The counter-propagating Rossby-wave perspective on baroclinic instability. Part III: Primitive-equation disturbances on the sphere

Baroclinic instability of perturbations described by the linearized primitive quations, growing on steady zonal jets on the sphere, can be understood in terms of the interaction of pairs of counter-propagating Rossby waves (CRWs). The CRWs can be viewed as the basic components of the dynamical system where the Hamiltonian is the pseudoenergy and each CRW has a zonal coordinate and pseudomomentum. The theory holds for adiabatic frictionless flow to the extent that truncated forms of pseudomomentum and pseudoenergy are globally conserved. These forms focus attention on Rossby wave activity. Normal mode (NM) dispersion relations for realistic jets are explained in terms of the two CRWs associated with each unstable NM pair. Although derived from the NMs, CRWs have the conceptual advantage that their structure is zonally untilted, and can be anticipated given only the basic state. Moreover, their zonal propagation, phase-locking and mutual interaction can all be understood by ‘PV-thinking’ applied at only two ‘home-bases’—potential vorticity (PV) anomalies at one home-base induce circulation anomalies, both locally and at the other home-base, which in turn can advect the PV gradient and modify PV anomalies there. At short wavelengths the upper CRW is focused in the mid-troposphere just above the steering level of the NM, but at longer wavelengths the upper CRW has a second wave-activity maximum at the tropopause. In the absence of meridional shear, CRW behaviour is very similar to that of Charney modes, while shear results in a meridional slant with height of the air-parcel displacement-structures of CRWs in sympathy with basic-state zonal angular-velocity surfaces. A consequence of this slant is that baroclinically growing eddies (on jets broader than the Rossby radius) must tilt downshear in the horizontal, giving rise to up-gradient momentum fluxes that tend to accelerate the barotropic component of the jet.

Supporting multi-organisational collaborative groups in the public sector

In this paper, the issues that arise in multi-organisational collaborative groups (MOCGs) in the public sector are discussed and how a technology-based group support system (GSS) could assist individuals within these groups. MOCGs are commonly used in the public sector to find solutions to multifaceted social problems. Finding solutions for such problems is difficult because their scope is outside the boundary of a single government agency. The standard approach to solving such problems is collaborative involving a diverse range of stakeholders. Collaborative working can be advantageous but it also introduces its own pressures. Conflicts can arise due to the multiple contexts and goals of group members and the organisations that they represent. Trust, communication and a shared interface are crucial to making any significant progress. A GSS could support these elements.

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.

Effects of body size and lifestyle on evolution of mammal life histories

It has recently been proposed that life-history evolution is subject to a fundamental size-dependent constraint. This constraint limits the rate at which biomass can be produced so that production per unit of body mass is inevitably slower in larger organisms than in smaller ones. Here we derive predictions for how changes in body size and production rates evolve in different lifestyles subject to this constraint. Predictions are tested by using data on the mass of neonate tissue produced per adult per year in 637 placental mammal species and are generally supported. Compared with terrestrial insectivores with generalized primitive traits, mammals that have evolved more specialized lifestyles have divergent massspecific production rates: (i) increased in groups that specialize on abundant and reliable foods: grazing and browsing herbivores (artiodactyls, lagomorphs, perissoclactyls, and folivorous rodents) and flesh-eating marine mammals (pinnipeds, cetaceans); and (ii) decreased in groups that have lifestyles with reduced death rates: bats, primates, arboreal, fossorial, and desert rodents, bears, elephants, and rhinos. Convergent evolution of groups with similar lifestyles is common, so patterns of productivity across mammalian taxa reflect both ecology and phylogeny. The overall result is that groups with different lifestyles have parallel but offset relationships between production rate and body size. These results shed light on the evolution of the fast-slow life-history continuum, suggesting that variation occurs along two axes corresponding to body size and lifestyle.

Protochordate Zic genes define primitive somite compartments and highlight molecular changes underlying neural crest evolution

The vertebrate Zic gene family encodes C2H2 zinc finger transcription factors closely related to the Gli proteins. Zic genes are expressed in multiple areas of developing vertebrate embryos, including the dorsal neural tube where they act as potent neural crest inducers. Here we describe the characterization of a Zic ortholog from the amphioxus Branchiostoma floridae and further describe the expression of a Zic ortholog from the ascidian Ciona intestinalis. Molecular phylogenetic analysis and sequence comparisons suggest the gene duplications that formed the vertebrate Zic family were specific to the vertebrate lineage. In Ciona maternal CiZic/Ci-macho1 transcripts are localized during cleavage stages by asymmetric cell division, whereas zygotic expression by neural plate cells commences during neurulation. The amphioxus Zic ortholog AmphiZic is expressed in dorsal mesoderm and ectoderm during gastrulation, before being eliminated first from midline cells and then from all neurectoderm during neurulation. After neurulation, expression is reactivated in the dorsal neural tube and dorsolateral somite. Comparison of CiZic and AmphiZic expression with vertebrate Zic expression leads to two main conclusions. First, Zic expression allows us to define homologous compartments between vertebrate and amphioxus somites, showing primitive subdivision of vertebrate segmented mesoderm. Second, we show that neural Zic expression is a chordate synapomorphy, whereas the precise pattern of neural expression has evolved differently on the different chordate lineages. Based on these observations we suggest that a change in Zic regulation, specifically the evolution of a dorsal neural expression domain in vertebrate neurulae, was an important step in the evolution of the neural crest.

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.

Symposium on 'nutrition interventions in high-risk groups' - CVD risk in South Asians: the importance of defining adiposity and influence of dietary polyunsaturated fat

The prevalence of the metabolic syndrome (MetS), CVD and type 2 diabetes (T2D) is known to be higher in populations from the Indian subcontinent compared with the general UK population. While identification of this increased risk is crucial to allow for effective treatment, there is controversy over the applicability of diagnostic criteria, and particularly measures of adiposity in ethnic minorities. Diagnostic cut-offs for BMI and waist circumference have been largely derived from predominantly white Caucasian populations and, therefore, have been inappropriate and not transferable to Asian groups. Many Asian populations, particularly South Asians, have a higher total and central adiposity for a similar body weight compared with matched Caucasians and greater CVD risk associated with a lower BMI. Although the causes of CVD and T2D are multi-factorial, diet is thought to make a substantial contribution to the development of these diseases. Low dietary intakes and tissue levels of long-chain (LC) n-3 PUFA in South Asian populations have been linked to high-risk abnormalities in the MetS. Conversely, increasing the dietary intake of LC n-3 PUFA in South Asians has proved an effective strategy for correcting such abnormalities as dyslipidaemia in the MetS. Appropriate diagnostic criteria that include a modified definition of adiposity must be in place to facilitate the early detection and thus targeted treatment of increased risk in ethnic minorities.