Voltammetry of oxygen in the room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide: One-electron reduction to form superoxide. Steady-state and transient behavior in the same cyclic voltammogram resulting from widely different diffusion coefficients of oxygen and superoxide

The electrochemical reduction of oxygen in two different room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide ([EMIM][N(Tf)(2)]) and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide ([N-6222][N(Tf)(2)]) was investigated by cyclic voltammetry at a gold microdisk electrode. Chronoamperometric measurements were made to determine the diffusion coefficient, D, and concentration, c, of the electroactive oxygen dissolved in the ionic liquid by fitting experimental transients to the Aoki model. [Aoki, K.; et al. J. Electroanal. Chem. 1981, 122, 19]. A theory and simulation designed for cyclic voltammetry at microdisk electrodes was then employed to determine the diffusion coefficient of the electrogenerated superoxide species, O-2(.-), as well as compute theoretical voltammograms to confirm the values of D and c for neutral oxygen obtained from the transients. As expected, the diffusion coefficient of the superoxide species was found to be smaller than that of the oxygen in both ionic liquids. The diffusion coefficients of O-2 and O-2(.-) in [N-6222][N(Tf)(2)], however, differ by more than a factor of 30 (D-O2 = 1.48 x 10(-10) m(2) s(-1), DO2.- = 4.66 x 10(-12) m(2) s(-1)), whereas they fall within the same order of magnitude in [EMIM][N(Tf)(2)] (D-O2 = 7.3 x 10(-10) m(2) s(-1), DO2.- = 2.7 x 10(-10) m(2) s(-1)). This difference in [N-6222][N(Tf)(2)] causes pronounced asymmetry in the concentration distributions of oxygen and superoxide, resulting in significant differences in the heights of the forward and back peaks in the cyclic voltammograms for the reduction of oxygen. This observation is most likely a result of the higher viscosity of [N-6222][N(Tf)(2)] in comparison to [EMIM][N(Tf)(2)], due to the structural differences in cationic component.

Sol-gel-entrapped nano silver catalysts-correlation between active silver species and catalytic behavior

Silver colloids prepared by reducing AgNO3 in aqueous solution with sodium citrate were embedded in alumina following two different preparation procedures resulting in samples containing 3 and 5 wt.% silver. Characterization of these materials using TEM. XPS, XAES, CP/MAS NMR, XRD, and adsorption-desorption isotherms of nitrogen showed that embedding the pre-prepared silver colloids into the alumina via the sol-gel procedure preserved the particle size of silver. However, as XAES demonstrates, the catalysts prepared in a sol-gel with a lower amount of water led to embedded colloids with a higher population of Ag+ species. The catalytic behaviors of the resultant catalysts were well correlated with the concentration of these species. Thus, the active silver species of the catalysts containing more Ag+ species selectively converts NO to N-2. However, subsequent thermal aging leads to an enhancement of the conversion of NO parallel to slight alteration of the selectivity with the appearance of low amounts of N2O despite an increase of Ag+ species. Accordingly, an optimal surface Ag-0/Ag+ ratio is probably needed, independently of the size of silver particles. It was found that this optimal ratio strongly depends on the operating conditions during the synthesis route. (C) 2010 Elsevier Inc. All rights reserved.

Stability and dynamical behavior in a lake-model and implications for regime shifts in real lakes

A modified abstract version of the Comprehensive Aquatic Simulation Model (CASM) is found to exhibit three types of folded bifurcations due to nutrient loading. The resulting bifurcation diagrams account for nonlinear dynamics such as regime shifts and cyclic changes between clear-water state and turbid state that have actually been observed in real lakes. In particular, pulse-perturbation simulations based on the model presented suggest that temporal behaviors of real lakes after biomanipulations can be explained by pulse-dynamics in complex ecosystems, and that not only the amplitude (manipulated abundance of organisms) but also the phase (timing) is important for restoring lakes by biomanipulation. Ecosystem management in terms of possible irreversible changes in ecosystems induced by regime shifts is also discussed. (c) 2007 Elsevier B.V All rights reserved.

Social support, network heterogeneity, and smoking behavior in women: The 10-town study

Purpose. Examine the associations among social support, network heterogeneity, and smoking behavior in a large sample of Finnish female municipal employees.

An evaluation of the effect of altering nutrition and nutritional strategies in early lactation on reproductive performance and estrous behavior of high-yielding Holstein-Friesian dairy cows

