Redox potentials and binding enhancement of fullerene and fullerene-cyclodextrin systems in water and dimethylsulfoxide

The formal redox potentials of electron transfer reactions of fullerene, methanofullerene, fullerene-cyclodextrin complex and methanofullerene conjugates with cyclodextrins in aqueous and dimethylsulfoxide solutions are reported. These new compounds are surface active and retain the redox activity of C₆₀ even in aqueous medium. Compounds have been characterized by an electrochemical admittance technique, which offers an advantage of separating faradaic and capacitive properties. Observed difference of formal redox potentials of the free fullerene forms and their cyclodextrin-containing compounds were used to determine the binding enhancement. Results are interpreted in terms of inter-molecular host-guest interactions of C₆₀-cyclodextrin conjugates.     

Neighborhood sociodemographics and change in built infrastructure

While increasing evidence suggests an association between physical infrastructure in neighborhoods and health outcomes, relatively little research examines how neighborhoods change physically over time and how these physical improvements are spatially distributed across populations. This paper describes the change over 25 years (1985–2010) in bicycle lanes, off-road trails, bus transit service and parks, and spatial clusters of changes in these domains relative to neighborhood sociodemographics in four US cities that are diverse in terms of geography, size, and population. Across all four cities we identified increases in bicycle lanes, off-road trails, and bus transit service, with spatial clustering in these changes that related to neighborhood sociodemographics. Overall, we found evidence of positive changes in physical infrastructure commonly identified as supportive of physical activity. However, the patterning of infrastructure change by sociodemographic change encourages attention to the equity in infrastructure improvements across neighborhoods.     

Impact of electrically formed interfacial layer and improved memory characteristics of IrOx/high-κx/W structures containing AlOx,GdOx, HfOx,and TaOx switching materials

Improved switching characteristics were obtained from high-κ oxides AlO_x, GdO_x, HfO_x, and TaO_x in IrO_x/high-κ_x/W structures because of a layer that formed at the IrO_x/high-κ_x interface under external positive bias. The surface roughness and morphology of the bottom electrode in these devices were observed by atomic force microscopy. Device size was investigated using high-resolution transmission electron microscopy. More than 100 repeatable consecutive switching cycles were observed for positive-formatted memory devices compared with that of the negative-formatted devices (only five unstable cycles) because it contained an electrically formed interfacial layer that controlled ‘SET/RESET’ current overshoot. This phenomenon was independent of the switching material in the device. The electrically formed oxygen-rich interfacial layer at the IrO_x/high-κ_x interface improved switching in both via-hole and cross-point structures. The switching mechanism was attributed to filamentary conduction and oxygen ion migration. Using the positive-formatted design approach, cross-point memory in an IrO_x/AlO_x/W structure was fabricated. This cross-point memory exhibited forming-free, uniform switching for >1,000 consecutive dc cycles with a small voltage/current operation of ±2 V/200 μA and high yield of >95% switchable with a large resistance ratio of >100. These properties make this cross-point memory particularly promising for high-density applications. Furthermore, this memory device also showed multilevel capability with a switching current as low as 10 μA and a RESET current of 137 μA, good pulse read endurance of each level (>10⁵ cycles), and data retention of >10⁴ s at a low current compliance of 50 μA at 85°C. Our improvement of the switching characteristics of this resistive memory device will aid in the design of memory stacks for practical applications.     

Derivation and validation of a binary multi-fluid Eulerian model for fluidized beds

The paper presents a multi-fluid Eulerian model derived from binary kinetic theory of granular flows, free path theory and an empirical friction theory. The effects of the inter- and inner-particle collisions, particle translational motions and particle–particle friction are included. As the effects due to fluiddynamic particle velocity differences and particle–particle friction are considered, some unconventional terms are produced compared with the previous models. Model validation using the data from Mathiesen et al. (2000) shows that the coupling terms give a stronger and more realistic particle–particle coupling because the effects due to the fluiddynamic velocity differences are considered. The model gives reasonable predictions of the particle volume fraction, particle velocities and velocity fluctuations. The model analysis reveals that the basic particle velocity fluctuations constitute 2 terms: the velocity fluctuations of the discrete particles, and the velocity fluctuations of the continuous fluid flow. Furthermore, the simulation results show that the velocity fluctuations of the continuous fluid flow are dominant in a binary riser flow.     

