New Molecular Species of Potential Interest to Atmospheric Chemistry: Isomers on the [H, S(2), Br] Potential Energy Surface

This work reports a state-of-the-art theoretical characterization of four new sulfur-bromine species and five transition states on the [H, S(2), Br] potential energy surface. Our highest level theoretical approach employed the method coupled cluster singles and doubles with perturbative contributions of connected triples, CCSD(T), along with the series of correlation-consistent basis sets and with extrapolation to the complete basis set (CBS) limit in the optimization of the geometrical parameters and to quantify the energetic quantities. The structural and vibrational frequencies here reported are unique and represent the most accurate investigation to date of these species. The global minimum corresponds to a skewed structure HSSBr with a disulfide bond; this is followed by a pyramidal-like structure, SSHBr, 18.85 kcal/mol above the minimum. Much higher in energy, we found another skewed structure, HSBrS (50.29 kcal/mol), with one S-Br dative-type bond, and another pyramidal-like one, HBrSS (109.80 kcal/mol), with two S-Br dative-type bonds. The interconversion of HSSBr into SSHBr can occur via a transfer of either the hydrogen or the bromine atom but involves a very high barrier of about 43 kcal/mol. These molecules are potentially a new route of coupling the sulfur and bromine chemistry in the atmosphere, and conditions of high concentration of H(2)S like in volcanic eruptions might contribute to their formation. We note that HSSBr can act as a reservoir molecule for the reaction between the radicals HSS and Br. Also, an assessment of the methods DFT/B3LYP/CBS and MP2/CBS relative to CCSD(T)/CBS provides insights on the expected performance of these methods on the characterization of polysulfides and also of more complex systems containing disulfide bridges.

Axial ligand influence on geometries, charge distributions and electronic structures of iron tetraazamacrocycle [Fe((II))TIM(X)(Y)](2+) complexes assessed by Density Functional Theory

We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H(2)O, NH(3), imidazole and CH(3)CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH(3)CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH(3)CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty pi* orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. (C) 2011 Elsevier Ltd. All rights reserved.

Solvent assisted decomposition of the tetrahedral intermediate of the transesterification reaction to biodiesel production. A density functional study

B3LYP/6-31 + G(d) calculations were employed to investigate the mechanism of the transesterification reaction between a model monoglyceride and the methoxide and ethoxide anions. The gas-phase results reveal that both reactions have essentially the same activation energy (5.9 kcal mol(-1)) for decomposition of the key tetrahedral intermediate. Solvent effects were included by means of both microsolvation and the polarizable continuum solvation model CPCM. Both solvent approaches reduce the activation energy, however, only the microsolvation model is able to introduce some differentiation between methanol and ethanol, yielding a lower activation energy for decomposition of the tetrahedral intermediate in the reaction with methanol (1.1 kcal mol(-1)) than for the corresponding reaction with ethanol (2.8 kcal mol(-1)), in line with experimental evidences. Analysis of the individual energy components within the CPCM approach reveals that electrostatic interactions are the main contribution to stabilization of the transition state. (C) 2009 Elsevier Ltd. All rights reserved.

Energy efficient envelope design for high-rise apartments

The energy required to create a comfortable living environment in  high-density cities in hot and humid climates usually demands a substantial electricity usage with an associated environmental burden. This paper describes an integrated passive design approach to reduce the cooling requirement for high-rise apartments through an improved building envelope design. The results show that a saving of 31.4% in annual required cooling energy and 36.8% in the peak cooling load for the BASECASE apartment can be achieved with this approach. However, all the passive strategies have marginal effect on latent cooling load, often less than 1%.

Conjugated linoleic acid decreases fat accretion in pigs evaluation by dual-energy X-ray absorptiometry

