Asymmetric organocatalysis and the nitro group functionality

The nitro group is an exceptionally versatile functional group, not only because it is essentially a masked amine, but also because its chemistry can be exploited in a number of useful ways. Asymmetric organocatalysis in particular has capitalized on the use of the nitro group towards the synthesis of a variety of nitrogen- containing targets. Perhaps of greatest interest is that this functional group has been shown to be invaluable within the rapidly expanding field of organocatalytic domino reactions. This review features selected examples of nitro group reactivity in organocatalysis to demonstrate its dynamism and utility.

Biochar alteration of the sorption of substrates and products in Soil Enzyme Assays

Pine wood and barley straw biochar amendments to Kettering and Cameroon sandy silt loam soils (15, 30, or 150 mg biochar g−1 soil) caused significant reductions (up to 80%,

The Joint UK Land Environment Simulator (JULES), model description – part 1: energy and water fluxes

This manuscript describes the energy and water components of a new community land surface model called the Joint UK Land Environment Simulator (JULES). This is developed from the Met Office Surface Exchange Scheme (MOSES). It can be used as a stand alone land surface model driven by observed forcing data, or coupled to an atmospheric global circulation model. The JULES model has been coupled to the Met Office Unified Model (UM) and as such provides a unique opportunity for the research community to contribute their research to improve both world-leading operational weather forecasting and climate change prediction systems. In addition JULES, and its forerunner MOSES, have been the basis for a number of very high-profile papers concerning the land-surface and climate over the last decade. JULES has a modular structure aligned to physical processes, providing the basis for a flexible modelling platform.

Urban surface energy balance models: model characteristics and methodology for a comparison study

Many urban surface energy balance models now exist. These vary in complexity from simple schemes that represent the city as a concrete slab, to those which incorporate detailed representations of momentum and energy fluxes distributed within the atmospheric boundary layer. While many of these schemes have been evaluated against observations, with some models even compared with the same data sets, such evaluations have not been undertaken in a controlled manner to enable direct comparison. For other types of climate model, for instance the Project for Intercomparison of Land-Surface Parameterization Schemes (PILPS) experiments (Henderson-Sellers et al., 1993), such controlled comparisons have been shown to provide important insights into both the mechanics of the models and the physics of the real world. This paper describes the progress that has been made to date on a systematic and controlled comparison of urban surface schemes. The models to be considered, and their key attributes, are described, along with the methodology to be used for the evaluation.

Tangeretin regulates platelet function through inhibition of phosphoinositide 3-Kinase and cyclic nucleotide signaling

OBJECTIVE: Dietary flavonoids have long been appreciated in reducing cardiovascular disease risk factors, but their mechanisms of action are complex in nature. In this study, the effects of tangeretin, a dietary flavonoid, were explored on platelet function, signaling, and hemostasis. APPROACH AND RESULTS: Tangeretin inhibited agonist-induced human platelet activation in a concentration-dependent manner. It inhibited agonist-induced integrin αIIbβ3 inside-out and outside-in signaling, intracellular calcium mobilization, and granule secretion. Tangeretin also inhibited human platelet adhesion and subsequent thrombus formation on collagen-coated surfaces under arterial flow conditions in vitro and reduced hemostasis in mice. Further characterization to explore the mechanism by which tangeretin inhibits platelet function revealed distinctive effects of platelet signaling. Tangeretin was found to inhibit phosphoinositide 3-kinase-mediated signaling and increase cGMP levels in platelets, although phosphodiesterase activity was unaffected. Consistent with increased cGMP levels, tangeretin increased the phosphorylation of vasodilator-stimulated phosphoprotein at S239. CONCLUSIONS: This study provides support for the ability and mechanisms of action of dietary flavonoids to modulate platelet signaling and function, which may affect the risk of thrombotic disease.

Protease-activated receptor 2 mediates eosinophil infiltration and hyperreactivity in allergic inflammation of the airway

Trypsin and mast cell tryptase can signal to epithelial cells, myocytes, and nerve fibers of the respiratory tract by cleaving proteinase-activated receptor 2 (PAR2). Since tryptase inhibitors are under development to treat asthma, a precise understanding of the contribution of PAR2 to airway inflammation is required. We examined the role of PAR2 in allergic inflammation of the airway by comparing OVA-sensitized and -challenged mice lacking or overexpressing PAR2. In wild-type mice, immunoreactive PAR2 was detected in airway epithelial cells and myocytes, and intranasal administration of a PAR2 agonist stimulated macrophage infiltration into bronchoalveolar lavage fluid. OVA challenge of immunized wild-type mice stimulated infiltration of leukocytes into bronchoalveolar lavage and induced airway hyperreactivity to inhaled methacholine. Compared with wild-type animals, eosinophil infiltration was inhibited by 73% in mice lacking PAR2 and increased by 88% in mice overexpressing PAR2. Similarly, compared with wild-type animals, airway hyperreactivity to inhaled methacholine (40 micro g/ml) was diminished 38% in mice lacking PAR2 and increased by 52% in mice overexpressing PAR2. PAR2 deletion also reduced IgE levels to OVA sensitization by 4-fold compared with those of wild-type animals. Thus, PAR2 contributes to the development of immunity and to allergic inflammation of the airway. Our results support the proposal that tryptase inhibitors and PAR2 antagonists may be useful therapies for inflammatory airway disease.

