Insight into the key aspects of the regeneration process in the NOx storage reduction (NSR) reaction probed using fast transient kinetics coupled with isotopically labelled (NO)-N-15 over Pt and Rh-containing Ba/Al2O3 catalysts

For the first time, the coupling of fast transient kinetic switching and the use of an isotopically labelled reactant (15NO) has allowed detailed analysis of the evolution of all the products and reactants involved in the regeneration of a NOx storage reduction (NSR) material. Using realistic regeneration times (ca. 1 s) for Pt, Rh and Pt/Rh-containing Ba/Al2O3 catalysts we have revealed an unexpected double peak in the evolution of nitrogen. The first peak occurred immediately on switching from lean to rich conditions, while the second peak started at the point at which the gases switched from rich to lean. The first evolution of nitrogen occurs as a result of the fast reaction between H2 and/or CO and NO on reduced Rh and/or Pt sites. The second N2 peak which occurs upon removal of the rich phase can be explained by reaction of stored ammonia with stored NOx, gas phase NOx or O2. The ammonia can be formed either by hydrolysis of isocyanates or by direct reaction of NO and H2.

The study highlights the importance of the relative rates of regeneration and storage in determining the overall performance of the catalysts. The performance of the monometallic 1.1%Rh/Ba/Al2O3 catalyst at 250 and 350 °C was found to be dependent on the rate of NOx storage, since the rate of regeneration was sufficient to remove the NOx stored in the lean phase. In contrast, for the monometallic 1.6%Pt/Ba/Al2O3 catalyst at 250 °C, the rate of regeneration was the determining factor with the result that the amount of NOx stored on the catalyst deteriorated from cycle to cycle until the amount of NOx stored in the lean phase matched the NOx reduced in the rich phase. On the basis of the ratio of exposed metal surface atoms to total Ba content, the monometallic 1.6%Pt/Ba/Al2O3 catalyst outperformed the Rh-containing catalysts at 250 and 350 °C even when CO was used as a reductant.

Thermotropic Ruthenium(II)-Containing Metallomesogens Based on Substituted 1,10-Phenanthroline Ligands

Imidazo[4,5-f]-1,10-phenanthroline and pyrazino[2,3-f]-1,10-phenanthroline substituted with long alkyl chains are versatile ligands for the design of metallomesogens because of the ease of ligand substitution. Whereas the ligands and the corresponding rhenium(I) complexes were not liquid-crystalline, mesomorphism was observed for the corresponding ionic ruthenium(II) complexes with chloride, hexafluorophosphate, and bistriflimide counterions. The mesophases were identified as smectic A phases by high-temperature small-angle X-ray scattering (SAXS) using synchrotron radiation. The transition temperatures depend on the anion, the highest temperatures being observed for the chloride salts and the lowest for the bistriflimide salts. The ruthenium(II) complexes are examples of luminescent ionic liquid crystals.

Genetic programming based formulation for fresh and hardened properties of self-compacting concrete containing pulverised fuel ash

Self-compacting concrete (SCC) flows into place and around obstructions under its own weight to fill the formwork completely and self-compact without any segregation and blocking. Elimination of the need for compaction leads to better quality concrete and substantial improvement of working conditions. This investigation aimed to show possible applicability of genetic programming (GP) to model and formulate the fresh and hardened properties of self-compacting concrete (SCC) containing pulverised fuel ash (PFA) based on experimental data. Twenty-six mixes were made with 0.38 to 0.72 water-to-binder ratio (W/B), 183–317 kg/m³ of cement content, 29–261 kg/m³ of PFA, and 0 to 1% of superplasticizer, by mass of powder. Parameters of SCC mixes modelled by genetic programming were the slump flow, JRing combined to the Orimet, JRing combined to cone, and the compressive strength at 7, 28 and 90 days. GP is constructed of training and testing data using the experimental results obtained in this study. The results of genetic programming models are compared with experimental results and are found to be quite accurate. GP has showed a strong potential as a feasible tool for modelling the fresh properties and the compressive strength of SCC containing PFA and produced analytical prediction of these properties as a function as the mix ingredients. Results showed that the GP model thus developed is not only capable of accurately predicting the slump flow, JRing combined to the Orimet, JRing combined to cone, and the compressive strength used in the training process, but it can also effectively predict the above properties for new mixes designed within the practical range with the variation of mix ingredients.

Modelling the performance of self-compacting SIFCON of cement slurries containing limestone powder using genetic programming technique

The paper explores the potential of applicability of Genetic programming approach (GP), adopted in this investigation, to model the combined effects of five independent variables to predict the mini-slump, the plate cohesion meter, the induced bleeding test, the J-fiber penetration value, and the compressive strength at 7 and 28 days of self-compacting slurry infiltrated fiber concrete (SIFCON). The variables investigated were the proportions of limestone powder (LSP) and sand, the dosage rates of superplasticiser (SP) and viscosity modifying agent (VMA), and water-to-binder ratio (W/B). Twenty eight mixtures were made with 10-50% LSP as replacement of cement, 0.02-0.06% VMA by mass of cement, 0.6-1.2% SP and 50-150% sand (% mass of binder) and 0.42-0.48 W/B. The proposed genetic models of the self-compacting SIFCON offer useful modelling approach regarding the mix optimisation in predicting the fluidity, the cohesion, the bleeding, the penetration, and the compressive strength.