Thirty female Large White × Landrace pigs (average weight 57·2 (SD 1·9) kg) were allocated to one of six dietary treatments containing 0, 1·25, 2·5, 5·0, 7·5 or 10·0 g 55 % conjugated linoleic acids (CLA) isomers (CLA-55)/kg diet and fed for 8 weeks. Each pig was scanned at 0, 28 and 56 d and again at post slaughter using dual-energy X-ray absorptiometry (DXA) to determine the temporal pattern of body composition responses. Values determined by DXA were adjusted using regression equations generated from validation experiments between chemically and DXA-predicted values. Overall, there was a significant linear reduction in fat content with the increasing levels of CLA in the diet (P=0·007, P=0·011, P=0·008 at week 4, week 8 and for the carcass, respectively). The greatest improvement was recorded at the early stages of CLA supplementation and for the highest dose of CLA (week 4, -19·2 % compared with week 8, -13·7 %). In the first 4 weeks of feeding CLA, pigs receiving 10 g CLA-55/kg diet deposited 93 g less fat/d than pigs fed basal diets (P=0·002) compared with only 6 g less fat than control animals in the final 4 weeks. Lean content and lean deposition rate were maximised at 5 and 2·5 g CLA-55/kg diet for the first 4 weeks (P=0·016) and the final 4 weeks of treatment (P=0·17), respectively. DXA estimates of bone mineral content and bone mineral density were not affected by CLA supplementation throughout the experiment. These data demonstrate that dietary CLA decreases body fat in a dose-dependent manner and that the response is greatest over the initial 4 weeks of treatment.

Energy absorption and crushing behaviour of foam-filled aluminium tubes

The crushing behaviour and energy absorption of foam filled aluminium tubular structures were investigated using the quasi-static compressive tests. The crushing behaviour of the tubular structures changed due to foam filling. The energy absorption of the foam filled tubular structures was improved significantly. Foam filling caused an interaction effect between the tube and the foam during progressive crushing, leading to an increase in the mean crushing load compared to that of the foam or tube itself. This interaction effect might be affected by several parameters such as the density of the foam, the properties of both the foam material and tube material, and the thickness and outer diameter of the tube. In particular, the interaction effect essentially depended on the ratio of the mean crushing force of the foam to that of the tube.

Consumption of 'extra' foods (energy-dense, nutrient poor) among children aged 16-24 months from western Sydney, Australia

Objective: This study evaluates the contribution of energy-dense, nutrient-poor ‘extra’ foods to the diets of 16–24-month-old children from western Sydney, Australia.

Design:   An analysis of cross-sectional data collected on participants in the Childhood Asthma Prevention Study (CAPS), a randomised trial investigating the primary prevention of asthma from birth to 5 years. We collected 3-day weighed food records, calculated nutrient intakes, classified recorded foods into major food groups, and further classified foods as either ‘core’ or ‘extras’ according to the Australian Guide to Healthy Eating.

Setting:  Pregnant women, whose unborn child was at risk of developing asthma because of a family history, were recruited from all six hospitals in western Sydney, Australia. Data for this study were collected in clinic visits and at participants’ homes at the 18-month assessment.

Participants: Four hundred and twenty-nine children participating in the CAPS study; 80% of the total cohort.

Results:  The mean consumption of ‘extra’ foods was xs223C150 g day− 1 and contributed 25–30% of the total energy, fat, carbohydrate and sodium to the diets of the study children. ‘Extra’ foods also contributed around 20% of fibre, 10% of protein and zinc, and about 5% of calcium. Children in the highest quintile of ‘extra’ foods intake had a slightly higher but not significantly different intake of energy from those in the lowest quintile. However, significant differences were evident for the percentage of energy provided by carbohydrate and sugars (higher) and protein and saturated fat (lower). The intake of most micronutrients was also significantly lower among children in the highest quintile of consumption. The intake of ‘extra’ foods was inversely associated with the intake of core foods.

Conclusions:  The high percentage of energy contributed by ‘extra’ foods and their negative association with nutrient density emphasise the need for dietary guidance for parents of children aged 1–2 years. These preliminary data on commonly consumed ‘extra’ foods and portion sizes may inform age-specific dietary assessment methods.

A study on energy performance of hotel buildings in Singapore

This paper presents a study on energy performance of Singapore's hotel buildings. Energy consumption data and other pertinent information were collected from 29 quality hotels through a national survey. Building features and operational characteristics contributing to the variations in hotel energy performance were discussed. The annual average total energy use intensity (EUI) in these hotels is 427 kWh/m2. Electricity and gas are used in all sampled hotels, and some hotels also use diesel to power standby generator or hot water boiler. We also investigated relationships between electricity consumption and number of occupied rooms in individual hotels; the weak correlations found indicate it is necessary to improve energy management when occupancy rate is low. Besides, Pearson correlations between hotel energy use intensity and possible explanatory indicators revealed that three-star hotels differ from high class establishments in energy use. Worker density and years after the last major energy retrofit were also found to be highly correlated to hotel building energy use intensity. Also discussed in this paper is the effect of weather conditions on electricity consumption of the hotels.

