Minimizing side reactions in chemoenzymatic dynamic kinetic resolution: organometallic and material strategies

Chemoenzymatic dynamic kinetic resolution (DKR) of rac-1-phenyl ethanol into R-1-phenylethanol acetate was investigated with emphasis on the minimization of side reactions. The organometallic hydrogen transfer (racemization) catalyst was varied, and this was observed to alter the rate and extent of oxidation of the alcohol to form ketone side products. The performance of highly active catalyst [(pentamethylcyclopentadienyl) IrCl2(1-benzyl,3-methyl-imidazol-2-ylidene)] was found to depend on the batch of lipase B used. The interaction between the bio- and chemo-catalysts was reduced by employing physical entrapment of the enzyme in silica using a sol-gel process. The nature of the gelation method was found to be important, with an alkaline method preferred, as an acidic method was found to initiate a further side reaction, the acid catalyzed dehydration of the secondary alcohol. The acidic gel was found to be a heterogeneous solid acid.

Material Deprivation, Economic Stress, and Reference Groups in Europe: An Analysis of EU-SILC 2009

In this article, we take advantage of the recent availability of data from the special module on material deprivation in the 2009 European Union Statistics on Income and Living Conditions to develop a more comprehensive understanding of the relationship between material deprivation and economic stress, the mediating and moderating roles played by cross-national differences in levels of income and income inequality, and the implications for competing perspectives on the nature of reference groups in Europe. The article establishes the critical role of basic deprivation, relating to inability to enjoy customary standards of living, in influencing economic stress levels. National income levels and inequality had no direct influence on economic stress. However, the impact of basic deprivation was stronger in countries with higher levels of income, indicating the crucial role of national reference groups. An interaction between basic deprivation and income inequality was also observed. However, contrary to the expectation that experiencing basic deprivation in a national context of high income inequality is likely to be particularly stressful, the consequences of such deprivation were most negative in low inequality countries. Experiencing basic deprivation where high income levels and lower inequality would lead to the expectation that such deprivation is eminently avoidable exacerbates its impact. © The Author 2013.

Understanding material deprivation: A comparative European analysis

In this paper, taking advantage of the inclusion of a special module on material deprivation in EU-SILC 2009. we provide a comparative analysis of patterns of deprivation. Our analysis identifies six relatively distinct dimensions of deprivation with generally satisfactory overall levels of reliability and mean levels of reliability across countries. Multi-level analysis based on 28 European countries reveals systematic variation in the importance of within and between country variation for a range of deprivation dimensions. The basic deprivation dimension is the sole dimension to display a graduated pattern of variation across countries. It also reveals the highest correlations with national and household income, the remaining deprivation dimensions and economic stress. It comes closest to capturing an underlying dimension of generalized deprivation that can provide the basis for a comparative European analysis of exclusion from customary standards of living. A multilevel analysis revealed that a range of household characteristics and household reference person socio-economic factors were related to basic deprivation and controlling for contextual differences in such factors allowed us to account for substantial proportions of both within and between country variance. The addition of macro-economic factors relating to average levels of disposable income and income inequality contributed relatively little further in the way of explanatory power. Further analysis revealed the existence of a set of significant interactions between micro socioeconomic attributes and country level gross national disposable income per capita. The impact of socio-economic differentiation was significantly greater where average income levels were lower. Or, in other words, the impact of the latter was greater for more disadvantaged socio-economic groups. Our analysis supports the suggestion that an emphasis on the primary role of income inequality to the neglect of differences in absolute levels of income may be misleading in important respects. (C) 2012 International Sociological Association Research Committee 28 on Social Stratification and Mobility. Published by Elsevier Ltd. All rights reserved.

Measuring material deprivation with EU-SILC: Lessons from the Irish survey

In this paper we consider the consequences for measurement of material deprivation, consistent poverty and economic vulnerability of the shift from the ECHP data set to the EU-SILC instrument. Despite the restricted number of deprivation items available in EU-SILC, we show that there is a substantial overlap between such measures when they are estimated using EU-wide and a set of Irish specific indicators. By placing the EU-wide measures in the context of the full range of Irish indicators, we demonstrate that they allow us to identify clusters of individuals sharply differentiated in terms of their multidimensional deprivation profiles. They also provide an understanding of the socio-economic factors associated with such differentiation that departs in only modest respects from that derived from the more comprehensive set of Irish specific indicators.

