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.

Participatory scenarios as a tool to link science and policy on food security under climate change in East Africa

How effective are multi-stakeholder scenarios building processes to bring diverse actors together and create a policy-making tool to support sustainable development and promote food security in the developing world under climate change? The effectiveness of a participatory scenario development process highlights the importance of ‘boundary work’ that links actors and organizations involved in generating knowledge on the one hand, and practitioners and policymakers who take actions based on that knowledge on the other. This study reports on the application of criteria for effective boundary work to a multi-stakeholder scenarios process in East Africa that brought together a range of regional agriculture and food systems actors. This analysis has enabled us to evaluate the extent to which these scenarios were seen by the different actors as credible, legitimate and salient, and thus more likely to be useful. The analysis has shown gaps and opportunities for improvement on these criteria, such as the quantification of scenarios, attention to translating and communicating the results through various channels and new approaches to enable a more inclusive and diverse group of participants. We conclude that applying boundary work criteria to multi-stakeholder scenarios processes can do much to increase the likelihood of developing sustainable development and food security policies that are more appropriate.

The influence of a decision support tool on real estate valuations

An appraisal task involves the rendering of market value, an unobservable and hypothetical construct. Direct feedback against this objective is typically not possible, so alternative feedback such as confirmation of previous appraised values may be employed. This may alter the appraiser’s perception of the valuation objective leading to divergence from the appraisal normative model. The real estate literature suggests appraisers have been susceptible to the influence of previous appraised values, often resulting in biased valuations. This research focuses on the efficacy of a decision support tool in eliminating or subduing this bias in the appraisal process.

An environmental uncertainty-based diagnostic reference tool for evaluating the performance of supply chain value streams

This research has responded to the need for diagnostic reference tools explicitly linking the influence of environmental uncertainty and performance within the supply chain. Uncertainty is a key factor influencing performance and an important measure of the operating environment. We develop and demonstrate a novel reference methodology based on data envelopment analysis (DEA) for examining the performance of value streams within the supply chain with specific reference to the level of environmental uncertainty they face. In this paper, using real industrial data, 20 product supply value streams within the European automotive industry sector are evaluated. Two are found to be efficient. The peer reference groups for the underperforming value streams are identified and numerical improvement targets are derived. The paper demonstrates how DEA can be used to guide supply chain improvement efforts through role-model identification and target setting, in a way that recognises the multiple dimensions/outcomes of the supply chain process and the influence of its environmental conditions. We have facilitated the contextualisation of environmental uncertainty and its incorporation into a specific diagnostic reference tool.

Modelling of control options for an outbreak of Mycoplasma gallisepticum in egg production: a decision support tool

Mycoplasma gallisepticum (MG) is a bacterium that causes respiratory disease in chickens, leading to reduced egg production. A dynamic simulation model was developed that can be used to assess the costs and benefits of control using antimicrobials or vaccination in caged or free range systems. The intended users are veterinarians and egg producers. A user interface is provided for input of flock specific parameters. The economic consequence of an MG outbreak is expressed as a reduction in expected egg output. The model predicts that either vaccination or microbial treatment can approximately halve potential losses from MG in some circumstances. Sensitivity analysis is used to test assumptions about infection rate and timing of an outbreak. Feedback from veterinarians points to the value of the model as a discussion tool with producers.

Fire history and the Global Charcoal Database: a new tool for hypothesis testing and data exploration

Version 1 of the Global Charcoal Database is now available for regional fire history reconstructions, data exploration, hypothesis testing, and evaluation of coupled climate–vegetation–fire model simulations. The charcoal database contains over 400 radiocarbon-dated records that document changes in charcoal abundance during the Late Quaternary. The aim of this public database is to stimulate cross-disciplinary research in fire sciences targeted at an increased understanding of the controls and impacts of natural and anthropogenic fire regimes on centennial-to-orbital timescales. We describe here the data standardization techniques for comparing multiple types of sedimentary charcoal records. Version 1 of the Global Charcoal Database has been used to characterize global and regional patterns in fire activity since the last glacial maximum. Recent studies using the charcoal database have explored the relation between climate and fire during periods of rapid climate change, including evidence of fire activity during the Younger Dryas Chronozone, and during the past two millennia.

