Prediction of the formation and stabilities of energetic salts and ionic liquids based on ab initio electronic structure calculations

A computational approach to predict the thermodynamics for forming a variety of imidazolium-based salts and ionic liquids from typical starting materials is described. The gas-phase proton and methyl cation acidities of several protonating and methylating agents, as well as the proton and methyl cation affinities of many important methyl-, nitro-, and cyano- substituted imidazoles, have been calculated reliably by using the computationally feasible DFT (B3LYP) and MP2 (extrapolated to the complete basis set limit) methods. These accurately calculated proton and methyl cation affinities of neutrals and anions are used in conjunction with an empirical approach based on molecular volumes to estimate the lattice enthalpies and entropies of ionic liquids, organic solids, and organic liquids. These quantities were used to construct a thermodynamic cycle for salt formation to reliably predict the ability to synthesize a variety of salts including ones with potentially high energetic densities. An adjustment of the gas phase thermodynamic cycle to account for solid- and liquid-phase chemistries provides the best overall assessment of salt formation and stability. This has been applied to imidazoles (the cation to be formed) with alkyl, nitro, and cyano substituents. The proton and methyl cation donors studied were as follows: HCl, HBr, HI, (HO)(2)SO2, HSO3CF3 (TfOH), and HSO3(C6H4)CH3 (TsOH); CH3Cl, CH3Br, CH3I, (CH3O)(2)SO2, CH3SO3CF3 (TfOCH3) and CH3SO3(C6H4)CH3 (TsOCH3). As substitution of the cation with electron-withdrawing groups increases, the triflate reagents appear to be the best overall choice as protonating and methylating agents. Even stronger alkylating agents should be considered to enhance the chances of synthetic success. When using the enthalpies of reaction for the gas-phase reactants (eq 6) to form a salt, a cutoff value of - 13 kcal mol(-1) or lower (more negative) should be used as the minimum value for predicting whether a salt can be synthesized.

Iterative Multiuser Detection and Decoding for DS-CDMA System With Space-Time Linear Dispersion

This paper considers a Q-ary orthogonal direct-sequence code-division multiple-access (DS-CDMA) system with high-rate space-time linear dispersion codes (LDCs) in time-varying Rayleigh fading multiple-input-multiple-output (MIMO) channels. We propose a joint multiuser detection, LDC decoding, Q-ary demodulation, and channel-decoding algorithm and apply the turbo processing principle to improve system performance in an iterative fashion. The proposed iterative scheme demonstrates faster convergence and superior performance compared with the V-BLAST-based DS-CDMA system and is shown to approach the single-user performance bound. We also show that the CDMA system is able to exploit the time diversity offered by the LDCS in rapid-fading channels.

Short, medium and long term load forecasting model and virtual load forecaster based on radial basis neural networks

Artificial neural networks (ANNs) can be easily applied to short-term load forecasting (STLF) models for electric power distribution applications. However, they are not typically used in medium and long term load forecasting (MLTLF) electric power models because of the difficulties associated with collecting and processing the necessary data. Virtual instrument (VI) techniques can be applied to electric power load forecasting but this is rarely reported in the literature. In this paper, we investigate the modelling and design of a VI for short, medium and long term load forecasting using ANNs. Three ANN models were built for STLF of electric power. These networks were trained using historical load data and also considering weather data which is known to have a significant affect of the use of electric power (such as wind speed, precipitation, atmospheric pressure, temperature and humidity). In order to do this a V-shape temperature processing model is proposed. With regards MLTLF, a model was developed using radial basis function neural networks (RBFNN). Results indicate that the forecasting model based on the RBFNN has a high accuracy and stability. Finally, a virtual load forecaster which integrates the VI and the RBFNN is presented.

A heuristic model for the simulation of the deformation of elastic and spongy material for virtual reality applications

This paper presents a practical algorithm for the simulation of interactive deformation in a 3D polygonal mesh model. The algorithm combines the conventional simulation of deformation using a spring-mass-damping model, solved by explicit numerical integration, with a set of heuristics to describe certain features of the transient behaviour, to increase the speed and stability of solution. In particular, this algorithm was designed to be used in the simulation of synthetic environments where it is necessary to model realistically, in real time, the effect on non-rigid surfaces being touched, pushed, pulled or squashed. Such objects can be solid or hollow, and have plastic, elastic or fabric-like properties. The algorithm is presented in an integrated form including collision detection and adaptive refinement so that it may be used in a self-contained way as part of a simulation loop to include human interface devices that capture data and render a realistic stereoscopic image in real time. The algorithm is designed to be used with polygonal mesh models representing complex topology, such as the human anatomy in a virtual-surgery training simulator. The paper evaluates the model behaviour qualitatively and then concludes with some examples of the use of the algorithm.

