Electrochemical detection and removal of lead in water using poly(propylene imine) modified re-compressed exfoliated graphite electrodes

Modification of exfoliated graphite (EG) electrode with generation 2 poly(propylene imine) dendrimer by electrodeposition resulted in an electrochemical sensor which was used to detect lead ions in water to a limit of 1 ppb and a linear response between 2.5 and 40 ppb using square wave anodic stripping voltammetry (SW-ASV). Pb(II) was also removed from spiked water sample using a 40-mm diameter unmodified EG electrode with an applied potential of -1,000 mV for 180 min. A removal efficiency of 99% was calculated from a 150 mL sample. The results obtained in both cases using SW-ASV, correlated with atomic absorption spectroscopy.

Automatic extraction of free-form surface features (FFSFs)

This paper presents a new algorithm for extracting Free-Form Surface Features (FFSFs) from a surface model. The extraction algorithm is based on a modified taxonomy of FFSFs from that proposed in the literature. A new classification scheme has been proposed for FFSFs to enable their representation and extraction. The paper proposes a separating curve as a signature of FFSFs in a surface model. FFSFs are classified based on the characteristics of the separating curve (number and type) and the influence region (the region enclosed by the separating curve). A method to extract these entities is presented. The algorithm has been implemented and tested for various free-form surface features on different types of free-form surfaces (base surfaces) and is found to correctly identify and represent the features irrespective of the type of underlying surface. The representation and extraction algorithm are both based on topology and geometry. The algorithm is data-driven and does not use any pre-defined templates. The definition presented for a feature is unambiguous and application independent. The proposed classification of FFSFs can be used to develop an ontology to determine semantic equivalences for the feature to be exchanged, mapped and used across PLM applications. (C) 2011 Elsevier Ltd. All rights reserved.

C-H functionalization of tertiary amines by cross dehydrogenative coupling reactions: solvent-free synthesis of alpha-aminonitriles and beta-nitroamines under aerobic condition

A solvent-free synthesis of alpha-aminonitriles and beta-nitroamines by oxidative cross-dehydrogenative coupling under aerobic condition is reported. A catalytic amount of molybdenum(VI) acetylacetonoate was found to catalyze cyanation of tertiary amines to form alpha-aminonitriles, whereas vanadium pentoxide was found to promote aza-Henry reaction to furnish beta-nitroamines. Both of these environmentally benign reactions are performed in the absence of solvents using molecular oxygen as an oxidant.

In-situ formation of graphene-lead oxide composite and its use in trace arsenic detection

Reduced graphene oxide-lead dioxide composite is formed when EGO coated surface is electrochemically reduced along with lead ions in the solution. This composite has been shown to be an excellent material for low level detection of arsenic. Various functional groups present on EGO, in a wide pH range of 2-11, are responsible for the favorable interaction between metal ion and the modified electrode surface and subsequent trace level detection. X-ray photoelectron spectroscopy and Raman spectroscopic techniques confirm the formation of composite and its composition. Thin layer of lead dioxide along with reduced exfoliated graphene oxide has been shown to be responsible for the enhanced activity of the surface. The detection limit of arsenic is found to be 10 nM. This study opens up the possibility of using the composites for sensing applications and possibly simultaneous detection of arsenic and lead. (C) 2011 Elsevier B.V. All rights reserved.

A novel free floating accelerometer force balance system for shock tunnel applications

In order to overcome the interference of the model mounting system with the external aerodynamics of the body during shock tunnel testing, a new free floating internally mountable balance system that ensures unrestrained model motion during testing has been designed, fabricated and tested. Minimal friction ball bearings are used for ensuring the free floating condition of the model during tunnel testing. The drag force acting on a blunt leading edge flat plate at hypersonic Mach number has been measured using the new balance system. Finite element model (FEM) and CFD are exhaustively used in the design as well as for calibrating the new balance system. The experimentally measured drag force on the blunt leading edge flat plate at stagnation enthalpy of 0.7 and 1.2 MJ/kg and nominal Mach number of 5.75 matches well with FEM results. The concept can also be extended for measuring all the three fundamental aerodynamic forces in short duration test facilities like free piston driven shock tunnels.