An analysis of UK policies for domestic energy reduction using an agent based tool

This paper introduces a new agent-based model, which incorporates the actions of individual homeowners in a long-term domestic stock model, and details how it was applied in energy policy analysis. The results indicate that current policies are likely to fall significantly short of the 80% target and suggest that current subsidy levels need re-examining. In the model, current subsidy levels appear to offer too much support to some technologies, which in turn leads to the suppression of other technologies that have a greater energy saving potential. The model can be used by policy makers to develop further scenarios to find alternative, more effective, sets of policy measures. The model is currently limited to the owner-occupied stock in England, although it can be expanded, subject to the availability of data.

Effect of "Pollutants" on the functionality of breathable roofing membranes in a bat roost

The performance of breathable roofing membranes (BRM’s) in buildings where bats roost have been investigated using experimental measurements and numerical simulations. Measurement techniques as outlined in BS EN ISO 12572 of membranes from manufacturers in its pure state and those that have been contaminated with bat urine, faeces and natural oils transmitted via fur because they were found in bat roost have been tested for their permeability functions. The findings from this shows that there are significant differences between the functionality of the pure samples compared to the contaminated samples, with an average of about 20-30% reduction in functionality. This paper integrates modelling techniques using a heat, air and mass software with a simulink interface on a Matlab platform to investigate the moisture transfer properties of the BRMs. The simulation results demonstrate high level of condensation formation when the BRM is contaminated as compared to when it is not.

Solution calorimetry as a tool for investigating drug interaction with intestinal fluid

Solution calorimetry offers a reproducible technique for measuring the enthalpy of solution (ΔsolH) of a solute dissolving into a solvent. The ΔsolH of two solutes, propranolol HCl and mannitol were determined in simulated intestinal fluid (SIF) solutions designed to model the fed and fasted states within the gut, and in Hanks’ balanced salt solution (HBSS) of varying pH. The bile salt and lipid within the SIF solutions formed mixed micelles. Both solutes exhibited endothermic reactions in all solvents. The ΔsolH for propranolol HCl in the SIF solutions differed from those in the HBSS and was lower in the fed state than the fasted state SIF solution, revealing an interaction between propranolol and the micellar phase in both SIF solutions. In contrast, for mannitol the ΔsolH was constant in all solutions indicating minimal interaction between mannitol and the micellar phases of the SIF solutions. In this study, solution calorimetry proved to be a simple method for measuring the enthalpy associated with the dissolution of model drugs in complex biological media such as SIF solutions. In addition, the derived power–time curves allowed the time taken for the powdered solutes to form solutions to be estimated.

The statistical downscaling model-decision centric (SDSM-DC): conceptual basis and applications

Regional climate downscaling has arrived at an important juncture. Some in the research community favour continued refinement and evaluation of downscaling techniques within a broader framework of uncertainty characterisation and reduction. Others are calling for smarter use of downscaling tools, accepting that conventional, scenario-led strategies for adaptation planning have limited utility in practice. This paper sets out the rationale and new functionality of the Decision Centric (DC) version of the Statistical DownScaling Model (SDSM-DC). This tool enables synthesis of plausible daily weather series, exotic variables (such as tidal surge), and climate change scenarios guided, not determined, by climate model output. Two worked examples are presented. The first shows how SDSM-DC can be used to reconstruct and in-fill missing records based on calibrated predictor-predictand relationships. Daily temperature and precipitation series from sites in Africa, Asia and North America are deliberately degraded to show that SDSM-DC can reconstitute lost data. The second demonstrates the application of the new scenario generator for stress testing a specific adaptation decision. SDSM-DC is used to generate daily precipitation scenarios to simulate winter flooding in the Boyne catchment, Ireland. This sensitivity analysis reveals the conditions under which existing precautionary allowances for climate change might be insufficient. We conclude by discussing the wider implications of the proposed approach and research opportunities presented by the new tool.