Levels and patterns of material deprivation in Ireland: After the 'Celtic tiger'

In this article we use the first full wave of the Irish component of the EU Statistics on Income and Living Conditions survey to evaluate conflicting interpretations of levels and patterns of material deprivation in Ireland after the 'Celtic Tiger'. Radical critics of Irish economic policies have seen the Irish case as a particularly good illustration of the tendency for globalization to be accompanied by widespread economic vulnerability and marginalization. Here, employing a multidimensional perspective we identify one fifth of the population as being economically vulnerable and one in 14 as vulnerable to maximal deprivation, in that they exhibit high risks of deprivation across a range of life-style deprivation dimensions. Current levels and depth of material deprivation are a good deal more modest than suggested by radical critics of the Irish experience of economic globalization.

On the filling factor of emitting material in the upper atmosphere of ε Eri (K2 V)

The emission measure distribution in the upper transition region and corona of e Eri is derived from observed emission-line fluxes. Theoretical emission measure distributions are calculated assuming that the radiation losses are balanced by the net conductive flux. We discuss how the area factor of the emitting regions as a function of temperature can be derived from a comparison between these emission measure distributions. It is found that the filling factor varies from ~0.2 in the mid-transition region to ~1.0 in the inner corona. The sensitivity of these results to the adopted ion fractions, the iron abundance and other parameters is discussed. The area factors found are qualitatively similar to the observed structure of the solar atmosphere, and can be used to constrain two-component models of the chromosphere. Given further observations, the method could be applied to investigate the trends in filling factors with indicators of stellar activity.

A material model for multiaxial stretching and stress relaxation of polypropylene under process conditions

Polypropylene sheets have been stretched at 160 °C to a state of large biaxial strain of extension ratio 3, and the stresses then allowed to relax at constant strain. The state of strain is reached via a path consisting of two sequential planar extensions, the second perpendicular to the first, under plane stress conditions with zero stress acting normal to the sheet. This strain path is highly relevant to solid phase deformation processes such as stretch blow moulding and thermoforming, and also reveals fundamental aspects of the flow rule required in the constitutive behaviour of the material. The rate of decay of stress is rapid, and such as to be highly significant in the modelling of processes that include stages of constant strain. A constitutive equation is developed that includes Eyring processes to model both the stress relaxation and strain rate dependence of the stress. The axial and transverse stresses observed during loading show that the use of a conventional Levy-Mises flow rule is ineffective, and instead a flow rule is used that takes account of the anisotropic state of the material via a power law function of the principal extension ratios. Finally the constitutive model is demonstrated to give quantitatively useful representation of the stresses both in loading and in stress relaxation.

Encouraging lifestyle behaviour change in mild cognitive impairment patients:development of appropriate educational material

Objectives: A healthy lifestyle may help maintain cognitive function and reduce the risk of developing dementia. This study employed a focus group approach in order to gain insight into opinions of mild cognitive impairment (MCI) patients, caregivers (CG) and health professionals (HP) regarding lifestyle and its relationship with cognition. The qualitative data were used to design, develop and pilot test educational material (EM) to help encourage lifestyle behaviour change. Method: Data gathering phase: structured interviews were conducted with HP (n = 10), and focus groups with MCI patients (n = 24) and CG (n = 12). EM was developed and pilot tested with a new group of MCI patients (n = 21) and CG (n = 6). Results: HP alluded to the lack of clinical trial evidence for a lifestyle and MCI risk link. Although they felt that lifestyle modifications should be recommended to MCI patients, they appeared hesitant in communicating this information and discussions were often patient-driven. MCI patients lacked awareness of the lifestyle cognition link. Participants preferred EM to be concise, eye-catching and in written format, with personal delivery of information favoured. Most pilot testers approved of the EM but were heterogeneous in terms of lifestyle, willingness to change and support needed to change. Conclusion: MCI patients need to be made more aware of the importance of lifestyle for cognition. EM such as those developed here, which are specifically tailored for this population would be valuable for HP who, currently, appear reticent in initiating lifestyle-related discussions. Following further evaluation, the EM could be used in health promotion activities targeting MCI patients.

