Radial density distribution of fractal clusters

The radial density distributions of fractal clusters generated in both DLCA and RLCA conditions by Monte-Carlo off-lattice cluster-cluster aggregation have been investigated. It has been computed by averaging a large number of clusters of same mass to form an average cluster, which is then considered as spherically symmetric. It is found that the radial density distribution, calculated using the mass center of the cluster as the center point, does not follow the fractal scaling, as sometimes assumed in the literature. An empirical model has been proposed to describe the dependence of the radial density distribution on the number of particles in the cluster. The obtained radial density distribution is used to compute permeability profile of the fractal cluster using several literature models, which is then applied to estimate the cluster hydrodynamic radius, R_h, by considering the cluster as a porous permeable object and using the solution of Brinkman equations for the fluid flow inside the cluster. The so obtained R_h values are compared to those in the literature, computed using the Kirkwood-Riseman (KR) theory. It has been found that, among the five permeability models examined, only the model proposed by Davis (Proceedings of the Institution of Mechanical Engineers Part B 1, 185) provides results in good agreement with those obtained using the KR model. Furthermore, it has been verified that the R_h values are insensitive to the model used for the density distribution.     

Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

Hybrid materials based on metal oxides and poly(organophosphazenes)

In this paper the sol-gel preparation of hybrid materials made of metal oxide and polytorganophosphazenel components is described. The main problem focused on during this research was to avoid phase separation in order to get homogeneous materials. This problem was pursued looking at the formation of genuine chemical bonds between the exploited polyphosphazenes and the inorganic composite networks. Investigations on the thermal, mechanical, and electroconductive properties of the synthesized, phosphazene-containing composite materials showed that these matrices presented improved mechanical and thermal features with respect to those of the original phosphazene macromolecule, while the ionic conductivities of the prepared molecular hybrids doped with lithium or silver trillate are of the same order of magnitude as those measured for the neat, original phosphazene substrate.Presented at the Ist Italian Workshop on Cyclo- and Polytphosphazenel Materials. February 15–16, 1996. at the CNR Research Area in Padova, Italy.     

4D video textures for interactive character appearance

4D Video Textures (4DVT) introduce a novel representation for rendering video‐realistic interactive character animation from a database of 4D actor performance captured in a multiple camera studio. 4D performance capture reconstructs dynamic shape and appearance over time but is limited to free‐viewpoint video replay of the same motion. Interactive animation from 4D performance capture has so far been limited to surface shape only. 4DVT is the final piece in the puzzle enabling video‐realistic interactive animation through two contributions: a layered view‐dependent texture map representation which supports efficient storage, transmission and rendering from multiple view video capture; and a rendering approach that combines multiple 4DVT sequences in a parametric motion space, maintaining video quality rendering of dynamic surface appearance whilst allowing high‐level interactive control of character motion and viewpoint. 4DVT is demonstrated for multiple characters and evaluated both quantitatively and through a user‐study which confirms that the visual quality of captured video is maintained. The 4DVT representation achieves >90% reduction in size and halves the rendering cost.     

Aphid deterrence by glucose esters in glandular trichome exudate of the wild tomato,Lycopersicon pennellii

Settling of the potato aphid,Macrosiphum euphorbiae, on feeding membranes was deterred by methanolic leaf rinses ofLycopersicon pennellii, or of its F₁ with tomato,L. esculentum. The active compounds in theL. pennellii rinsates were identified as 2,3,4-tri-O-acylglucoses bearing short to medium chain length fatty acids. These compounds are localized in the glandular exudate of the type IV trichomes and may accumulate to levels in excess of 400 g/cm². In choice assays, purified glucose esters fromL. pennellii reduced aphid settling at concentrations as low as 25 g/cm²; at concentrations of 150 g/cm² or more, all aphids avoided treated areas. Glucose esters were also active in deterring aphid settling in no-choice assays. At 100 g/ cm², these esters resulted in increased levels of mortality after 48 hr.     

Reactive Compatibilizer Precursors for LDPE/PA6 Blends, 4

Summary: The effectiveness of some thermoplastic elastomers grafted with maleic anhydride (MA) or with glycidyl methacrylate (GMA) as compatibilizer precursors (CPs) for blends of low density polyethylene (LDPE) with polyamide‐6 (PA) has been studied. The CPs were produced by grafting different amounts of MA or GMA onto a styrene‐block‐(ethylene‐co‐1‐butene)‐block‐styrene copolymer (SEBS) (KRATON G 1652), either in the melt or in solution. A commercially available SEBS‐g‐MA copolymer with 1.7 wt.‐% MA (KRATON FG 1901X) was also used. The effect of the MA concentration and of other characteristics of the SEBS‐g‐MA CPs was also studied. The specific interactions between the CPs and the blends components were investigated through characterizations of the binary LDPE/CP and PA/CP blends, in the whole composition range. It was demonstrated that the SEBS‐g‐GMA copolymers display poor compatibilizing effectiveness due to cross‐linking resulting from reactions of the epoxy rings of these CPs with both the amine and the carboxyl end groups of PA. On the contrary, the compatibilizing efficiency of the MA‐grafted elastomers, as revealed by the thermal properties and the morphology of the compatibilized blends, was shown to be excellent. The results of this study confirm that the anhydride functional groups possess considerably higher efficiency, for the reactive compatibilization of LDPE/PA blends, than those of the ethylene‐acrylic acid and ethylene‐glycidyl methacrylate copolymers investigated in previous works.

