Characterization of poly(vinyl alcohol)/sodium bromide polymer electrolytes for electrochemical cell applications

Sodium‐ion conducting polymer electrolytes based on poly(vinyl alcohol) complexed with sodium bromide were prepared with a solution‐casting technique. The structure of these films was determined with X‐ray diffraction, and the complexation of the salt with the polymer was confirmed with Fourier transform infrared spectroscopy studies. Electrical conductivity was measured with an alternating‐current impedance analyzer in the frequency range of 100 Hz to 1 MHz and in the temperature range of 303–373 K. It was observed that the magnitude of conductivity increased with the increase in the salt concentration as well as the temperature. The nature of the charge transport in these polymer electrolyte films was determined with both Wagner's polarization technique and the Watanabe technique. The dominant conducting species were found to be ions, particularly anions. Optical absorption studies were performed in the wavelength range of 200–600 nm, and the absorption edge, direct band gap, and indirect band gap values were evaluated. Electrochemical cells were fabricated, and their discharge characteristics were studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modeling of transient natural convection heat transfer in electric ovens

Prediction of transient natural convection heat transfer in vented enclosures has multiple applications such as understanding of cooking environment in ovens and heat sink performance in electronic packaging industry. The thermal field within an oven has significant impact on quality of cooked food and reliable predictions are important for robust design and performance evaluation of an oven. The CFD modeling of electric oven involves three-dimensional, unsteady, natural convective flow-thermal field coupled with radiative heat transfer. However, numerical solution of natural convection in enclosures with openings at top and bottom (ovens) can often lead to non-physical solutions such as reverse flow at the top vent, partly a function of initialization and sometimes dependent on boundary conditions. In this paper, development of a physics based robust CFD methodology is discussed. This model has been developed with rigorous experimental support and transient validation of this model with experiments show less than 3% discrepancy for a bake cycle. There is greater challenge in simulating a broil cycle, where the fluid inside the cavity is stably stratified and is also highlighted. A comparative analyses of bake and broil cycle thermal fields inside the oven are also presented.     

CO2 absorption kinetics and equilibrium solubility measurements in potassium salts of renewable amino acids from plant- and animal-protein

Aqueous solutions containing alkaline salts of natural amino acids, such as those from protein in plant seeds or high protein animal-based waste, are green CO₂-separation solvents. In the present work, potassium salts of nine such amino acids were chosen for an in-depth study: alanine, arginine, aspartic acid, glutamic acid, glycine, leucine, proline, serine, and valine. The kinetics of CO₂ absorption in aqueous solutions of these salts was studied using a stirred cell. From the measurements of the absorption rate at different salt concentrations (molarity 0.1 and higher), CO₂ partial pressures (5–25 kPa), and temperatures (298–308 K), values of the reaction order, rate constant, and activation energy were determined. Additionally, the liquid-side mass transfer coefficient (0.005 cm/s) was also found. Potassium salts of proline, glycine, and arginine were most reactive and, hence, were chosen for equilibrium study. The loading capacity of these salts was measured at 308 K in a vapour–liquid equilibrium setup at near-ambient pressure. On the contrary, the other chosen acids were comparatively less reactive with CO₂.     

Experimental investigation on the effect of MgO and TiO2 nanoparticles in stepped solar still

This work aims at augmenting the amount of potable water using MgO and TiO₂ in stepped solar still. Experiments were carried out for the climatic conditions of Chennai, India, with two different concentrations of nanofluids inside a stepped basin under three different cases. Results show that there is an improvement in yield of fresh water from stepped solar still by 33.18% and 41.05% using 0.1% and 0.2% volume concentration of TiO₂ nanofluid, respectively, whereas the freshwater yield from stepped still with MgO nanofluids improved by 51.7% and 61.89%. Furthermore, the economic analysis revealed that the cost of potable water from the modified solar still reduced from 0.029 to 0.016 $/kg. Similarly, the useful annual energy, yearly cost per kilogram, and annual cost per kilowatt hour are significantly profitable with the use of MgO nanofluid in the stepped basin and found as 512.46 kWh, 0.025 $/kg, and 0.026 $/kWh, respectively. It is also found that the cost of potable water from the modified still significantly increases as the amount of fresh water produced is decreased with increased fabrication cost of the solar still.     

A first-principle investigation into effect of B- and BN-doped $$\hbox {C}_{60}$$ in lowering dehydrogenation of $$\hbox {MXH}_{4}$$MXH4 (where M $$=$$= Na,Li and X $$=$$= Al,B)

The present paper reports the effect of B- and BN-doped \(\hbox {C}_{60}\) as catalysts for lowering the dehydrogenation energy in \(\hbox {MXH}_{4}\) clusters (M = Na and Li, X = Al and B) using density functional calculations. \(\hbox {MXH}_{4}\) interacts strongly with B-doped \(\hbox {C}_{60}\) and weakly with BN-doped \(\hbox {C}_{60}\) in comparison with pure \(\hbox {C}_{60}\) with binding energy 0.56–0.80 and 0.05–0.34 eV, respectively. The hydrogen release energy \((E_{\mathrm{HRE}})\) of \(\hbox {MXH}_{4}\) decreases sharply in the range of 38–49% when adsorbed on B-doped \(\hbox {C}_{60}\); however, with BN-doped \(\hbox {C}_{60}\) the decrease in the \(E_{\mathrm{HRE}}\) varies in the range of 6–20% as compared with pure \(\hbox {MXH}_{4}\) clusters. The hydrogen release energy of second hydrogen atom in \(\hbox {MXH}_{4}\) decreases sharply in the range of 1.7–41% for BN-doped \(\hbox {C}_{60}\) and decreases in the range of 0.2–11.3% for B-doped \(\hbox {C}_{60}\) as compared with pure \(\hbox {MXH}_{4}\) clusters. The results can be explained on the basis of charge transfer within \(\hbox {MXH}_{4}\) cluster and with the doped \(\hbox {C}_{60}\).     

