Urea-Functionalized Self-Assembled Molecular Prism for Heterogeneous Catalysis in Water

Reaction of a ditopic urea ``strut'' (L-1) with cis-(tmen)Pd(NO3)(2) yielded a 3+3] self-assembled molecular triangle (T)L-1 = 1,4-di(4-pyridylureido)benzene; tmen = N,N,N',N'-tetrame-thylethane-1,2-diamine]. Replacing cis-(tmen)Pd(NO3)(2) in the above reaction with an equimolar mixture of Pd(NO3)(2) and a clip-type donor (L-2) yielded a template-free multicomponent 3D trigonal prism (P) decorated with multiple urea moieties L-2 = 3,3'-(1H-1,2,4-triazole-3,5-diyl)dipyridine]. This prism (P) was characterized by NMR. spectroscopy, and the structure was confirmed by X-ray crystallography. The P was employed as an effective hydrogen-bond-donor catalyst for Michael reactions of a series of water-insoluble nitro-olefins in an aqueous medium. The P showed better catalytic activity compared to the urea based ligand L-1 and the triangle T. Moreover, the confined nanospace of P in addition to large product outlet windows makes this 3D architecture a perfect molecular vessel to catalyze Diels-Alder reactions of 9-hydroxymethylanthracene with N-substituted maleimide in the aqueous medium. The present results demonstrate new observations on catalytic aqueous Diels-Alder and Michael reactions in heterogeneous fashion employing a discrete 3D architecture of Pd(II). The prism was recycled by simple filtration and reused several tithes without significant loss of activity.

A Global Constraint On Relative Rotation To Avoid Lumped Compliant Mechanisms In Topology Optimization

Some of the well known formulations for topology optimization of compliant mechanisms could lead to lumped compliant mechanisms. In lumped compliance, most of the elastic deformation in a mechanism occurs at few points, while rest of the mechanism remains more or less rigid. Such points are referred to as point-flexures. It has been noted in literature that high relative rotation is associated with point-flexures. In literature we also find a formulation of local constraint on relative rotations to avoid lumped compliance. However it is well known that a global constraint is easier to handle than a local constraint, by a numerical optimization algorithm. The current work presents a way of putting global constraint on relative rotations. This constraint is also simpler to implement since it uses linearized rotation at the center of finite-elements, to compute relative rotations. I show the results obtained by using this constraint oil the following benchmark problems - displacement inverter and gripper.

Wave propagation in multi-walled carbon nanotube

In this paper, wave propagation in multi-walled carbon nanotubes (MWNTs) are studied by modeling them as continuum multiple shell coupled through van der Waals force of interaction. The displacements, namely, axial, radial and circumferential displacements vary along the circumferential direction. The wave propagation are simulated using the wavelet based spectral finite element (WSFE) method. This technique involves Daubechies scaling function approximation in time and spectral element approach. The WSFE Method allows the study of wave properties in both time and frequency domains. This is in contrast to the conventional Fourier transform based analysis which are restricted to frequency domain analysis. Here, first, the wavenumbers and wave speeds of carbon nanotubes (CNTs) are Studied to obtain the characteristics of the waves. These group speeds have been compared with those reported in literature. Next, the natural frequencies of a single-walled carbon nanotube (SWNT) are studied for different values of the radius. The frequencies of the first five modes vary linearly with the radius of the SWNT. Finally, the time domain responses are simulated for SWNT and three-walled carbon nanotubes.

Numerical studies on columnar-to-equiaxed transition in directional solidification of binary alloys

A numerical study on columnar-to-equiaxed transition (CET) during directional solidification of binary alloys is presented using a macroscopic solidification model. The position of CET is predicted numerically using a critical cooling rate criterion reported in literature. The macroscopic solidification model takes into account movement of solid phase due to buoyancy, and drag effect on the moving solid phase because of fluid motion. The model is applied to simulate the solidification process for binary alloys (Sn-Pb) and to estimate solidification parameters such as position of the liquidus, velocity of the liquidus isotherm, temperature gradient ahead of the liquidus, and cooling rate at the liquidus. Solidification phenomena under two cooling configurations are studied: one without melt convection and the other involvin thermosolutal convection. The numerically predicted positions of CET compare well with those of experiments reported in literature. Melt convection results in higher cooling rate, higher liquidus isotherm velocities, and stimulation of occurrence of CET in comparison to the nonconvecting case. The movement of solid phase aids further the process of CET. With a fixed solid phase, the occurrence of CET based on the same critical cooling rate is delayed and it occurs at a greater distance from the chill.

Breakage of viscous and non-Newtonian drops in stirred dispersions

A model of breakage of drops in a stirred vessel has been proposed to account for the effect of rheology of the dispersed phase. The deformation of the drop is represented by a Voigt element. A realistic description of the role of interfacial tension is incorporated by treating it as a restoring force which passes through a maximum as the drop deforms and eventually reaching a zero value at the break point. It is considered that the drop will break when the strain of the drop has reached a value equal to its diameter. An expression for maximum stable drop diameter, dmax, is derived from the model and found to be applicable over a wide range of variables, as well as to data already existing in literature. The model could be naturally extended to predict observed values of dmax when the dispersed phase is a power law fluid or a Bingham plastic.