Investigation of the postcure reaction and surface energy of epoxy resins using time-of-flight secondary ion mass spectrometry and contact-angle measurements

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to investigate correlations between the molecular changes and postcuring reaction on the surface of a diglycidyl ether of bisphenol A and diglycidylether of bisphenol F based epoxy resin cured with two different amine-based hardeners. The aim of this work was to present a proof of concept that ToF-SIMS has the ability to provide information regarding the reaction steps, path, and mechanism for organic reactions in general and for epoxy resin curing and postcuring reactions in particular. Contact-angle measurements were taken for the cured and postcured epoxy resins to correlate changes in the surface energy with the molecular structure of the surface. Principal components analysis (PCA) of the ToFSIMS positive spectra explained the variance in the molecular information, which was related to the resin curing and postcuring reactions with different hardeners and to the surface energy values. The first principal component captured information related to the chemical phenomena of the curing reaction path, branching, and network density based on changes in the relative ion density of the aliphatic hydrocarbon and the C₇H₇O⁺ positive ions. The second principal component captured information related to the difference in the surface energy, which was correlated to the difference in the relative intensity of the C_xH_yN_z⁺ ions of the samples. PCA of the negative spectra provided insight into the extent of consumption of the hardener molecules in the curing and postcuring reactions of both systems based on the relative ion intensity of the nitrogen-containing negative ions and showed molecular correlations with the sample surface energy.

Relationship between indices of adiposity obtained by peripheral quantitative computed tomography and dual-energy X-ray absorptiometry in pre-pubertal children

Background/Aim: The study investigated the relationship between indices of adiposity measured by peripheral quantitative computed tomography (pQCT) and dual-energy X-ray absorptiometry (DXA) in pre-pubertal children.

Subjects and methods: DXA-derived per cent body fat (%BF) was measured in 284 boys and 288 girls, aged 7–10 years. Cross-sections of the forearm (n=427) and lower leg (n=560) were obtained by pQCT to measure total cross-sectional area of the limb (Total CSA), Muscle CSA, Fat CSA, %Fat CSA (Fat CSA/Total CSA×100) and muscle density.

Results: Peripheral QCT-derived %Fat CSA in the forearm and lower leg correlated strongly with DXA-derived %BF (r=0.83–0.89, p<0.01) in both boys and girls. However, forearm and lower leg %Fat CSA were higher than whole body %BF by 5% and 10%, respectively. A better prediction of whole-body %BF was achieved by including %Fat CSA, muscle density and height into a hierarchical regression model. Using sex-specific regression equations, 87.7% of the boys and 83.7% of the girls had a predicted %BF within 3% units of the %BF obtained by DXA.

Conclusion: In pre-pubertal children, pQCT measures of adiposity are strongly associated with whole-body per cent body fat. This reproducible method could be an alternative technique to estimate body composition in this population.

Time and energy constraints in demanding phases of the annual cycle : an example of time limitation in refuelling migratory swans

The daily metabolizable energy intake of an animal is potentially limited by either the available feeding time or by its capacity to process energy. Animals are generally considered not to be time-limited but rather to be energy-processing-limited. This is concluded from the common observation that an animal's feeding time per day increases with a decrease in food density. We argue that such changes in feeding time are in theory also expected when no constraints are operating. Thus, a study of the constraints on energy intakes of free-living animals should be performed during demanding phases of the year. As an example, we collected data on time and energy budgets of Bewick's swan (Cygnus columbianus bewickii) refuelling during migration on fennel pondweed (Potamogeton pectinatus) tubers in two years differing two-fold in tuber biomass density. As predicted by time limitation, the feeding time (defined as the time with the head submerged) did not change in response to a change in food biomass density, both within and between years (averaging 12.2 h d⁻¹). Contrary to energy-processing limitation, and again in line with time limitation, the daily metabolizable energy intake varied, being greater in the year with high than in the year with low food densities. We conclude that more studies are needed of animals operating under demanding conditions before it can be assessed whether free-living animals are generally energy-processing- or time-limited.

