic rossby waves over (slowly varying) topography

Actual energy paths of long, extratropical baroclinic Rossby waves in the ocean are difficult to describe simply because they depend on the meridional-wavenumber-to-zonal-wavenumber ratio tau, a quantity that is difficult to estimate both observationally and theoretically. This paper shows, however, that this dependence is actually weak over any interval in which the zonal phase speed varies approximately linearly with tau, in which case the propagation becomes quasi-nondispersive (QND) and describable at leading order in terms of environmental conditions (i.e., topography and stratification) alone. As an example, the purely topographic case is shown to possess three main kinds of QND ray paths. The first is a topographic regime in which the rays follow approximately the contours f/h(alpha c) = a constant (alpha(c) is a near constant fixed by the strength of the stratification, f is the Coriolis parameter, and h is the ocean depth). The second and third are, respectively, "fast" and "slow" westward regimes little affected by topography and associated with the first and second bottom-pressure-compensated normal modes studied in previous work by Tailleux and McWilliams. Idealized examples show that actual rays can often be reproduced with reasonable accuracy by replacing the actual dispersion relation by its QND approximation. The topographic regime provides an upper bound ( in general a large overestimate) of the maximum latitudinal excursions of actual rays. The method presented in this paper is interesting for enabling an optimal classification of purely azimuthally dispersive wave systems into simpler idealized QND wave regimes, which helps to rationalize previous empirical findings that the ray paths of long Rossby waves in the presence of mean flow and topography often seem to be independent of the wavenumber orientation. Two important side results are to establish that the baroclinic string function regime of Tyler and K se is only valid over a tiny range of the topographic parameter and that long baroclinic Rossby waves propagating over topography do not obey any two-dimensional potential vorticity conservation principle. Given the importance of the latter principle in geophysical fluid dynamics, the lack of it in this case makes the concept of the QND regimes all the more important, for they are probably the only alternative to provide a simple and economical description of general purely azimuthally dispersive wave systems.

Quasi-biennial oscillation and tracer distributions in a coupled chemistry-climate model

[ 1] We have used a fully coupled chemistry-climate model (CCM), which generates its own wind and temperature quasi-biennial oscillation (QBO), to study the effect of coupling on the QBO and to examine the QBO signals in stratospheric trace gases, particularly ozone. Radiative coupling of the interactive chemistry to the underlying general circulation model tends to prolong the QBO period and to increase the QBO amplitude in the equatorial zonal wind in the lower and middle stratosphere. The model ozone QBO agrees well with Stratospheric Aerosol and Gas Experiment II and Total Ozone Mapping Spectrometer satellite observations in terms of vertical and latitudinal structure. The model captures the ozone QBO phase change near 28 km over the equator and the column phase change near +/- 15 degrees latitude. Diagnosis of the model chemical terms shows that variations in NOx are the main chemical driver of the O-3 QBO around 35 km, i.e., above the O-3 phase change.

Testing the limits of quasi-geostrophic theory: application to observed laboratory flows outside the quasi-geostrophic regime

We compare laboratory observations of equilibrated baroclinic waves in the rotating two-layer annulus, with numerical simulations from a quasi-geostrophic model. The laboratory experiments lie well outside the quasi-geostrophic regime: the Rossby number reaches unity; the depth-to-width aspect ratio is large; and the fluid contains ageostrophic inertia–gravity waves. Despite being formally inapplicable, the quasi-geostrophic model captures the laboratory flows reasonably well. The model displays several systematic biases, which are consequences of its treatment of boundary layers and neglect of interfacial surface tension and which may be explained without invoking the dynamical effects of the moderate Rossby number, large aspect ratio or inertia–gravity waves. We conclude that quasi-geostrophic theory appears to continue to apply well outside its formal bounds.

Perturbed Rankine vortices in surface quasi-geostrophic dynamics

An analytical dispersion relation is derived for linear perturbations to a Rankine vortex governed by surface quasi-geostrophic dynamics. Such a Rankine vortex is a circular region of uniform anomalous surface temperature evolving under quasi-geostrophic dynamics with uniform interior potential vorticity. The dispersion relation is analysed in detail and compared to the more familiar dispersion relation for a perturbed Rankine vortex governed by the Euler equations. The results are successfully verified against numerical simulations of the full equations. The dispersion relation is relevant to problems including wave propagation on surface temperature fronts and the stability of vortices in quasi-geostrophic turbulence.

