Origin of double dinitrogen release feature during fast switching between lean and rich cycles for NOx storage reduction catalysts

The performance of NOx storage and reduction over 1.5 wt% Pt/20 wt% KNO3/K2Ti8O17 and 1.5 wt% Pt/K2Ti8O17 catalysts has been investigated using combined fast transient kinetic switching and isotopically labelled (NO)-N-15 at 350 degrees C. The evolution of product N-2 has revealed two significant peaks during 60 s lean/1.3 s rich switches. It also found that the presence of CO2 in the feed affects the release of N-2 in the second peak. Regardless of the presence/absence of water in the feed, only one peak of N-2 was observed in the absence of CO2. Gas-phase NH3 was not observed in any of the experiments. However, in the presence of CO2 the results obtained from in situ DRIFTS-MS analysis showed that isocyanate species are formed and stored during the rich cycles, probably from the reaction between NOx and CO, in which CO was formed via the reverse water-gas shift reaction. 

Evaluation and mechanistic investigation of a AuPd alloy catalyst for the hydrocarbon selective catalytic reduction (HC-SCR) of NOx

The ability of a gold palladium bimetallic catalyst to selectively oxidise toluene has been used to enhance the hydrocarbon selective catalytic reduction of NOx, a reaction in which the interaction of partial oxidation intermediates is considered important. The combination of gold with palladium has a synergistic effect, producing a catalyst that is more active for NOx conversion than the arithmetic sum of the corresponding mono-metallic materials. Three regimes in the conversion profile of the AuPd catalyst are proposed relating to production and consumption of toluene derived species, such as benzaldehyde and benzonitrile. The possible role of these reaction intermediates in the toluene HC-SCR reaction is examined. Using 15NO, the formation of N2 and N2O is observed via the direct interaction between the nitrogen atom of benzonitrile and 15NO. The higher activity of the bimetallic catalyst for the NOx reduction reaction by toluene is discussed in the context of these partial oxidation intermediates.

Promoting Dignity for All: Human Rights Approaches in the Post-2015 Climate Change, Disaster Risk Reduction and Sustainable Development Frameworks

This article takes as its starting point the potentially negative human rights implications that the effects of climate change, disasters and development practices can have on individuals and communities. It argues that key international instruments, including the post-2015 successors to the Kyoto Protocol, Hyogo Framework for Action on disaster risk reduction and the Millennium Development Goals, appear to be moving towards an express acknowledgment of the relevance of international human rights law as an important mechanism to minimise potential harms that may arise. This raises the question as to the appropriate role of the UN human rights monitoring and accountability mechanisms in identifying the relevant rights-holders and duty-bearers. The article therefore provides an examination of the linkages between climate change and international human rights law, as well as discussion of the human rights considerations and accountability mechanisms for disasters and sustainable development. The article concludes by arguing that despite differential understandings between disciplines as to the meaning of key terms such as ‘vulnerability’ and ‘resilience’, international human rights law provides a comprehensive basis for promoting international and national accountability. It follows that a greater level of coordination and coherence between the human rights approaches of the various post-2015 legal and policy frameworks is warranted as a means of promoting the dignity of those most affected by climate change, disasters and developmental activities.

Assessing the effectiveness of a DRA versus DRA with an activity schedule procedure on the reduction of problem behaviour

Differential Reinforcement of Alternative behaviour (DRA) (Athens & Vollmer, 2010; Cooper, Heron, & Heward, 2007) is a procedure that consists in withholding reinforcement for the targeted inappropriate behaviour while reinforcing behaviours, i.e., that have the same function, but socially more acceptable topographies. DRA has repeatedly proven to be effective in reducing problem behaviours in individuals with autism (Campbell, 2003). On the other hand, a number of single-subject research studies have provided evidence for the use of activity schedules as a means to decrease aggressive behaviour (Dooley et al., 2001; Flannery & Hemer, 1994; Lalli, Casey, Goh, & Merlinoet al., 1994). The purpose of the present study was to evaluate the effectiveness of DRA in combination with the use of an activity schedule. We compared the impact of the visual activities schedule used in combination with a DRA procedure versus the impact of the DRA procedure used alone on problem behaviour of a boy diagnosed with an Autism Spectrum Disorder. An alternating treatments design was used to compare the rate of behaviour problems in each of the two treatment conditions. DRA was delivered as treatment A, while the combination of the activities schedule and DRA was treatment B.

The reduction of serum soluble Flt-1 in patients with neovascular age-related macular degeneration

PURPOSE: To evaluate serum soluble Flt-1 (sFlt-1) in age-related degeneration (AMD) patients.

DESIGN: Case control study.

