Formation of sulfur surface species on a commercial NO<Subscript>x</Subscript>-storage reduction catalyst

The influence of SO₂ exposure under lean (oxidizing) and rich (reducing) reaction conditions on the storage and oxidation/reduction function of a commercial NO_x storage-reduction catalyst was investigated by temperature-programmed uptake experiments and high temperature XRD. Both the storage capacity and the oxidation/reduction function of the catalyst were deactivated by SO₂ exposure under lean and rich reaction conditions. The deactivation of the storage component, i.e. the loss of the NO_x storage capacity, resulted mainly from the formation of Ba-sulfates accumulating in the bulk phase, which have a high thermal stability (>800°C) and, therefore, cannot be removed under the typical operation conditions of a NSR catalyst. For the oxidation function only a temporarily deactivation during lean reaction conditions was observed. Besides the formation of SO^2- ₄ species on the storage component at the beginning of the SO₂ exposure under rich conditions, an adsorption of SO₂ on the noble metal component was observed resulting in the formation of sulfur deposits. The oxidation of these sulfur species with a subsequent spillover of SO^2- ₄ species to the storage component during lean conditions could accelerate the deactivation of the storage capacity.     

Microhydrodynamical modeling of transverse susceptibility of magnetic inks (Theory of ‘DIMAG’)

The time and field dependence of the transverse susceptibility, χ_t, of a suspension of single domain ferromagnetic Brownian particles in a viscous fluid is calculated. Magnetic interactions are taken into account through the mean field model. The model is used to interpret (so far qualitatively) the so-called DIMAG experiment, in which a DC field is applied to the ink sample for a short period of time and a small perpendicular AC field probes χ_t before, during and after the DC field impact. The relative increase in χ_t, after the DC field is switched on was used earlier to characterize the dispersion quality of inks. We show that in the systems with negative interactions (acicular particles) this increase has a maximum when plotted as a function of the DC field. The maximum shifts to higher fields as the interaction increases, which corresponds to what happens in the DIMAG testing of less dispersed inks.     

An approximate analysis of drying operation of wet fabric

This study describes an approximate theoretical analysis of drying a moving wet fabric exposed to constant radiant heat and hot air blown normal to its surface. By considering the problem as a combination of heat and mass transfer processes, the governing dimensionless groups are identified and their influence on the residence time is established. These groups are then utilized in the prediction of either the residence time or the total length of travel needed to achieve a specific drying level of the fabric.     

Analysis of periodic 3D viscous flows using a quadratic discrete Galerkin boundary element method

A discrete Galerkin boundary element technique with a quadratic approximatión of the variables was developed to simulate the three-dimensional (3D) viscous flow established in periodic assemblages of particles in suspensions and within a periodic porous medium. The Batchelor's unit-cell approach is used. The Galerkin formulation effectively handles the discontinuity in the traction arising in flow boundaries with edges or corners, such as the unit cell in this case. For an ellipsoidal dilute suspension over the range of aspect ratio studied (1 to 54), the numerical solutions of the rotational velocity of the particles and the viscosity correction were found to agree with the analytic values within 0.2% and 2% respectively, even with coarse meshes. In a suspension of cylindrical particles the calculated period of rotation agreed with the experimental data. However, Burgers' predictions for the correction to the suspension viscosity were found to be 30% too low and therefore the concept of the equivalent ellipsoidal ratio is judged to be inadequate. For pressure-driven flow through a fixed bed of fibres, the prediction on the permeability was shown to deviate by as much as 10% from the value calculated based on approximate permeability additivity rules using the corresponding values for planar flow past a periodic array of parallel cylinders. These applications show the versatility of the technique for studying viscous flows in complicated 3D geometries.     

Multiple photosynthetic reaction centres composed of supramolecular assemblies of zinc porphyrin dendrimers with a fullerene acceptor

Multiple photosynthetic reaction centres have successfully been constructed using supramolecular complexes of zinc porphyrin dendrimers [D(ZnP)(n): n = 4, 8, 16] with fulleropyrrolidine bearing a pyridine ligand (C(60)py). Efficient energy migration occurs completely between the ZnP units of dendrimers prior to the electron transfer with increasing the generation of dendrimers to attain an extremely long charge-separation lifetime.     