SEM micrograph of the 75/25 LD08/PA blend (with 2 phr SEBSMA1).     

An ensemble evolutionary constraint-based approach to understand the emergence of metabolic phenotypes

Constraint-based modeling is largely used in computational studies of metabolism. We propose here a novel approach that aims to identify ensembles of flux distributions that comply with one or more target phenotype(s). The methodology has been tested on a small-scale model of yeast energy metabolism. The target phenotypes describe the differential pattern of ethanol production and O₂ consumption observed in “Crabtree-positive” and “Crabtree-negative” yeasts in changing environment (i.e., when the upper limit of glucose uptake is varied). The ensembles were obtained either by selection among sampled flux distributions or by means of a search heuristic (genetic algorithm). The former approach provided indication about the probability to observe a given phenotype, but the resulting ensembles could not be unambiguously partitioned into “Crabtree-positive” and “Crabtree-negative” clusters. On the contrary well-separated clusters were obtained with the latter method. The cluster analysis further allowed identification of distinct groups within each target phenotype. The method may thus prove useful in characterizing the design principles underlying metabolic plasticity arising from evolving physio-pathological or developmental constraints.     

Catalytic combustion over platinum group catalysts: fuel-lean versus fuel-rich operation

Performance data are presented for methane oxidation on alumina-supported Pd, Pt, and Rh catalysts under both fuel-rich and fuel-lean conditions. Catalyst activity was measured in a micro-scale isothermal reactor at temperatures between 300 and 800 °C. Non-isothermal (near adiabatic) temperature and reaction data were obtained in a full-length (non-differential) sub-scale reactor operating at high pressure (0.9 MPa) and constant inlet temperature, simulating actual reactor operation in catalytic combustion applications.

Under fuel-lean conditions, Pd catalyst was the most active, although deactivation occurred above 650 °C, with reactivation upon cooling. Rh catalyst also deactivated above 750 °C, but did not reactivate. Pt catalyst was active above 600 °C. Fuel-lean reaction products were CO₂ and H₂O for all three catalysts.

The same catalysts tested under fuel-rich conditions demonstrated much higher activity. In addition, a ‘lightoff’ temperature was found (between 450 and 600 °C), where a stepwise increase in reaction rate was observed. Following ‘lightoff’ partial oxidation products (CO, H₂) appeared in the mixture, and their concentration increased with increasing temperature. All three catalysts exhibited this behavior.

High-pressure (0.9 MPa) sub-scale reactor and combustor data are shown, demonstrating the benefits of fuel-rich operation over the catalyst for ultra-low emissions combustion.     

Electrochemical characterization of 8-hydroxyquinoline-5-sulphonate/aluminium(III) aqueous solutions

8-Hydroxyquinoline-5-sulphonate/Al(III) aqueous solutions were studied both by potentiometric titrations and voltammetric measurements, in order to obtain the number, the stoichiometry and the stability constants of the complexes formed at equilibrium, and to evaluate the redox and (electro)kinetic properties of the free ligand and of the metal/ligand complexes. The complexes formed in 0.2 m (Na)Cl aqueous solution (stability log beta values ± standard deviation) are AlL⁺ (8.95 ± 0.05), AlL₂⁻ (17.43 ± 0.03) and AlL₃³⁻ (24.58 ± 0.05), where “L” denotes the free ligand in the completely deprotonated form (L²⁻, pK_a1 = 3.910 ± 0.008, pK_a2 = 8.319 ± 0.004). AlL₃³⁻ is the predominant Al(III) species in a very wide range of pH, metal and ligand concentrations and metal-to-ligand ratios. The free ligand shows an oxidation wave at 0.62 V versus SCE. The proposed oxidation mechanism includes a first reversible one-electron oxidation of the ligand, followed by a coupling reaction and by a second reversible one-electron oxidation, and finally by a decomposition reaction. The addition of Al(III) lowers the intensity of the oxidation wave due to the formation of the redox-inactive complex AlL₃³⁻. A residual low signal was attributed to the free ligand produced by the complex dissociation, AlL₃³⁻ = AlL₂⁻ + L²⁻. All the kinetic parameters involved in the ligand oxidation and in the complex disruption were calculated on the basis of the agreement between experimental and simulated linear sweep and cyclic voltammetries. Correctness of the mechanisms proposed was further confirmed “a posteriori” by the agreement between potentiometric and linear sweep voltammetric results. The low residual signal observed in the presence of fully formed complex was attributed to the free ligand produced by the complex dissociation, having a kinetic constant estimated 0.2 s⁻¹.