Genes related to sex steroids, neural growth, and social-emotional behavior are associated with autistic traits, empathy, and Asperger syndrome

Genetic studies of autism spectrum conditions (ASC) have mostly focused on the "low functioning" severe clinical subgroup, treating it as a rare disorder. However, ASC is now thought to be relatively common ( approximately 1%), and representing one end of a quasi-normal distribution of autistic traits in the general population. Here we report a study of common genetic variation in candidate genes associated with autistic traits and Asperger syndrome (AS). We tested single nucleotide polymorphisms in 68 candidate genes in three functional groups (sex steroid synthesis/transport, neural connectivity, and social-emotional responsivity) in two experiments. These were (a) an association study of relevant behavioral traits (the Empathy Quotient (EQ), the Autism Spectrum Quotient (AQ)) in a population sample (n=349); and (b) a case-control association study on a sample of people with AS, a "high-functioning" subgroup of ASC (n=174). 27 genes showed a nominally significant association with autistic traits and/or ASC diagnosis. Of these, 19 genes showed nominally significant association with AQ/EQ. In the sex steroid group, this included ESR2 and CYP11B1. In the neural connectivity group, this included HOXA1, NTRK1, and NLGN4X. In the socio-responsivity behavior group, this included MAOB, AVPR1B, and WFS1. Fourteen genes showed nominally significant association with AS. In the sex steroid group, this included CYP17A1 and CYP19A1. In the socio-emotional behavior group, this included OXT. Six genes were nominally associated in both experiments, providing a partial replication. Eleven genes survived family wise error rate (FWER) correction using permutations across both experiments, which is greater than would be expected by chance. CYP11B1 and NTRK1 emerged as significantly associated genes in both experiments, after FWER correction (P<0.05). This is the first candidate-gene association study of AS and of autistic traits. The most promising candidate genes require independent replication and fine mapping.

The role of protecting groups in the formation of organogels through a nano-fibrillar network formed by self-assembling terminally protected tripeptides

A series of eight synthetic self-assembling terminally blocked tripeptides have been studied for gelation. Some of them form gels in various aromatic solvents including benzene, toluene, xylene, and chlorobenzene. It has been found that the protecting groups play an important role in the formation of organogels. It has been observed that, if the C-terminal has been changed from methyl ester to ethyl ester the gelation property does not change significantly (keeping the N-terminal protecting group same), while the change of the protecting group from ethyl ester to isopropyl ester completely abolishes the gelation property. Similarly, keeping the identical C-terminal protecting group (methyl ester) the results of the gelation study indicate that the substitution of N-terminal protection Boc-(tert-butyloxycarbonyl) to Cbz-(benzyloxycarbonyl) does change the gelation property insignificantly, while the change from Boc- to pivaloyl (Piv-) or acetyl (Ac-) group completely eliminates the gelation property. Morphological studies of the dried gels of two of the peptides indicate the presence of an entangled nano-fibrillar network that might be responsible for gelation. FTIR studies of the gels demonstrate that an intermolecular hydrogen bonding network is formed during gelation. Results of X-ray powder diffraction studies for these gelator peptides in different states (dried gels, gel, and bulk solids) reflected that the structure in the wet gel is distinctly different from the dried gel and solid state structures. Single crystal X-ray diffraction studies of a non-gelator peptide, which is structurally similar to the gelator molecules reveal that the peptide forms an antiparallel beta-sheet structure in crystals. (c) 2007 Elsevier Ltd. All rights reserved.

Development of tyrosinase labile protecting groups for amines

The development of two novel protecting groups for amines is described. Thus, a range of amines have been converted to ureas, and the deprotection of these upon exposure to mushroom tyrosinase (E.C. 1.14.18.1) has been demonstrated.