Planform structure of turbulent free convection on horizontal surfaces

The planform structure of turbulent free convection over a heated horizontal surface has been visualized and analyzed for different boundary conditions at the top and for different aspect ratios, for flux Rayleigh numbers ranging from 10 exp 8 - 10 exp 10. The different boundary conditions correspond to Rayleigh-Benard convection, open convection with evaporation at the top and with an imposed external flow on the heated boundary. Without the external flow the planform is one randomly oriented line plume. At large Ra, these line plumes seem to align along the diagonal, persumably due to a large-scale flow along as visualized in the side view. When the external flow is imposed, the line plumes clearly align in the direction of external flow. Flow visualization reveals that at these Ra, the shear tends to break the plumes which otherwise would reach the opposite boundary. (Author)

Synthesis of free standing carbon nanosheet using electron cyclotron resonance plasma enhanced chemical vapor deposition

Carbon nanosheets (CNSs) have been synthesized by electron cyclotron resonance (ECR) plasma enhanced chemical vapor deposition (PECVD) using a mixture of acetylene and argon gases on copper foil as the substrate. Micrometer-wide carbon sheets consisting of several atomic layers thick graphene sheets have been synthesized by controlled decomposition of carbon radicals in ECR-PECVD. Raman spectroscopy of these films revealed characteristics of a disordered graphitic sheet. Thick folded carbon-sheets and a semi transparent freestanding CNSs have been observed by scanning electron microscopy. This is a promising technique to synthesize free standing CNSs and can be used in the fabrication of nanoelecronic devices in future. (C) 2012 Elsevier B.V. All rights reserved.

Influence of the Methane-Zeolite A Interaction Potential on the Concentration Dependence of Self-diffusivity

Studies on the diffusion of methane in a zeolite structure type LTA (as per IZA nomenclature) have indicated that different types of methane zeolite potentials exist in the literature in which methane is treated within the united-atom model. One set of potentials, referred to as model A, has a methane oxygen diameter of 3.14 angstrom, while another set of potential parameters, model B, employs a larger value of 3.46 angstrom. Fritzsche and co-workers (1993) have shown that these two potentials lead to two distinctly different energetic barriers for the passage of methane through the eight-ring window in the cation-free form of zeolite A. Here, we compute the variation of the self-diffusivity (D) with loading (c) for these two types of potentials and show that this slight variation in the diameter changes the concentration dependence qualitatively: thus, D decreases monotonically with c for model A, while D increases and goes through a maximum before finally decreasing for model B. This effect and the surprising congruence of the diffusion coefficients for both models at high loadings is examined in detail at the molecular level. Simulations for different temperatures reveal the Arrhenius behaviour of the self-diffusion coefficient. The apparent activation energy is found to vary with the loading. We conclude that beside the cage-to-cage jumps, which are essential for the migration of the guest molecules, at high concentrations migration within the cage and guest guest interactions with other molecules become increasingly dominant influences on the diffusion coefficient and make the guest zeolite interaction less important for both model A and model B.

Free Energy Barriers for Escape of Water Molecules from Protein Hydration Layer

Free energy barriers separating interfacial water molecules from the hydration layer at the surface of a protein to the bulk are obtained by using the umbrella sampling method of free energy calculation. We consider hydration layer of chicken villin head piece (HP-36) which has been studied extensively by molecular dynamics simulations. The free energy calculations reveal a strong sensitivity to the secondary structure. In particular, we find a region near the junction of first and second helix that contains a cluster of water molecules which are slow in motion, characterized by long residence times (of the order of 100 ps or more) and separated by a large free energy barrier from the bulk water. However, these ``slow'' water molecules constitute only about 5-10% of the total number of hydration layer water molecules. Nevertheless, they play an important role in stabilizing the protein conformation. Water molecules near the third helix (which is the important helix for biological function) are enthalpically least stable and exhibit the fastest dynamics. Interestingly, barrier height distributions of interfacial water are quite broad for water surrounding all the three helices (and the three coils), with the smallest barriers found for those near the helix-3. For the quasi-bound water molecules near the first and second helices, we use well-known Kramers' theory to estimate the residence time from the free energy surface, by estimating the friction along the reaction coordinate from the diffusion coefficient by using Einstein relation. The agreement found is satisfactory. We discuss the possible biological function of these slow, quasi-bound (but transient) water molecules on the surface.