Socioeconomic status and bone mineral density in a population-based sample of men

Overall, socioeconomic status (SES) is inversely associated with poorer health outcomes. However, current literature provides conflicting data of the relationship between SES and bone mineral density (BMD) in men. In an age-stratified population-based randomly selected cross-sectional study of men (n = 1467) we assessed the association between SES and lifestyle exposures in relation to BMD. SES was determined by matching the residential address for each subject with Australian Bureau of Statistics 2006 census data for the study region. BMD was measured at the spine and femoral neck by dual energy X-ray absorptiometry. Lifestyle variables were collected by self-report. Regression models were age-stratified into younger and older groups and adjusted for age, weight, dietary calcium, physical activity, and medications known to affect bone. Subjects with spinal abnormalities were excluded from analyses of BMD at the spine. In younger men, BMD was highest at the spine in the mid quintiles of SES, where differences were observed compared to quintile 1 (1–7%, p < 0.05). In older men, the pattern of BMD across SES quintiles was reversed, and subjects from mid quintiles had the lowest BMD, with differences observed compared to quintile 5 (1–7%, p < 0.05). Differences in BMD at the spine across SES quintiles represent a potential 1.5-fold increase in fracture risk for those with the lowest BMD. There were no differences in BMD at the femoral neck. Further research is warranted which examines the mechanisms that may underpin differences in BMD across SES quintiles and to address the current paucity of data in this field of enquiry.

Electrophoretic deposition of YSZ thin-film electrolyte for SOFCs utilizing electrostatic-steric stabilized suspensions obtained via high energy ball milling

This manuscript describes a facile alternative route to make thin-film yttria-stabilized zirconia (YSZ) electrolyte by liquid-phase assisted electrophoretic deposition utilizing electrostatic-steric stabilized YSZ suspension followed by sintering. Very fine YSZ particles in ball-milled suspension facilitate their sustained dispersion through electrostatic mechanism as evidenced by their higher zeta potentials. Binder addition into the ball-milled suspension is also demonstrated to contribute complementary steric hindrance effects on suspension stability. As the consequence, the film quality and sinterability improve in the sequence of film made from non ball-milled suspension, film made from ball-milled suspension and film made from ball-milled suspension with binder addition. The specific deposition mechanisms pertaining to each suspension are also postulated and discussed below. A very thin dense electrolyte layer of ∼10 μm can be achieved via electrophoretic deposition route utilizing ball-milled suspension and binder addition. This in turn, makes the electrolyte resistance a more negligible part of the overall cell resistance. Further on, we also tested the performance of SOFC utilizing as-formed 10 μm YSZ electrolyte i.e. YSZ-NiO|YSZ|LSM (La0.8Sr0.2MnO3-δ), whereby a maximum power density of ∼850 mW cm−2 at 850 °C was demonstrated.

Intelligent energy management for plug-in hybrid electric vehicles : the role of ITS infrastructure in vehicle electrification

The desire to reduce carbon emissions due to transportation sources has led over the past decade to the development of new propulsion technologies, focused on vehicle electrification (including hybrid, plug-in hybrid and battery electric vehicles). These propulsion technologies, along with advances in telecommunication and computing power, have the potential of making passenger and commercial vehicles more energy efficient and environment friendly. In particular, energy management algorithms are an integral part of plug-in vehicles and are very important for achieving the performance benefits. The optimal performance of energy management algorithms depends strongly on the ability to forecast energy demand from the vehicle. Information available about environment (temperature, humidity, wind, road grade, etc.) and traffic (traffic density, traffic lights, etc.), is very important in operating a vehicle at optimal efficiency. This article outlines some current technologies that can help achieving this optimum efficiency goal. In addition to information available from telematic and geographical information systems, knowledge of projected vehicle charging demand on the power grid is necessary to build an intelligent energy management controller for future plug-in hybrid and electric vehicles. The impact of charging millions of vehicles from the power grid could be significant, in the form of increased loading of power plants, transmission and distribution lines, emissions and economics (information are given and discussed for the US case). Therefore, this effect should be considered in an intelligent way by controlling/scheduling the charging through a communication based distributed control.

Reactions of Nb2 and Nb3 with CO, D2, N2, and O2 : reconciling experimental kinetics with density functional theory-calculated reaction profiles

 Calculated energy profiles for the reactions of neutral Nb₂ and Nb₃ metal clusters with CO, D₂, N₂, and O₂ are presented. In each reaction path, both a physisorption energy minimum, where the reactant remains intact, and a chemisorption energy minimum, where the reactant has dissociated, are calculated and linked by saddle points. We calculate branching ratios for the forward (dissociative) and reverse reactions which we compare with the experimental kinetic data. It is found that a combination of average thermal energies and barrier heights leads to wide variation in branching ratios which compares favourably to previously determined experimental reaction rates.