Effect of seasonal variation on the composition and properties of raw milk destined for processing in the UK

The composition and physical properties of raw milk from a commercial herd were studied over a one year period in order to understand how best to utilise milk for processing throughout the year. Protein and fat levels demonstrated seasonal trends, while minerals and many physical properties displayed considerable variations, which were apparently unrelated to season. However, rennet clotting time, ethanol stability and foaming ability were subject to seasonal variation. Many significant interrelationships in physico-chemical properties were found. It is clear that the milk supply may be more suited to the manufacture of different products at different times of the year or even on a day to day basis. Subsequent studies will report on variation in production and quality of products manufactured from the same milk samples described in the current study and will thus highlight potential advantages of seasonal processing of raw milk.

Biodiversity, cultural pathways, and human health: a framework

Direct contact with biodiversity is culturally important in a range of contexts. Many people even join conservation organisations to protect biodiversity that they will never encounter first-hand. Despite this, we have little idea how biodiversity affects people's well-being and health through these cultural pathways. Human health is sensitive to apparently trivial psychological stimuli, negatively affected by the risk of environmental degradation, and positively affected by contact with natural spaces. This suggests that well-being and health should be affected by biodiversity change, but few studies have begun to explore these relationships. Here, we develop a framework for linking biodiversity change with human cultural values, well-being, and health. We argue that better understanding these relations might be profoundly important for biodiversity conservation and public health.

Potential sources of mouth drying in beverages fortified with dairy proteins: a comparison of casein and whey-rich ingredients

Oral nutritional supplement drinks (ONS) are beverages high in dairy proteins that are prescribed to individuals at risk of malnutrition. Consumption of ONS is poor in elderly care facilities, with patients commenting that the sensory attributes of these drinks reduce their enjoyment and willingness to consume. Mouth drying is an attribute of ONS found to build with repeated consumption, which may further limit liking of these products. This study investigated the sources of drying sensations by sequential profiling, with a trained sensory panel rating a range of model milk systems and ONS over repeated sips and during after-effects. Sequential profiling found that fortification of milk with both caseinate and whey protein concentrate significantly increased the perception of mouth drying over repeated consumption, increasing by between 35 and 85% over consumption of 40mL. Enrichment of ONS with either whey protein concentrate or milk protein concentrate to a total protein content of 8.7% (wt/wt) resulted in whey and casein levels of 4.3:4.4% and 1.7:7.0% respectively. The product higher in whey protein was substantially more mouth drying, implying that whey proteins may be the most important contributor to mouth drying in ONS. However, efforts to mask mouth drying of protein-fortified milk by increasing sweetness or fat level were unsuccessful at the levels tested. Increasing the viscosity of protein-fortified milk led to a small but significant reduction in mouth drying. However, this approach was not successful when tested within complete ONS. Further analysis is required into the mechanism of protein-derived mouth drying to mask negative sensations and improve the enjoyment and consumption of protein-rich ONS.

Multivalency in healable supramolecular polymers: the effect of supramolecular cross-link density on the mechanical properties and healing of noncovalent polymer networks

Polymers with the ability to heal themselves could provide access to materials with extended lifetimes in a wide range of applications such as surface coatings, automotive components and aerospace composites. Here we describe the synthesis and characterisation of two novel, stimuli-responsive, supramolecular polymer blends based on π-electron-rich pyrenyl residues and π-electron-deficient, chain-folding aromatic diimides that interact through complementary π–π stacking interactions. Different degrees of supramolecular “cross-linking” were achieved by use of divalent or trivalent poly(ethylene glycol)-based polymers featuring pyrenyl end-groups, blended with a known diimide–ether copolymer. The mechanical properties of the resulting polymer blends revealed that higher degrees of supramolecular “cross-link density” yield materials with enhanced mechanical properties, such as increased tensile modulus, modulus of toughness, elasticity and yield point. After a number of break/heal cycles, these materials were found to retain the characteristics of the pristine polymer blend, and this new approach thus offers a simple route to mechanically robust yet healable materials.