Comparative performances of birnessite and cryptomelane MnO as electrode material in neutral aqueous lithium salt for supercapacitor application

Na-doped Birnessite-type manganese oxide (d-MnO) has been synthesized using the chemical method and characterized through X-ray diffraction and SEM, showing the lamellar structure and high crystal structure. A comparative study of the electrochemical performances of this material with those of the commercial Cryptomelane-type MnO has then been undertaken in ten neutral aqueous electrolytes for supercapacitor applications. Aqueous electrolytes, containing a lithium salt, LiX (where X = SO , NO, CHCO , CHSO, ClO , CHCO, TFSI, Beti, BOB, or Lact), have been first prepared under neutral pH conditions to reach the salt concentration, providing the maximum in conductivity. Their transport properties are then investigated through conductivities, viscosities, and self-diffusion coefficient measurements. Second, the thermal behaviors of these electrolytic aqueous solutions are then evaluated by using a differential scanning calorimeter from (213.15 to 473.15) K in order to access their liquid range temperatures. Cyclic voltammograms (CV) in three electrode configurations are thereafter investigated using Na Birnessite and Cryptomelane as working electrode material from (-0.05 to 1.5) V versus Ag/AgCl at various sweep rates from (2 to 100) mV·s. According to anion nature/structure and manganese oxide material type, different CV responses are observed, presenting a pure capacitive profile for Beti or CH CO and an additional pseudocapacitive signal for the smallest anions, such as ClO and NO . The capacitances, energies, and efficiencies are finally calculated. These results indicate clearly that electrolytes based on a mineral lithium salt under neutral pH condition and high salt concentration (up to 5 mol·L) have better electrochemical performances than organic ones, up to 1.4 V with good material stability and capacity retention. The relationship between transport properties, electrostatic and steric hindrance considerations of hydrated ions, and their electrochemical performances is discussed in order to understand further the lithium intercalation-deintercalation processes in the lamellar or tunnel structure of investigated MnO. © 2013 American Chemical Society.

Evidence and Spatial Planning for Sustainable Development: A Model for Spatially Allocating Material Flows

The aspiration the spatial planning should act as the main coordinating function for the transition to a sustainable society is grounded on the assumption that it is capable of incorporating both a strong evidence base of environmental accounting for policy, coupled with opportunities for open, deliberative decision-making. While there are a number of increasingly sophisticated methods (such as material flow analysis and ecological footprinting) that can be used to longitudinally determine the impact of policy, there are fewer that can provide a robust spatial assessment of sustainability policy. In this paper, we introduce the Spatial Allocation of Material Flow Analysis (SAMFA) model, which uses the concept of socio-economic metabolism to extrapolate the impact of local consumption patterns that may occur as a result of the local spatial planning process at multiple spatial levels. The initial application the SAMFA model is based on County Kildare in the Republic of Ireland, through spatial temporal simulation and visualisation of construction material flows and associated energy use in the housing sector. Thus, while we focus on an Ireland case study, the model is applicable to spatial planning and sustainability research more generally. Through the development and evaluation of alternative scenarios, the model appears to be successful in its prediction of the cumulative resource and energy impacts arising from consumption and development patterns. This leads to some important insights in relation to the differential spatial distribution of disaggregated allocation of material balance and energy use, for example that rural areas have greater resource accumulation (and are therefore in a sense “less sustainable”) than urban areas, confirming that rural housing in Ireland is both more material and energy intensive. This therefore has the potential to identify hotspots of higher material and energy use, which can be addressed through targeted planning initiatives or focussed community engagement. Furthermore, due to the ability of the model to allow manipulation of different policy criteria (increased density, urban conservation etc), it can also act as an effective basis for multi-stakeholder engagement.