Analysis of human chorionic gonadotropin-monoclonal antibody interaction in BIAcore

Kinetic studies of macromolecular ligand-ligate interaction have generated ample interest since the advent of plasmon resonance based instruments like BIAcore. Most of the studies reported in literature assume a simple 1 : 1 Langmuir binding and complete reversibility of the system. However we observed that in a high affinity antigen-antibody system [human chorionic gonadotropin-monoclonal antibody (hCG-mAb)] dissociation is insignificant and the sensogram data cannot be used to measure the equilibrium and kinetic parameters. At low concentrations of mAb the complete sensogram could be fitted to a single exponential. Interestingly we found that at higher mAb concentrations, the binding data did not conform to a simple bimolecular model. Instead, the data fitted a two-step model, which may be because of surface heterogeneity of affinity sites. In this paper, we report on the global fit of the sensograms. We have developed a method by which a single two-minute sensogram can be used in high affinity systems to measure the association rate constant of the reaction and the functional capacity of the ligand (hCG) immobilized on the chip. We provide a rational explanation for the discrepancies generally observed in most of the BIAcore sensograms

Influence of Hydrophilic Surface Specificity on the Structural Properties of Confined Water

The influence of chemical specificity of hydrophilic surfaces on the structure of confined water in the subnanometer regime is investigated using grand canonical Monte Carlo Simulations. The structural variations for water confined between hydroxylated silica surfaces are contrasted with water confined between mica surfaces. Although both surfaces are hydrophilic, our Study shows that hydration of potassium ions on the mica surface has a strong influence on the water Structure and solvation force response of confined water. In contrast to the disrupted hydrogen bond network observed for water confined between Mica Surfaces, water between silica surfaces retains its hydrogen bond network displaying bulklike structural features down to surface separations as small as 0.45 nm. Hydrogen bonding of all invariant contact water layer with the surface silanol groups aids in maintaining a constant number of hydrogen bonds per water molecule for the silica surfaces. As a consequence water depletion and rearrangement upon decreasing confinement is a strong function of the hydrophilic surface specificity, particularly at smaller separations. An oscillatory solvation force response is only observed for water confined between Silica surfaces, and bulklike features are observed for both Surfaces above a surface separation of about 1.2 nm. We evaluate and contrast the water density, dipole moment distributions, pi pair correlation functions, and solvation forces as a function of the surface separation.

Ce0.67Cr0.33O2.11: A New Low-Temperature O-2 Evolution Material and H-2 Generation Catalyst by Thermochemical Splitting of Water

Ce0.67Cr0.33O2.11 was synthesized by hydrothermal method using diethylenetriamine as complexing agent (Chem. Mater. 2008, 20, 7268). Ce0.67Cr0.33O2.11 being the only compound likes UO2+delta to have excess oxygen, it releases a large proportion of its lattice oxygen (0.167 M [O]/mole of compound) at relatively low temperature (465 degrees C) directly and it has been utilized for generation of H-2 by thermo-splitting of water. An almost stoichiometric amount of H-2 (0.152 M/Mole of compound) is generated at much lower temperature (65 degrees C). There is an almost comparable amount of oxygen release and hydrogen generation over this material at very low temperature comparedto other CeO2-MOx (Mn, Fe, Cu, and Ni) mixed-oxide solid solutions (O-2 evolution >= 1300 degrees C and H-2 generation at 1000 degrees C). The reversible nature of oxygen release and intake of this material is attributed to its fluorite Structure and coupling between the Ce4+/Ce3+ and Cr4+/6+/Cr3+ redox couples. Compound shows reversible oxygen release and intake by H2O absorption and subsequent hydrogen release to gain parent structure and hence this material can be utilized for generation of H-2 at very low temperature by thermo-chemical splitting of water.

Abatement of fluoride from water using manganese dioxide-coated activated alumina

Batch adsorption of fluoride onto manganese dioxide-coated activated alumina (MCAA) has been studied. Adsorption experiments were carried out at various pH (3–9), time interval (0–6 h), adsorbent dose (1–16 g/l), initial fluoride concentration (1–25 mg/l) and in the presence of different anions. Adsorption isotherms have been modeled using Freundlich, Langmuir and Dubinin–Raduskevich isotherms and adsorption followed Langmuir isotherm model. Kinetic studies revealed that the adsorption followed second-order rate kinetics. MCAA could remove fluoride effectively (up to 0.2 mg/l) at pH 7 in 3 h with 8 g/l adsorbent dose when 10 mg/l of fluoride was present in 50 ml of water. In the presence of other anions, the adsorption of fluoride was retared. The mechanism of fluoride uptake by MCAA is due to physical adsorption as well as through intraparticle diffusion which was confirmed by kinetics, Dubinin–Raduskevich isotherm, zeta-potential measurements and mapping studies of energy-dispersive analysis of X-ray.