The three-dimensional morphology of simulated and observed convective storms over southern England

A set of high-resolution radar observations of convective storms has been collected to evaluate such storms in the UK Met Office Unified Model during the DYMECS project (Dynamical and Microphysical Evolution of Convective Storms). The 3-GHz Chilbolton Advanced Meteorological Radar was set up with a scan-scheduling algorithm to automatically track convective storms identified in real-time from the operational rainfall radar network. More than 1,000 storm observations gathered over fifteen days in 2011 and 2012 are used to evaluate the model under various synoptic conditions supporting convection. In terms of the detailed three-dimensional morphology, storms in the 1500-m grid-length simulations are shown to produce horizontal structures a factor 1.5–2 wider compared to radar observations. A set of nested model runs at grid lengths down to 100m show that the models converge in terms of storm width, but the storm structures in the simulations with the smallest grid lengths are too narrow and too intense compared to the radar observations. The modelled storms were surrounded by a region of drizzle without ice reflectivities above 0 dBZ aloft, which was related to the dominance of ice crystals and was improved by allowing only aggregates as an ice particle habit. Simulations with graupel outperformed the standard configuration for heavy-rain profiles, but the storm structures were a factor 2 too wide and the convective cores 2 km too deep.

Multilevel research in the field of organizational behavior: an empirical look at 10 years of theory and research

During the last 30 years, significant debate has taken place regarding multilevel research. However, the extent to which multilevel research is overtly practiced remains to be examined. This article analyzes 10 years of organizational research within a multilevel framework (from 2001 to 2011). The goals of this article are (a) to understand what has been done, during this decade, in the field of organizational multilevel research and (b) to suggest new arenas of research for the next decade. A total of 132 articles were selected for analysis through ISI Web of Knowledge. Through a broad-based literature review, results suggest that there is equilibrium between the amount of empirical and conceptual papers regarding multilevel research, with most studies addressing the cross-level dynamics between teams and individuals. In addition, this study also found that the time still has little presence in organizational multilevel research. Implications, limitations, and future directions are addressed in the end. Organizations are made of interacting layers. That is, between layers (such as divisions, departments, teams, and individuals) there is often some degree of interdependence that leads to bottom-up and top-down influence mechanisms. Teams and organizations are contexts for the development of individual cognitions, attitudes, and behaviors (top-down effects; Kozlowski & Klein, 2000). Conversely, individual cognitions, attitudes, and behaviors can also influence the functioning and outcomes of teams and organizations (bottom-up effects; Arrow, McGrath, & Berdahl, 2000). One example is when the rewards system of one organization may influence employees’ intention to quit and the existence or absence of extra role behaviors. At the same time, many studies have showed the importance of bottom-up emergent processes that yield higher level phenomena (Bashshur, Hernández, & González-Romá, 2011; Katz-Navon & Erez, 2005; Marques-Quinteiro, Curral, Passos, & Lewis, in press). For example, the affectivity of individual employees may influence their team’s interactions and outcomes (Costa, Passos, & Bakker, 2012). Several authors agree that organizations must be understood as multilevel systems, meaning that adopting a multilevel perspective is fundamental to understand real-world phenomena (Kozlowski & Klein, 2000). However, whether this agreement is reflected in practicing multilevel research seems to be less clear. In fact, how much is known about the quantity and quality of multilevel research done in the last decade? The aim of this study is to compare what has been proposed theoretically, concerning the importance of multilevel research, with what has really been empirically studied and published. First, this article outlines a review of the multilevel theory, followed by what has been theoretically “put forward” by researchers. Second, this article presents what has really been “practiced” based on the results of a review of multilevel studies published from 2001 to 2011 in business and management journals. Finally, some barriers and challenges to true multilevel research are suggested. This study contributes to multilevel research as it describes the last 10 years of research. It quantitatively depicts the type of articles being written, and where we can find the majority of the publications on empirical and conceptual work related to multilevel thinking.

Genetic, structural, and molecular insights into the function of ras of complex proteins domains

Ras of complex proteins (ROC) domains were identified in 2003 as GTP binding modules in large multidomain proteins from Dictyostelium discoideum. Research into the function of these domains exploded with their identification in a number of proteins linked to human disease, including leucine-rich repeat kinase 2 (LRRK2) and death-associated protein kinase 1 (DAPK1) in Parkinson’s disease and cancer, respectively. This surge in research has resulted in a growing body of data revealing the role that ROC domains play in regulating protein function and signaling pathways. In this review, recent advances in the structural informa- tion available for proteins containing ROC domains, along with insights into enzymatic function and the integration of ROC domains as molecular switches in a cellular and organismal context, are explored.