Nitrogen donor ligands bearing N-H groups: Effect on catalytic and cytotoxic activity of molybdenum eta(3)-allyldicarbonyl complexes

Reactions of [Mo(eta(3)-C3H5)Br(CO)(2)(NCMe)(2)] with the bidentate nitrogen ligands 2-(2'-pyridyl)imidazole (L1), 2-(2'-pyridyl)benzimidazole (L2), N,N'-bis(2'-pyridinecarboxamido)-1,2-ethane (L3), and 2,2'-bisimidazole (L4) led to the new complexes [Mo(eta(3)-C3H5)Br(CO)(2)(L)] (L = L1, 1; L2, 2; L4, 4) and [{Mo(eta(3)-C3H5) Br(CO)(2)}(2)(mu-L-3)] (3). The reaction of complexes 2 and 3 with Tl[CF3SO3] afforded [Mo(eta(3)-C3H5)(CF3SO3)(CO)(2)(L2)] (2T) and [{Mo(eta(3)-C3H5)(CF3SO3)(CO)(2)}(2)(mu-L-3)] (3T). Complexes 3 and 2T were structurally characterized by single crystal X-ray diffraction, showing the facial allyl/carbonyls arrangement and the formation of the axial isomer. In 2T, two molecules are assembled in a hydrogen bond dimer. The four complexes 1-4 were tested as precursors in the catalytic epoxidation of cyclooctene and styrene, in the presence of t-butylhydroperoxide (TBHP), with moderate conversions and turnover frequencies for complexes 1-3 and very low ones for 4. The increasing number of N-H groups in the complexes seems to be responsible for the loss of catalytic activity, compared with other related systems. The cytotoxic activities of all the complexes were evaluated against HeLa cells. The results showed that compounds 1,2,4, and 2T exhibited significant activity, complexes 2 and 2T being particularly promising. (C) 2008 Elsevier B.V. All rights reserved.

Thermally responsive elastomeric supramolecular polymers featuring flexible aliphatic hydrogen-bonding end-groups

The present paper details the synthesis, characterization, and preliminary physical analyses of a series of polyisobutylene derivatives featuring urethane and urea end-groups that enable supramolecular network formation to occur via hydrogen bonding. These polymers are readily accessible from relatively inexpensive and commercially available starting materials using a simple two-step synthetic approach. In the bulk, these supramolecular networks were found to possess thermoreversible and elastomeric characteristics as determined by temperature-dependent rheological analysis. These thermoreversible and elastomeric properties make these supramolecular materials potentially very useful in applications such as adhesives and healable surface coatings.

One-pot synthesis and characterization of soluble poly(aryl ether-ketone)s having pendant carboxyl groups

Aromatic poly(ether-ketone)s having pendant carboxyl groups have been obtained by direct, one-pot, Friedel-Crafts copolycondensation of 4,4'-diphenoxybenzophenone with a mixture of terephthaloyl chloride (TC) and trimellitic anhydride acid chloride (TAAC), over a wide range of TAAC/TC molar ratios, in the presence of anhydrous aluminum chloride. The syntheses were performed as precipitation-polycondensations, and the polymers were obtained in particulate form. Besides globular particles of polymer, small quantities of elongated, needlelike particles were observed when the mole ratio TAAC/TC was less than 1. Use of X-ray microdiffraction with synchrotron radiation has revealed that the needlelike material consists of a cyclic compound containing 10 phenylene units, i.e., the crystals are of a [2 + 2] macrocyclic dimer. The polymers obtained are soluble in strong acids and in mixtures of methanesulfonic acid or trifluoroacetic acid with chlorinated hydrocarbons. The molecular structures of the polymers were confirmed by H-1 and C-13 NMR spectroscopy. Reaction of TAAC with 4,4'-diphenoxybenzophenone produced mainly meta-orientation of the resulting ketone linkages. The size of the polymer particles, their molecular weights, and the melting behavior of the products obtained depend on the TAAC/TC ratio used. Ortho-keto acid residues, formed during reaction of anhydride groups of TAAC with 4,4'-diphenoxybenzophenone, exhibit ring-chain tautomerism. A carboxyl-containing aromatic polyketone derived from p-terphenyl, and thus having with no ether linkages in the main chain, was prepared by analogous chemistry, and functional derivatives of carboxy-substituted polyketones were also obtained and characterized.