METHODS: Fifty-six non-AMD participants, fifty-three early AMD patients and ninety-seven neovascular AMD patients from Belfast in Northern Ireland. Serum samples were collected from each patient. Serum sFlt-1 was measured by human sVEGFR1/sFlt-1 ELISA kit. The results were analyzed by Excel and SPSS.

RESULTS: Serum sFlt-1 concentration of non-AMD, early AMD, and neovascular AMD were 90.8±2.9 pg/mL (±SEM), 88.2±2.6 pg/mL and 79.9±2.2 pg/mL. sFlt-1 from neovascular AMD patients was significantly decreased compared to non-AMD and early AMD patients (ANOVA, p<0.01). For each 10 point increase in sFlt-1, the odds for having neovascular AMD compared with non-AMD and neovascular AMD decreases by 27.8% OR=0.722 (95% CI: 0.588-0.888, p=0.002) and 27.0% OR=0.730 (95% CI: 0.594-0.898, p=0.003), respectively. In patients over 73 years of age, serum sFlt-1 <80 pg/mL was associated with a >6-fold higher risk of neovascular AMD.

CONCLUSIONS: Reduced serum sFlt-1 differentiates those patients with neovascular AMD from both early AMD and non-AMD participants. In those aged over 73, serum sFlt <80 pg/mL seems to indicate a particularly high risk of neovascular AMD. Our results indicate serum sFlt-1 could be a biomarker for development of neovascular AMD.

Nanoencapsulation of ABT-737 and camptothecin enhances their clinical potential through synergistic antitumor effects and reduction of systemic toxicity

The simultaneous delivery of multiple cancer drugs in combination therapies to achieve optimal therapeutic effects in patients can be challenging. This study investigated whether co-encapsulation of the BH3-mimetic ABT-737 and the topoisomerase I inhibitor camptothecin (CPT) in PEGylated polymeric nanoparticles (NPs) was a viable strategy for overcoming their clinical limitations and to deliver both compounds at optimal ratios. We found that thrombocytopenia induced by exposure to ABT-737 was diminished through its encapsulation in NPs. Similarly, CPT-associated leukopenia and gastrointestinal toxicity were reduced compared with the administration of free CPT. In addition to the reduction of dose-limiting side effects, the co-encapsulation of both anticancer compounds in a single NP produced synergistic induction of apoptosis in both in vitro and in vivo colorectal cancer models. This strategy may widen the therapeutic window of these and other drugs and may enhance the clinical efficacy of synergistic drug combinations.

Quantum yield measurements for the photocatalytic oxidation of Acid Orange 7 (AO7) and reduction of 2,6-dichloroindophenol (DCIP) on transparent TiO2 films of various thickness

This work comprises the photoactivity assessment of transparent sol–gel TiO2 coatings of various thickness using two test systems. The initial rates of both photocatalytic reactions, namely the oxidative bleaching of Acid Orange 7 (AO7) and the reductive bleaching of 2,6-dichlorindophenol (DCIP) increase linearly with increasing titania film thickness as well as with increasing absorbed light flux. The latter work revealed quantum yields (QY) of 0.19% and 92% for the AO7 and DCIP test system, respectively. The low QY for the AO7 oxidation is due to the combination of a slow irreversible reduction of oxygen and also for the oxidation of AO7, thus favouring the high efficiency for electron–hole recombination that is typical for aqueous organic pollutants. In contrast, the very high QY for the photocatalysed reduction of DCIP is due to the presence of a vast excess of glycerol which traps the photogenerated holes efficiently and so allow time for the slower reduction of dye to take place. Furthermore, the oxidation of glycerol results in the generation of highly reducing R-hydroxyalkyl radicals that are able to also reduce DCIP. As a consequence of this ‘current doubling’ effect, the observed QY (92%) is much higher than the apparent theoretical value of 50%.

Distributed Consensus Charging for Current Unbalance Reduction

Electric Vehicle (EV) technology has developed rapidly in recent years, with the result that increasing levels of EV penetration are expected on electrical grids in the near future. The increasing electricity demand due to EVs is expected to provide many challenges for grid companies, and it is expected that it will be necessary to reinforce the current electrical grid infrastructure to cater for increasing loads at distribution level. However, by harnessing the power of Vehicle to Grid (V2G) technologies, groups of EVs could be harnessed to provide ancillary services to the grid. Current unbalance occurs at distribution level when currents are unbalanced between each of the phases. In this paper a distributed consensus algorithm is used to coordinate EV charging in order to minimise current unbalance. Simulation results demonstrate that the proposed algorithm is effective in rebalancing phase currents.