Reproductive performance in the high-yielding dairy cow has severely decreased in the last 40 yr. The aim of this study was to compare the effectiveness of 4 nutritional strategies in improving the reproductive performance of high-yielding dairy cows. It was hypothesized that offering cows a high-starch ration in early lactation would enhance the onset of luteal activity, and that decreasing the severity of negative energy balance in the early postcalving period would improve reproductive parameters. Nutritional regimens aimed at improving fertility were applied to 96 Holstein-Friesian dairy animals. Upon calving, animals were allocated in a balanced manner to one of 4 dietary treatments. Primiparous animals were balanced according to live weight, body condition score and calving date. Multiparous animals were balanced according to parity, previous lactation milk yield, liveweight, body condition score and calving date. Treatment 1 was based on an industry best practice diet (control) to contain 170 g of crude protein/kg of dry matter. Treatment 2 was an individual cow feeding strategy, whereby the energy balance (EB) of individual animals was managed so as to achieve a predetermined target daily EB profile (+/- 10 MJ/d). Treatment 3 was a high-starch/high-fat combination treatment, whereby an insulinogenic (high-starch) diet was offered in early lactation to encourage cyclicity and followed by a lipogenic (low-starch, high-fat) diet to promote embryo development. Treatment 4 was a low-protein diet, containing 140 g of crude protein/kg of dry matter, supplemented with protected methionine at an inclusion level of 40 g per animal per day. The nutritional strategies implemented in this study had no statistically significant effects on cow fertility measures, which included the onset of luteal activity, conception rate, in-calf rate, and the incidence of atypical cycles. The individual cow feeding strategy improved EB in early lactation but had no benefit on conception rate to first insemination. However, conception rate to second insemination, 100-d pregnancy rate (from the commencement of breeding), and overall pregnancy rate tended to be higher in this group. The high-starch/high-fat treatment tended to decrease the proportion of delayed ovulations and increase the proportion of animals cycling by d 50 postcalving. Animals that failed to conceive to first insemination had a significantly longer luteal phase in the first cycle postpartum and a longer inter-ovulatory interval in the second cycle postpartum. With regards to estrous behavior, results indicate that as the size of the sexually active group increased, the intensity of estrus and the expression of mounting or attempting to mount another cow also increased. Furthermore, cows that became pregnant displayed more intense estrous behavior than cows that failed to become pregnant.

MODELED DIFFUSION-CONTROLLED RESPONSE AND RECOVERY BEHAVIOR OF A NAKED OPTICAL FILM SENSOR WITH A HYPERBOLIC-TYPE RESPONSE TO ANALYTE CONCENTRATION

The diffusion-controlled response and recovery behaviour of a naked optical film sensor (i.e., with no protective membrane) with a hyperbolic-type response [i.e., S0/S = (1 + Kc), where S is the measured value of the absorbance or luminescence intensity of one form of the sensor dye in the presence of the analyte, S0 is the observed value of S in the absence of analyte and K is a constant] to changes in analyte concentration, c, in a system under test is approximated using a simple model, and described more accurately using a numerical model; in both models it is assumed that the system under test represents an infinite reservoir. Each model predicts the variations in the response and recovery times of such an optical sensor, as a function of the final external analyte concentration, the film thickness (I) and the analyte diffusion coefficient (D). From an observed signal versus time profile for a naked optical film sensor it is shown how values for K and D/I2 can be extracted using the numerical model. Both models provide a qualitative description of the often cited asymmetric nature of the response and recovery for hyperbolic-type response naked optical film sensors. It is envisaged that the models will help in the interpretation of the response and recovery behaviour exhibited by many naked optical film sensors and might be especially apposite when the analyte is a gas.

Life Cycle Assessment guidelines for the sustainable production and recycling of aggregates:The Sustainable Aggregates Resource Management project (SARMa)

The mining/quarrying industry is a sector of industry where there are very few Life Cycle Assessment (LCA) tools, and where the role of LCA has been poorly investigated. A key issue is the integration of three inter-dependent life cycles: Project, Asset and Product. Given the unique features of mining LCAs, this Note from the Field presents a common methodology implemented within the Sustainable Aggregates Resource Management (SARMa) Project (www.sarmaproject.eu) in order to boost adoption of LCA in the aggregate industry in South Eastern Europe. The proposed methodology emphasises the importance of resource efficiency and recycling in the context of a Sustainable Supply Mix of aggregates for the construction industry. Through its adoption, aggregate producers, recyclers, and governmental planners would gain confidence with LCA tools and conduct consistent and meaningful life cycle analyses of natural and recycled aggregates. © 2011 Elsevier Ltd. All rights reserved.

Effect of shotpeening on sliding wear and tensile behavior of titanium implant alloys

Titanium has good biocompatibility and so its alloys are used as implant materials, but they suffer from having poor wear resistance. This research aims to improve the wear resistance and the tensile strength of titanium alloys potentially for implant applications. Titanium alloys Ti–6Al–4V and Ti–6Al–7Nb were subjected to shotpeening process to study the wear and tensile behavior. An improvement in the wear resistance has been achieved due to surface hardening of these alloys by the process of shotpeening. Surface microhardness of shotpeened Ti–6Al–4V and Ti–6Al–7Nb alloys has increased by 113 and 58 HV(0.5), respectively. After shotpeening, ultimate tensile strength of Ti–6Al–4V increased from 1000 MPa to 1150 MPa, higher than improvement obtained for heat treated titanium specimens. The results confirm that shotpeening pre-treatment improved tensile and sliding wear behavior of Ti–6Al–4V and Ti–6Al–7Nb alloys. In addition, shotpeening increased surface roughness.