Cation complexation by chemically modified calixarenes. 11. Complexation and extraction of alkali cations by calix[5]- and -[6]arene ketones. Crystal and molecular structures of calix[5]arene ketones and Na+ and Rb+ complexes

A series of four calix[5]arenes and three calix[6]arenes (R-calixarene-OCH2COR1) (R = H or Bu-t) with alkyl ketone residues (R-1 = Me or Bu-t) on the lower rim have been synthesized, and their affinity for complexation of alkali cations has been assessed through phase-transfer experiments and stability constant measurements. The conformations of these ketones have been probed by H-1 NMR and X-ray diffraction analysis, and by molecular mechanics calculations. Pentamer 3 (R R-1 = Bu-t) possesses a symmetrical cone conformation in solution and a very distorted cone conformation in the solid state. Pentamer 5 (R = H, R-1 = Bu-t) exists in a distorted 1,2-alternate conformation in the solid state, but in solution two slowly interconverting conformations, one a cone and the other presumed to be 1,2-alternate, can be detected. X-ray structure analysis of the sodium and rubidium perchlorate complexes of 3 reveal the cations deeply encapsulated by the ethereal and carbonyl oxygen atoms in distorted cone conformations which can be accurately reproduced by molecular mechanics calculations. The phase-transfer and stability constant data reveal that the extent of complexation depends on calixarene size and the nature of the alkyl residues adjacent to the ketonic carbonyls with tert-butyl much more efficacious than methyl.

Manipulating Interaction Strengths and the Consequences for Trivariate Patterns in a Marine Food Web

We are experiencing a global extinction crisis as a result of climate change and human-induced alteration of natural habitats, with large predators at high trophic levels in food webs being particularly vulnerable. Unfortunately, there is a scarcity of food web data that can be used to assess how species extinctions alter the structure and stability of temporally and spatially replicated networks. We established a series of large experimental mesocosms in a shallow subtidal benthic marine system and constructed food webs for each replicate. After 6 months of community assembly, we removed large predators from the core communities of 20 experimental food webs, based on the strength of their trophic interactions, and monitored the changes in the networks' structure and stability over an 8-month period. Our analyses revealed the importance of allometric relationships and size-structuring in natural communities as a means of preserving food web structure and sustainability, despite significant changes in the diversity, stability and productivity of the system.

Macroecological patterns and niche structure in a new marine food web

The integration of detailed information on feeding interactions with measures of abundance and body mass of individuals provides a powerful platform for understanding ecosystem organisation. Metabolism and, by proxy, body mass constrain the flux, turnover and storage of energy and biomass in food webs. Here, we present the first food web data for Lough Hyne, a species rich Irish Sea Lough. Through the application of individual-and size-based analysis of the abundance-body mass relationship, we tested predictions derived from the metabolic theory of ecology. We found that individual body mass constrained the flux of biomass and determined its distribution within the food web. Body mass was also an important determinant of diet width and niche overlap, and predator diets were nested hierarchically, such that diet width increased with body mass. We applied a novel measure of predator-prey biomass flux which revealed that most interactions in Lough Hyne were weak, whereas only a few were strong. Further, the patterning of interaction strength between prey sharing a common predator revealed that strong interactions were nearly always coupled with weak interactions. Our findings illustrate that important insights into the organisation, structure and stability of ecosystems can be achieved through the theoretical exploration of detailed empirical data.

Mass media and polarisation processes in the bounded confidence model of opinion dynamics