FAST

We propose Frontier Allocation Synchronized by Token passing (FAST), a distributed algorithm for online terrain coverage using multiple mobile robots, ensuring mutually exclusive selection of frontier cells. Many existing approaches cover the terrain in an irregular fashion, without considering the usability of the already covered region. For instance, in the task of floor cleaning in an office building, these approaches do not guarantee the cleanliness of large unbroken areas until a majority of the task is complete. FAST on the other hand, incrementally traverses the terrain generating structured trajectories for each robot. Following a structured trajectory for coverage path planning is proven to be a very powerful approach in literature. This renders large portions of the terrain usable even before the completion of the coverage task. The novel map representation techniques used in FAST render it scalable to large terrains, without affecting the volume of communication among robots. Moreover, the distributed nature of FAST allows incorporation of fault-tolerance mechanisms. Empirical investigations on maps of varied complexities and sizes both in simulation and on an experimental test-bed demonstrate that the proposed algorithm performs better than some of the benchmark approaches in terms of coverage completion time and less redundant coverage.     

4D Biofabrication: 3D Cell Patterning Using Shape‐Changing Films

A novel approach for fabrication of 3D cellular structures using new thermosensitive shape‐changing polymer films with photolithographically patterned surface—4D biofabrication is reported. The surface of shape‐changing polymer films is patterned to selectively adsorb cells in specific regions. The 2D cell pattern is converted to the 3D cell structure after temperature‐induced folding of the polymer films. This approach has a great potential in the field of tissue engineering and bioscaffolds fabrication.     

Phenyl Selenosulfides as Cathode Materials for Rechargeable Lithium Batteries

The Se? Se bond in an organo‐diselenide (RSeSeR, R is an organic group) can break in a 2e^? reduction reaction, but it has limited capacity as a cathode material for rechargeable lithium‐ion batteries. To increase its capacity, redox active species (e.g., sulfur) can be added in the middle of the selenium atoms. Herein, phenyl diselenide (PDSe, PhSeSePh) is mixed with sulfur to form two hybrid compounds with 1:1 and 1:2 molar ratios, which almost double and triple the capacity of PDSe, respectively. Theoretical calculations suggest that phenyl selenosulfide (PDSe‐S, PhSe‐S‐SePh) and phenyl selenodisulfide (PDSe‐S₂, PhSe‐SS‐SePh) can form via addition reactions, which is supported by mass spectrometry analysis. The hybrid materials exhibit three highly reversible redox plateaus and enhanced cycling stability due to the reduced solubility of the discharge products. PDSe‐S and PDSe‐S₂ show initial capacities of 252 and 330 mAh g^?1, respectively, followed by stable cycling performance with a capacity retention of >73% after 200 cycles at C/5 rate. In addition, they show steady rate capabilities. This study reports a novel strategy to increase the electrochemical performance of organo‐diselenide by addition of sulfur.     

Reactivity of Hydroxamate Ions in Cationic Vesicular Media for the Cleavage of Carboxylate Esters

The hydrolysis of carboxylate esters viz. p‐nitrophenyl acetate (PNPA), p‐nitrophenyl butyrate (PNPB) and p‐nitrophenyl octanoate (PNPO) in the presence of cationic vesicles of the surfactant dioctadecyldimethylammonium bromide (DODAC) by different hydroxamate ions i.e. acetohydroxamate (AHA^?), benzohydroxamate (BHA^?) and salicylhydroxamate (SHA^?) were studied. The kinetic data was supported by spectrophotometric measurements. The effects of vesicular size on the reaction have been discussed. The differential reactivity under endo‐ and exovesicular conditions has also been evaluated. Critical vesicle concentrations (CVC) of cationic vesicular surfactants were determined from conductometric and fluorimetric measurements at 300 K. Fluorescence probe pyrene and pyrene‐1‐carboxaldehyde have been used for determination of CVC. Further, thermodynamic parameters viz. Standard Gibb's energy (?G°), enthalpy (?H°), and entropy (?S°) of vesicles has also been evaluated within a temperature range of 303.15–328.15 K.     

In Vivo Delivery and Activation of Masked Fluorogenic Hydrolase Substrates by Endogenous Hydrolases in C. elegans

Protein expression and localization are often studied in vivo by tagging molecules with green fluorescent protein (GFP), yet subtle changes in protein levels are not easily detected. To develop a sensitive in vivo method to amplify fluorescence signals and allow cell‐specific quantification of protein abundance changes, we sought to apply an enzyme‐activated cellular fluorescence system in vivo by delivering ester‐masked fluorophores to Caenorhabditis elegans neurons expressing porcine liver esterase (PLE). To aid uptake into sensory neuron membranes, we synthesized two novel fluorogenic hydrolase substrates with long hydrocarbon tails. Recombinant PLE activated these fluorophores in vitro. In vivo activation occurred in sensory neurons, along with potent activation in intestinal lysosomes quantifiable by imaging and microplate and partially attributable to gut esterase 1 (GES‐1) activity. These data demonstrate the promise of biorthogonal hydrolases and their fluorogenic substrates as in vivo neuronal imaging tools and for characterizing endogenous C. elegans hydrolase substrate specificities.