The Functionality of the three-sited Ferroxidase center of E. coli Bacterial Ferritin (EcFtnA)

At least three ferritins are found in the bacterium Escherichia coli, the heme-containing bacterioferritin (EcBFR) and two non-heme bacterial ferritins (EcFtnA and EcFtnB). In addition to the conserved A- and B-sites of the diiron ferroxidase center, EcFtnA has a third iron-binding site (the C-site) of unknown function that is nearby the diiron site. In the present work, the complex chemistry of iron oxidation and deposition in EcFtnA has been further defined through a combination of oximetry, pH stat, stopped-flow and conventional kinetics, UV-visible, fluorescence and EPR spectroscopic measurements on the wildtype protein and site-directed variants of the A-, B- and C-sites. The data reveal that, while H2O2 is a product of dioxygen reduction in EcFtnA and oxidation occurs with a stoichiometry of Fe(II)/O2 ~ 3:1, most of the H2O2 produced is consumed in subsequent reactions with a 2:1 Fe(II)/H2O2 stoichiometry, thus suppressing hydroxyl radical formation. While the A- and B-sites are essential for rapid iron oxidation, the C-site slows oxidation and suppresses iron turnover at the ferroxidase center. A tyrosyl radical, assigned to Tyr24 near the ferroxidase center, is formed during iron oxidation and its possible significance to the function of the protein is discussed. Taken as a whole, the data indicate that there are multiple iron-oxidation pathways in EcFtnA with O2 and H2O2 as oxidants. Furthermore, the data are inconsistent with the C-site being a transit site, providing iron to the A- and B-sites, and does not support a universal mechanism for iron oxidation in all ferritins as recently proposed.

Effects of orange juice formulation on prebiotic functionality using an in vitro colonic model sytem

A three-stage continuous fermentative colonic model system was used to monitor in vitro the effect of different orange juice formulations on prebiotic activity. Three different juices with and without Bimuno, a GOS mixture containing galactooligosaccharides (B-GOS) were assessed in terms of their ability to induce a bifidogenic microbiota. The recipe development was based on incorporating 2.75g B-GOS into a 250 ml serving of juice (65°Brix of concentrate juice). Alongside the production of B-GOS juice, a control juice - orange juice without any additional Bimuno and a positive control juice, containing all the components of Bimuno (glucose, galactose and lactose) in the same relative proportions with the exception of B-GOS were developed. Ion Exchange Chromotography analysis was used to test the maintenance of bimuno components after the production process. Data showed that sterilisation had no significant effect on concentration of B-GOS and simple sugars. The three juice formulations were digested under conditions resembling the gastric and small intestinal environments. Main bacterial groups of the faecal microbiota were evaluated throughout the colonic model study using 16S rRNA-based fluorescence in situ hybridization (FISH). Potential effects of supplementation of the juices on microbial metabolism were studied measuring short chain fatty acids (SCFAs) using gas chromatography. Furthermore, B-GOS juices showed positive modulations of the microbiota composition and metabolic activity. In particular, numbers of faecal bifidobacteria and lactobacilli were significantly higher when B-GOS juice was fermented compared to controls. Furthermore, fermentation of B-GOS juice resulted in an increase in Roseburia subcluster and concomitantly increased butyrate production, which is of potential benefit to the host. In conclusion, this study has shown B-GOS within orange juice can have a beneficial effect on the fecal microbiota.

Functionality of several cake ingredients: a comprehensive approach

The roles of some cake ingredients – oil, a leavening agent, and inulin – in the structure and physicochemical properties of batter and cakes were studied in four different formulations. Oil played an important role in the batter stability, due to its contribution to increasing batter viscosity and occluding air during mixing. The addition of the leavening agent was crucial to the final height and sponginess of the cakes. When inulin was used as a fat replacer, the absence of oil caused a decrease in the stability of the batter, where larger air bubbles were occluded. Inulin dispersed uniformly in the batter could create a competition for water with the flour components: gluten was not properly hydrated and some starch granules were not fully incorporated into the matrix. Thus, the development of a continuous network was disrupted and the cake was shorter and softer; it contained interconnected air cells in the crumb, and was easily crumbled. The structure studies were decisive to understand the physicochemical properties.