Reduction of the temperature sensitivity of Halomonas hydrothermalis by iron starvation combined with microaerobic conditions

The limits to biological processes on Earth are determined by physicochemical parameters, such as extremes of temperature and low water availability. Research into microbial extremophiles has enhanced our understanding of the biophysical boundaries which define the biosphere. However, there remains a paucity of information on the degree to which rates of microbial multiplication within extreme environments are determined by the availability of specific chemical elements. Here, we show that iron availability and composition of the gaseous phase (aerobic vs. microaerobic) determine susceptibility of a marine bacterium, Halomonas hydrothermalis, to sub-optimal and elevated temperature and salinity by impacting rates of cell division (but not viability). In particular, iron starvation combined with microaerobic conditions (5 % v/v of O2, 10 % v/v of CO2, reduced pH) reduced sensitivity to temperature across the 13 °C range tested. These data demonstrate that nutrient limitation interacts with physicochemical parameters to determine biological permissiveness for extreme environments. The interplay between resource availability and stress tolerance, therefore, may shape the distribution and ecology of microorganisms within Earth's biosphere.

Determining the Effect of Plasma Pre-Treatment on Antimony Tin Oxide to Support Pt@Pd and the Oxygen Reduction Reaction Activity

This article reveals the effect of plasma pre-treatment on antimony tin oxide (ATO) nanoparticles. The effect is to allow Pt@Pd to be deposited homogeneously on the ATO surface with high dispersion and narrow particle size distribution. The Pt@Pd core–shell catalyst was prepared using the polyol method and shows a dramatic improvement towards ORR activity and durability.

Microelectrode Voltammetry of Dioxygen Reduction in a Phosphonium Cation-Based Room-Temperature Ionic Liquid: Quantitative Studies

Microelectrode voltammetry is used to study the electrochemical reduction of dioxygen, O-2, in the room-temperature ionic liquid trihexyl(tetradecyl)phosphonium trifluorotris(pentafluoroethyl)phosphate [P6,6,6,14][FAP]. The nature of the unusual voltammetric waves is quantitatively modeled via digital simulation with the aim of clarifying apparent inconsistencies in the literature. The reduction is shown to proceed via a two-electron reaction and involve the likely capture of a proton from the solvent system. The oxidative voltammetric signals seen at fast scan rates are interpreted as resulting from the reoxidation of HO2 center dot. In the presence of large amounts of dissolved carbon dioxide the reductive currents decrease by a factor of ca. two, consistent with the trapping of the superoxide radical, O-2(center dot), intermediate in the two-electron reduction process.

Photoelectrochemistry with quinone radical anions - Photoassisted reduction of halobenzenes and carbonyl compounds

Photoexcited electrochemically generated quinone radical anions reduced 1,2-dibromobenzene to bromobenzene, 1,4-dibromobenzene to bromobenzene and 4-chlorobenzonitrile to benzonitrile. In the presence of anthracene, 2-bromophenyl-, 4-bromophenyl- and 4-cyanophenyl-anthracenes were formed. With acetaldehyde, acetone, acetophenone, benzaldehyde and benzophenone, the major products were the corresponding pinacols, with small amounts of the two-electron secondary alcohols. In acetonitrile as solvent, cinnamonitriles, hydrocinnamonitriles and phenylglutaronitriles were formed in addition to the alcohols. Glyoxylic acid was reduced to tartaric, glycolic and malic acids. The reduction of CO₂ was unsuccessful.

One-Electron Reduction of 2-Nitrotoluene, Nitrocyclopentane, and 1-Nitrobutane in Room Temperature Ionic Liquids: A Comparative Study of Butler–Volmer and Symmetric Marcus–Hush Theories Using Microdisk Electrodes

The voltammetry for the reduction of 2-nitrotoluene at a gold microdisk electrode is reported in two ionic liquids: trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate ([P-14,P-6,P-6,P-6][FAP]) and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Emim][NTf2]). The reduction of nitrocyclopentane (NCP) and 1-nitrobutane (BuN) was investigated using voltammetry at a gold microdisk electrode in the ionic liquid [P-14,P-6,P-6,P-6][FAP]. Simulated voltammograms, generated through the use of ButlerVolmer theory and symmetric MarcusHush theory, were compared to experimental data, with both theories parametrizing the data similarly well. An experimental value for the Marcusian parameter, 1 was also determined in all cases. For the reduction of 2-nitrotoluene, this was 0.5 +/- 0.1 eV in both solvents, while for NCP and BuN in [P-14,P-6,P-6,P-6][FAP], it was 2 +/- 0.1 and 5 +/- 0.1 eV, respectively. This is attributed to the localization of charge on the nitro group and the primary nitro alkyls increased interaction with the environment, resulting in a larger reorganization energy.