New ionic liquids containing an appended hydroxyl functionality from the atom-efficient, one-pot reaction of 1-methylimidazole and acid with propylene oxide

New ionic liquids containing ( 2- hydroxypropyl)- functionalized imidazolium cations have been synthesized by the atom- efficient, room temperature reaction of 1- methylimidazole with acid and propylene oxide; the acid providing the anionic component of the resultant ionic liquids. The incorporation of the secondary hydroxyl- functionality in the cation causes some interesting modifications to the behavior of these ionic liquids, increasing hydrophilicity and resulting in the unprecedented formation of liquid - liquid biphases with acetone. The single crystal structure of 1-( 2- hydroxypropyl)- 3- methylimidazolium tetraphenylborate, prepared by metathesis of the corresponding chloride- containing ionic liquid, has also been determined.

Alpha-1-antitrypsin aerosolized augmentation abrogates neutrophil elastase-induced expression of cathepsin B and matrix metalloprotease 2 in vivo and in vitro

Background: Neutrophil elastase (NE) activity is increased in lung diseases such as a1-antitrypsin (A1AT) deficiency and pneumonia. It has recently been shown to induce expression of cathepsin B and matrix metalloprotease 2 (MMP-2) in vitro and in a mouse model. It is postulated that increased cathepsin B and MMP-2 in acute and chronic lung diseases result from high levels of extracellular NE and that expression of these proteases could be inhibited by A1AT augmentation therapy.

Methods: Cathepsin and MMP activities were assessed in bronchoalveolar lavage (BAL) fluid from patients with A1AT deficiency, pneumonia and control subjects. Macrophages were exposed to BAL fluid rich in free NE from patients with pneumonia following pretreatment with A1AT. MMP-2, cathepsin B, secretory leucoprotease inhibitor (SLPI) and lactoferrin levels were determined in BAL fluid from A1AT-deficient patients before and after aerosolisation of A1AT.

Results: BAL fluid from both patients with pneumonia and those with A1AT deficiency containing free NE had increased cathepsin B and MMP-2 activities compared with BAL fluid from healthy volunteers. The addition of A1AT to BAL fluid from patients with pneumonia greatly reduced NE-induced cathepsin B and MMP-2 expression in macrophages in vitro. A1AT augmentation therapy to A1AT-deficient individuals also reduced cathepsin B and MMP-2 activity in BAL fluid in vivo. Furthermore, A1AT-deficient patients had higher levels of SLPI and lactoferrin after A1AT augmentation therapy.

Conclusion: These findings suggest a novel role for A1AT inhibition of NE-induced upregulation of MMP and cathepsin expression both in vitro and in vivo.

An investigation into the behaviour of concrete containing seawater-neutralised bauxite refinery residues in silage effluent

The farm production of silage as a winter-feed supplement is widespread. However, the bins in which silage is produced are subject to acidic and microbial attacks. Both these types of attack can lead to a weakening and failure of the concretes, especially on the outer lip of the open side of the silage pit. Consequently, the development of an acid-resistant concrete that can extend the life span of silage bins on farms could lead to considerable cost savings for farmers and, hence, can improve farm productivity. This paper reports on test results of an investigation into the behaviour of concrete containing seawater-neutralised bauxite refinery residues (Bauxsol™) exposed to sulphuric acid environments in the laboratory and to silage effluents. The concrete manufactured had a fixed water–cement ratio of 0.55 and natural sand was replaced with the Bauxsol™ at 0%, 5%, 10%, 15% and 20% by cement mass. Results indicated that the use of Bauxsol™ as a sand replacement material improved the behaviour of concrete both in sulphuric acid in the laboratory as well as in the silage effluent. Consequently, it is concluded that the Bauxsol™ can be used to replace 10% of natural sand to produce concrete that is resistant to silage effluents, providing an extended service life over conventional concretes used in silage pits.

Neural Network Modeling of Rheological Parameters of Grouts Containing Viscosity-Modifying Agent

The development of artificial neural network (ANN) models to predict the rheological behavior of grouts is described is this paper and the sensitivity of such parameters to the variation in mixture ingredients is also evaluated. The input parameters of the neural network were the mixture ingredients influencing the rheological behavior of grouts, namely the cement content, fly ash, ground-granulated blast-furnace slag, limestone powder, silica fume, water-binder ratio (w/b), high-range water-reducing admixture, and viscosity-modifying agent (welan gum). The six outputs of the ANN models were the mini-slump, the apparent viscosity at low shear, and the yield stress and plastic viscosity values of the Bingham and modified Bingham models, respectively. The model is based on a multi-layer feed-forward neural network. The details of the proposed ANN with its architecture, training, and validation are presented in this paper. A database of 186 mixtures from eight different studies was developed to train and test the ANN model. The effectiveness of the trained ANN model is evaluated by comparing its responses with the experimental data that were used in the training process. The results show that the ANN model can accurately predict the mini-slump, the apparent viscosity at low shear, the yield stress, and the plastic viscosity values of the Bingham and modified Bingham models of the pseudo-plastic grouts used in the training process. The results can also predict these properties of new mixtures within the practical range of the input variables used in the training with an absolute error of 2%, 0.5%, 8%, 4%, 2%, and 1.6%, respectively. The sensitivity of the ANN model showed that the trend data obtained by the models were in good agreement with the actual experimental results, demonstrating the effect of mixture ingredients on fluidity and the rheological parameters with both the Bingham and modified Bingham models.