Vortex characteristics due to nozzle clogging in water caster mould: modelling and validation

In continuous slab casting, clogging in the submerged entry nozzle (SEN) ports leads to flow asymmetry and vortex formation in the mould. Knowledge of vortexing and its influence on product quality is fundamental for defect-free production. In this study, the interconnected effects of nozzle clogging and SEN submergence depth, variation on flow asymmetry and vortex characteristics in a 0.4 scale water caster have been characterised by CFD investigation and validated with experimental results from the authors’ previous work. Mean flow velocities at the sub-meniscus and near the port exit predicted by the computational model are compared with the time-averaged values of the impeller probe velocity measurements and found to be in reasonable agreement. Three different clogging conditions (0, 33 and 66% in the left port of the SEN) for SEN submergence depth of 60?mm are studied and the 66% clogging produced vortices having largest diameter, which is consistent with the experimental observations. The effects of SEN submergence depth on flow asymmetry and vortexing are investigated with three different conditions – 40, 60 and 80?mm. It is found that the shallow SEN submergence depth (40?mm) produces vortices of largest diameter and the flow is most stable for a SEN submergence depth of 60?mm among the three cases. Vortex bending towards the SEN as noticed in the experimental observations is also observed in the computational study. This work illustrates the possibility of capturing features of vortexing using validated CFD model.     

Aroma profiles of five basil (Ocimum basilicum L.) cultivars grown under conventional and organic conditions

A headspace solid-phase microextraction (HS-SPME) method coupled to gas chromatography–ion trap mass spectrometry (GC–ITMS) has been developed and applied for profiling of volatile compounds released from five Ocimum basilicum L. cultivars grown under both organic and conventional conditions. Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC–TOFMS) was employed for confirmation of identity of volatiles extracted from the basil headspace by SPME.     

Sonochemical Activation of Al/Ni Hydrogenation Catalyst

This paper proposes a sonochemical approach to the nanostructuring of Al/Ni catalyst with high content of accessible Ni centers and a high reusability. The surface and bulk composition as well as pore size distribution of this catalyst are controlled synergistically by adjusting the ultrasound intensity in aqueous solution. Sonochemical activation of Al/Ni alloy leads to formation of mesoporous Al/Ni metallic based frameworks with surface area up to 125 m² g^?1, and regular distribution of nickel active center in the porous matrix. One of the opportunities of porous Al/Ni catalyst is that due to a time‐resolved controllable formation of protective oxide layer it can be stored and handled under air in comparison to traditional Raney catalysts which need inert conditions. The Al/Ni catalyst is characterized by scanning electron microscopy (SEM), electron diffraction spectroscopy (EDS), X‐ray photoelectron spectroscopy (XPS), confocal scanning fluorescence microscopy (CSFM), solid‐state NMR experiments, and powder X‐ray diffraction analysis (PXRD). The catalytic activity was investigated for the hydrogenation of acetophenone.     

3D-FE-Analysis of CT-specimens including viscoplastic material behavior and nonlocal damage

In order to describe the time-dependent inelastic behavior of steel structures up to failure, a material model is developed within the framework of thermodynamics considering viscoplastic material behavior, isotropic hardening, softening, and isotropic ductile damage. Since softening and damage lead to localization of deformations, the model is extended by a non-local implicit gradient formulation. An additional gradient equation is formulated for the local damage variable in order to achieve results independent of the finite-element discretization. The approach is verified by 3D-structural analysis of CT-specimens.     

Electrospinning formaldehyde‐crosslinked zein solutions

In order to develop zein fibers with improved physical properties and solvent resistance, formaldehyde was used as a crosslinking reagent before spinning. The crosslinking reaction was carried out in either acetic acid or ethanolic HCl where the amount of crosslinking reagent was between 1 and 6%. Reactions were carried out at various times and temperatures. When carried out in acetic acid, the maximum amount of formaldehyde that could be used was 1.5% as gelation occurred at higher levels. In ethanolic HCl, 6% formaldehyde could be incorporated into zein. All solutions were successfully electrospun, producing predominantly ribbon and round fibers; the morphology was strongly dependent on solvent and spinning solids. The formaldehyde‐crosslinked zein fabrics had double the tensile strength of control fabrics. SDS‐PAGE analysis clearly showed crosslinking had occurred. Electrospun fabrics from all formaldehyde‐treated zein solutions required an additional heating step in order to be resistant to dissolution in acetic acid, a known very good solvent for zein. Copyright © 2011 Society of Chemical Industry