Behaviour of Bi-material interface cracks in the presence of material nonlinearity of adherends

The well known features of crack face interpenetration/contact at the tip of an interface crack is re-examined using finite element analysis and assuming material nonlinear properties for the adherends. It was assumed in literature that the crack tips are fully open at all load levels in the presence of material nonlinearity of the adherends. Analysis for the case of remote tension shows that even in the presence of material nonlinearity, crack tip closes at small load levels and opens above a certain load level. Mixed-mode fracture parameters are evaluated for the situation when the crack tips are fully open. Due to the presence of nonlinearity, the mixed-mode fracture parameters are measured with the symmetric and anti-symmetric components of J-integral. The present analysis explains the sequence of events at the interface crack tip with progressively increasing remote tension load for the case of adherends with material nonlinear behaviour.

Enhanced adsorption capacity of activated alumina by impregnation with alum for removal of As(V) from water

Alum-impregnated activated alumina (AIAA) was investigated in the present work as an adsorbent for the removal of As(V) from water by batch mode. Adsorption study at different pH values shows that the efficiency of AIAA is much higher than as such activated alumina and is suitable for treatment of drinking water. The adsorption isotherm experiments indicated that the uptake of As(V) increased with increasing As(V) concentration from 1 to 25 mg/l and followed Langmuir-type adsorption isotherm. Speciation diagram shows that in the pH range of 2.8–11.5, arsenate predominantly exists as H2AsO4− and HAsO42− species and hence it is presumed that these are the major species being adsorbed on the surface of AIAA. Intraparticle diffusion and kinetic studies revealed that adsorption of As(V) was due to physical adsorption as well as through intraparticle diffusion. Effect of interfering ions revealed that As(V) sorption is strongly influenced by the presence of phosphate ion. The presence of arsenic on AIAA is depicted from zeta potential measurement, scanning electron microscopy (SEM) and energy-dispersive analysis of X-ray (EDAX) mapping study. Alum-impregnated activated alumina successfully removed As(V) to below 40 ppb (within the permissible limit set by WHO) from water, when the initial concentration of As(V) is 10 mg/l.

The use of circular surface aerators in wastewater treatment tanks

Aeration experiments were conducted in different sized baffled and unbaffled circular surface aeration tanks to study their relative performance on oxygen transfer process while aerating the same volume of water. Experiments were carried out with the objective of ascertaining the effect of baffle on oxygen transfer coefficient k. Simulation equations govern the oxygen transfer coefficient with the theoretical power per unit volume, X and actual power per unit volume, P-V. It has been found that, for any given X, circular tanks with baffle produce higher values of k than unbaffled circular tanks, but in terms of actual power consumption unbaffled tanks consume less power when compared to baffled circular tanks to achieve the same value of k. It has been found that in terms of energy consumption, epsilon, baffled tanks consume more energy than unbaffled tanks at any value of X. This suggests that the unbaffled circular tank gives a better performance as far as energy consumption is concerned and hence better economy. An example illustrating the energy conservation to aerate the same volume of water in both types of aerators is given. (c) 2007 Society of Chemical Industry.

Stability of an unsupported vertical circular excavation in clays under undrained condition

By using the axisymmetric finite elements static limit analysis formulation, proposed recently by the authors, the stability numbers (gamma H/c(o)) for an unsupported vertical circular excavation in clays, whose cohesion increases with depth, have been determined under undrained condition; gamma = unit weight, H., height of the excavation and c(o) = cohesion along ground surface. The results are obtained for various values of H/b and m; where b = the radius of the excavation and m = a non-dimensional parameter which accounts for the rate of the increase of cohesion with depth. The values of the stability numbers increase continuously both with increases in H/b and m. The results obtained in this study compare well with those available in literature.(C) 2009 Elsevier Ltd. All rights reserved.

Macro fiber composite (MFC) as a delamination sensor in antisymmetric laminates

The change in extension-twist Coupling due to delamination in antisymmetric laminates is experimentally measured. Experimental results are compared with the results from analytical expression existing in literature and finite element analysis. The application of the Macro-Fiber Composite (MFC) developed at the NASA Langley Research Center for sensing the delamination in the laminates is investigated. While many applications have been reported in the literature using the MFC as an actuator, here its use as a twist sensor has been studied. The real-life application envisaged is structural health monitoring of laminated composite flexbeams taking advantage of the symmetry in the structure. Apart from the defect detection under symmetric conditions, other methods of health monitoring for the same structure are reported for further validation. Results show that MFC works well as a sensor.

Heat transfer to newtonian fluids in coiled pipes in laminar flow

Data on pressure drop and heat transfer to aqueous solutions of glycerol flowing in different types of coiled pipes are presented for laminar flow in the range of NRe from 80 to 6000. An empirical correlation is set up which can account the present data as well as the data available in literature within ±10 per cent deviation. Conventional momentum and heat transfer analogy equation is used to analyse the present data.