Vibrational spectroscopic (FTIR and FTRaman) investigation using ab initio (HF) and DFT (LSDA and B3LYP) analysis on the structure of Toluic acid

The FTRaman and FTIR spectra for Toluic acid (TA) have been recorded in the region 4000-100 cm(-1) and compared with the harmonic vibrational frequencies calculated using HF/DFT (LSDA and B3LYP) method BY employing 6-311G (d, p) basis set with appropriate scale factors. IR intensities and Raman activities are also calculated by HF and DFT (LSDA/B3LYP) methods. Optimized geometries of the molecule have been interpreted and compared with the reported experimental values for benzoic acid and some substituted benzoic acids. The experimental geometrical parameters show satisfactory agreement with the theoretical prediction from HF and DFT. The scaled vibrational frequencies at B3LYP/6-311G (d, p) seem to coincide with the experimentally observed values with acceptable deviations. The theoretical spectrograms (IR and Raman) have been constructed and compared with the experimental FT-IR and FT-Raman spectra. Some of the vibrational frequencies of the TA are effected upon profusely with the methyl substitutions in comparison to benzoic acid and these differences are interpreted.     

Electrochemical, catalytic and antimicrobial activity of N-functionalized tetraazamacrocyclic binuclear nickel(II) complexes

The five binuclear nickel(II) complexes have been synthesized by the Schiff base condensation of 1,8-[bis(3-formyl-2-hydroxy-5-methyl)benzyl]-l,4,8,11-tetraazacyclo-tetradecane (PC) with appropriate aliphatic diamines and nickel(II) perchlorate. All the five complexes were characterized by elemental and spectral analysis. The electronic spectra of the complexes show three d-d transition in the range of 550-1055 nm due to 3A2g→3T2g(F), 3A2g→3T1g(F) and 3A2g→3T1g(P). These spin allowed electronic transitions are characteristic of an octahedral Ni2+ center. Electrochemical studies of the complexes show two irreversible one electron reduction waves at cathodic region. The reduction potential of the complexes shifts towards anodically upon increasing the chain length of the macrocyclic ring. All the nickel(II) complexes show two irreversible one electron oxidation waves at anodic region. The oxidation potential of the complexes shift towards anodically upon increasing the chain length of the macrocyclic ring. The catalytic activities of the complexes were observed to be increase with increase the macrocyclic ring size. The observed rate constant values for the catalytic hydrolysis of 4-nitrophenyl phosphate are in the range of 5.85×10(-3) to 9.14×10(-3) min(-1). All the complexes were screened for antimicrobial activity.     

Direct electrodeposition of porous platinum honeycomb structures

Honeycomb platinum was electrodeposited from an aqueous solution of K₂PtCl₄ and H₂SO₄ in a simple one step procedure using hydrogen bubbles as a dynamic template. SEM studies revealed the structure to consist of interconnecting pores with sizes from 5 to 10 μm, with fine structure consisting of nodules of 100 to 200 nm with sharp extrusions that exhibited excellent electrocatalytic activity for methanol oxidation. The simplicity of the method and the quality of the surfaces prepared suggest applications in catalysis where a convenient method to prepare high surface area platinum in one step is desirable.     

A microfabricated deformability-based flow cytometer with application to malaria

Malaria resulting from Plasmodium falciparum infection is a major cause of human suffering and mortality. Red blood cell (RBC) deformability plays a major role in the pathogenesis of malaria. Here we introduce an automated microfabricated "deformability cytometer" that measures dynamic mechanical responses of 10(3) to 10(4) individual RBCs in a cell population. Fluorescence measurements of each RBC are simultaneously acquired, resulting in a population-based correlation between biochemical properties, such as cell surface markers, and dynamic mechanical deformability. This device is especially applicable to heterogeneous cell populations. We demonstrate its ability to mechanically characterize a small number of P. falciparum-infected (ring stage) RBCs in a large population of uninfected RBCs. Furthermore, we are able to infer quantitative mechanical properties of individual RBCs from the observed dynamic behavior through a dissipative particle dynamics (DPD) model. These methods collectively provide a systematic approach to characterize the biomechanical properties of cells in a high-throughput manner.