This paper presents a social simulation in which we add an additional layer of mass media communication to the social network 'bounded confidence' model of Deffuant et al (2000). A population of agents on a lattice with continuous opinions and bounded confidence adjust their opinions on the basis of binary social network interactions between neighbours or communication with a fixed opinion. There are two mechanisms for interaction. 'Social interaction' occurs between neighbours on a lattice and 'mass communication' adjusts opinions based on an agent interacting with a fixed opinion. Two new variables are added, polarisation: the degree to which two mass media opinions differ, and broadcast ratio: the number of social interactions for each mass media communication. Four dynamical regimes are observed, fragmented, double extreme convergence, a state of persistent opinion exchange leading to single extreme convergence and a disordered state. Double extreme convergence is found where agents are less willing to change opinion and mass media communications are common or where there is moderate willingness to change opinion and a high frequency of mass media communications. Single extreme convergence is found where there is moderate willingness to change opinion and a lower frequency of mass media communication. A period of persistent opinion exchange precedes single extreme convergence, it is characterized by the formation of two opposing groups of opinion separated by a gradient of opinion exchange. With even very low frequencies of mass media communications this results in a move to central opinions followed by a global drift to one extreme as one of the opposing groups of opinion dominates. A similar pattern of findings is observed for Neumann and Moore neighbourhoods.

Devolution and the politics of development in Northern Ireland

The reintroduction of devolution in Northern Ireland is widely interpreted as the working out of the Belfast Agreement (1998) which aimed to embed political consensus in shared institutions of the state. However, such analysis tends to be limited with regard to wider political economy readings of the devolution project and historic struggles to find an appropriate institutional fix to manage different
forms of crisis. Peace and stability have, it is argued, permitted Northern Ireland's reentry to global markets and circuits of capital with new governance structures being assembled to reconfigure `post- conflict' economic space. We argue that the onset of devolution has promoted a mix between ethnosectarian resource competition and a constantly expanding neoliberal model of governance.
Devolved neoliberal structures that sustain social polarisation may perpetuate strategies of resistance that could cut across and challenge ethnosectarian politics and deepening social segregation.

Functional and biochemical characterisation of the Escherichia coli major facilitator superfamily multidrug transporter MdtM

Multidrug resistance (MDR) occurs when bacteria simultaneously acquire resistance to a broad spectrum of structurally dissimilar compounds to which they have not previously been exposed. MDR is principally a consequence of the active transport of drugs out of the cell by proteins that are integral membrane transporters. We characterised and purified the putative Escherichia coli MDR transporter, MdtM, a 410 amino acid residue protein that belongs to the large and ubiquitous major facilitator superfamily. Functional characterisation of MdtM using growth inhibition and whole cell transport assays revealed its role in intrinsic resistance of E. coli cells to the antimicrobials ethidium bromide and chloramphenicol. Site-directed mutagenesis studies implied that the MdtM aspartate 22 residue and the highly conserved arginine at position 108 play a role in proton recognition. MdtM was homologously overexpressed and purified to homogeneity in dodecyl maltopyranoside detergent solution and the oligomeric state and stability of the protein in a variety of detergent solutions was investigated using size-exclusion HPLC. Purified MdtM is monomeric and stable in dodecyl maltopyranoside solution and binds chloramphenicol with nanomolar affinity in the same detergent. This work provides a firm foundation for structural studies on this class of multidrug transporter protein.

Chemical influences on the luminescence of ruthenium diimine complexes and its response to oxygen

Different luminescent, hydrophillic ruthenium diimine cationic complexes are rendered soluble in the hydrophobic medium of a plasticised polymer through ion-pair coupling with a hydrophobic anion, such as tetraphenyl berate. Based on this approach, a number of different oxygen sensitive films, i.e., luminescent, thin plastic films which respond to oxygen-the latter quenches the luminescence were prepared, using the polymer, cellulose acetate, plasticised with tributylphosphate. Of the resultant thin oxygen sensitive films tested, the one containing the luminescent ion-pair ruthenium (II) tris(4,7-diphenyl-1,IO-phenanthroline) ditetraphenyl berate, [Ru(dpp)(3)(2+)(Ph4B-)(2)], was found to be the most sensitive, and its response characteristics were subsequently studied as a function of plasticiser content, temperature and stability in use, and with age. The major response characteristics, i.e., film sensitivity towards oxygen and response and recovery times, depend very strongly upon the overall level of plasticiser present in film; the film is more sensitive and faster in response and recovery the greater the level of plasticiser employed. Thus, the response of the film towards oxygen can be tuned by varying the level of plasticiser in the film. Film sensitivity towards oxygen is largely independent on temperature, whereas its response and recovery times decrease with increasing temperature (E-a = -10.3+/-0.4 kJ mol(-1)). The sensitivity of a typical luminescent film is very stable when used continuously over a 24-h period, decreases by ca. 20% with age when stored at ambient temperature over a period of 29 days, but very little over the same period of time when stored in the freezer section of a fridge. (C) 1997 Elsevier Science S.A.