Novel and efficient protocol for the syntheses of N-1 substituted thiohydantoin and a bicyclothiohydantoin under solvent-free conditions

A novel approach for the synthesis of N-1 substituted thiohydantoin has been developed to give quantitative yields of the desired products. The efficient synthesis of bis-thiohydantoin derivative and bicyclothiohydantoin has extended scope and applicability of present method. Solvent-free conditions and very easy work-up procedure make the reaction convenient and eco-friendly. All the products were characterized by spectroscopic techniques and elemental analysis, and finally the structure of representative ;compound was also confirmed by X-ray crystallography. (C) 2012 Elsevier Ltd. All rights reserved.

Flow visualization in turbulent free convection over horizontal smooth and grooved surfaces

The present paper discusses the flow visualization for turbulent free convection in a tank of water with the bottom surface being a smooth or a grooved surface and the top of the water surface exposed to ambient. The grooved surface is of parallel 90 degrees V-grooves with groove height of 10 mm and groove width of 20 mm. The experiment is carried out with aspect ratio (AR) of 2.9 and Rayleigh number (Ra) in the range, 1.3 x 10(7) - 4 x 10(7). Here AR is the aspect ratio (= width of fluid layer/height of fluid layer). Heat flux at the bottom surface is from electrical heating. From the pH-dye visualization, interesting flow structures are observed and these structures are analyzed with the help of plumes dynamics and temperature variations with time. (C) 2011 Elsevier Ltd. All rights reserved.

Chemically functionalized glassy carbon spheres: a new covalent bulk modified composite electrode for the simultaneous determination of lead and cadmium

A new type of covalent bulk modified glassy carbon composite electrode has been fabricated and utilized in the simultaneous determination of lead and cadmium ions in aqueous medium. The covalent bulk modification was achieved by the chemical reduction of 2-hydroxybenzoic acid diazonium tetrafluroborate in the presence of hypophosphorous acid as a chemical reducing agent. The covalent attachment of the modifier molecule was examined by studying Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and the surface morphology was examined by scanning electron microscopy images. The electrochemistry of modified glassy carbon spheres was studied by its cyclic voltammetry to decipher the complexing ability of the modifier molecules towards Pb2+ and Cd2+ ions. The developed sensor showed a linear response in the concentration range 1-10 mu M with a detection limit of 0.18 and 0.20 mu M for lead and cadmium, respectively. The applicability of the proposed sensor has been checked by measuring the lead and cadmium levels quantitatively from sewage water and battery effluent samples.

Geosphere laminations in free groups

We construct for free groups, which are codimension one analogues of geodesic laminations on surfaces. Other analogues that have been constructed by several authors are dimension-one instead of codimension-one. Our main result is that the space of such laminations is compact. This in turn is based on the result that crossing, in the sense of Scott-Swarup, is an open condition. Our construction is based on Hatcher's normal form for spheres in the model manifold.

Defect-Free Hyperbranched Polydithioacetal via Melt Polymerization

Degree of branching (DB) describes the level of structural perfection of a hyperbranched polymer when compared to its defect-free analogue, namely the dendrimer. The strategy most commonly used to achieve high DB values, specifically while using AB(2) type self-condensations, is to design an AB2 monomer wherein the reaction of the first B-group leads to an enhancement of the reactivity of the second one. In the present study, we show that an AB2 monomer carrying a dimethylacetal unit and a thiol group undergoes a rapid self-condensation in the melt under acid-catalysis to yield a hyperbranched polydithioacetal with no linear defects. NMR studies using model systems reveal that the intermediate monothioacetal is relatively unstable under the polymerization conditions and transforms rapidly to the dithioacetal; because this second step occurs irreversibly during polymer formation, it leads to a defect-free hyperbranched polydithioacetal. TGA studies of the polymerization process provided some valuable insights into the kinetics of polymerization. An additional virtue of this approach is that the numerous terminal dimethylacetal groups are very labile and can be quantitatively transformed by treatment with a variety of functional thiols; the terminal dimethylacetals were, thus, reacted with various thiols, such as dodecanethiol, benzyl mercaptan, ethylmercaptopropionate, and so on, to demonstrate the versatility of these systems as sulfur-rich hyperscaffolds to anchor different kinds of functionality on their periphery.