Structural and Molecular Biology of Type I Galactosemia: Disease-associated Mutations

Type I galactosemia results from reduced galactose 1-phosphate uridylyltransferase (GALT) activity. Signs of disease include damage to the eyes, brain, liver, and ovaries. However, the exact nature and severity of the pathology depends on the mutation(s) in the patient's genes and his/her environment. Considerable enzymological and structural knowledge has been accumulated and this provides a basis to explain, at a biochemical level, impairment in the enzyme in the more than 230 disease-associated variants, which have been described. The most common variant, Q188R, occurs close to the active site and the dimer interface. The substitution probably disrupts both UDP-sugar binding and homodimer stability. Other alterations, for example K285N, occur close to the surface of the enzyme and most likely affect the folding and stability of the enzyme. There are a number of unanswered questions in the field, which require resolution. These include the possibility that the main enzymes of galactose metabolism form a supramolecular complex and the need for a high resolution crystal structure of human GALT. (C) 2011 IUBMB IUBMB Life, 63(11): 949-954, 2011

The Governance of Sexual Offending Across Europe: Penal Policies, Political Economies and the Institutionalization of Risk

This article examines why England and Wales have comparatively one of the most stringent systems for the governance of sexual offending within Western Europe. While England and Wales, like the USA, have adopted broadly exclusionary, managerialist penal policies based around incapacitation and targeted surveillance, many other Western European countries have opted for more inclusionary therapeutic interventions. Divergences in state approaches to sex offender risk, particularly in relation to notification and vetting schemes, are initially examined with reference to the respective theoretical frameworks of ‘policy transfer’ and differing political economies. Chiefly, however, differences in penal policies are attributed to the social and political construction of risk and its control. There may be multiple expressions of risk relating to expert, lay, moral or emotive aspects. It is argued, however, that it is the particular convergence and alignment of these dimensions on the part of the various stakeholders in the UK – government, media, public and professional – that leads to risk becoming institutionalized in the form of punitive regulatory policies for managing the dangerous.

The C-terminal domain of the Salmonella enterica WbaP (UDP-galactose:Und-P galactose-1-phosphate transferase) is sufficient for catalytic activity and specificity for undecaprenyl monophosphate

Two families of membrane enzymes catalyze the initiation of the synthesis of O-antigen lipopolysaccharide. The Salmonella enterica Typhimurium WbaP is a prototypic member of one of these families. We report here the purification and biochemical characterization of the WbaP C-terminal (WbaP(CT)) domain harboring one putative transmembrane helix and a large cytoplasmic tail. An N-terminal thioredoxin fusion greatly improved solubility and stability of WbaP(CT) allowing us to obtain highly purified protein. We demonstrate that WbaP(CT) is sufficient to catalyze the in vitro transfer of galactose (Gal)-1-phosphate from uridine monophosphate (UDP)-Gal to the lipid carrier undecaprenyl monophosphate (Und-P). We optimized the in vitro assay to determine steady-state kinetic parameters with the substrates UDP-Gal and Und-P. Using various purified polyisoprenyl phosphates of increasing length and variable saturation of the isoprene units, we also demonstrate that the purified enzyme functions highly efficiently with Und-P, suggesting that the WbaP(CT) domain contains all the essential motifs to catalyze the synthesis of the Und-P-P-Gal molecule that primes the biosynthesis of bacterial surface glycans.

Effects of species loss and nutrients on biodiversity:Anthropogenic impacts on marine biodiversity: effects of enhanced nutrients and species loss on the biodiversity and ecosystem functioning of rocky shores

The focus of this study was to disentangle the effects of multiple stressors on biodiversity, ecosystem functioning and stability. This project examined the effects of anthropogenic increased nutrient loads on the diversity of coastal ecosystems and the effects of loss of species on ecosystem functioning. Specifically, the direct effect of sewage outfalls on benthic communities was assessed using a fully replicated survey that incorporated spatial and temporal variation. In addition, two field experiments examined the effects of loss of species at multiple trophic levels, and tested for potential interactive effects with enhanced nutrient concentration conditions on benthic assemblage structure and ecosystem functioning. This research addressed priority issues outlined in the Biodiversity Knowledge Programme for Ireland (2006) and also aimed to deliver information relevant to European Union (EU) directives (the Water Framework Directive [WFD], the Habitats Directive and the Marine Strategy Framework Directive).