Kinetic evidence for low chemical processivity in ncd and Eg5

We have examined the formation of hydroxyphenols, nitrophenols, and the minor products 4-nitrosophenol, benzoquinone, 2,2'-biphenol, and 4,4'-biphenol from the reaction of peroxynitrite with phenol in the presence and absence of added carbonate. In the absence of added carbonate, the product yields of nitrophenols and hydroxyphenols have different pH profiles. The rates of nitration and hydroxylation also have different pH profiles and match the trends observed for the product yields. At a given pH, the sum of the rate constants for nitration and hydroxylation is nearly identical to the rate constant for the spontaneous decomposition of peroxynitrite. The reaction of peroxynitrite with phenol is zero-order in phenol, both in the presence and absence of added carbonate. In the presence of added carbonate, hydroxylation is inhibited, whereas the rate of formation and yield of nitrophenols increase. The combined maximum yield of o- and p-nitrophenols is 20 mol% (based on the initial concentration of peroxynitrite) and is about fourfold higher than the maximal yield obtained in the absence of added carbonate. The o/p ratio of nitrophenols is the same in the presence and absence of added carbonate. These results demonstrate that hydroxylation and nitration occur via two different intermediates. We suggest that the activated intermediate formed in the isomerization of peroxynitrous acid to nitrate, ONOOH*, is the hydroxylating species. We propose that intermediate 1, O=N-OO-CO2-, or secondary products derived from it, is (are) responsible for the nitration of phenol. The possible mechanisms responsible for nitration are discussed.     

Adhesive Contact of a Membrane with a Hemispherical Indenter: Theoretical Analysis and Model Liquid System

The axisymmetric Laplace equation is solved numerically to extract contact-angle data for a flat liquid/vapor interface contacting a submerged hemispherical solid. The liquid/vapor interface is treated as a membrane, with a membrane tension equal to the surface energy of the liquid. By measuring the vertical displacement of the membrane and the projected contact area the membrane makes with the hemisphere, the contact angle and correspondingly the driving force for motion of the contact line can be measured. We show that characteristic receding and advancing contact angles can be obtained by measuring the contact radii formed upon initial contact between the interface and hemisphere and final contact just prior to detachment of the interface, respectively. Use of the technique is illustrated with a model experiment involving the contact of an air/water interface with a poly(methyl methacrylate) surface.     

Dyadic perfectionism as a predictor of relationship continuity and distress among college students.

This study examined the nature and impact of dyadic perfectionism over a 3-month interval within a sample of 116 college students who were currently involved in an intimate heterosexual relationship. Dyadic perfectionism scores were stable and correlated as expected with scores on concurrent measures of adult attachment orientations and relationship satisfaction. Logistic regression analyses revealed that, controlling for initial commitment status and adult attachment orientations, Time 1 dyadic perfectionism scores significantly and uniquely predicted relationship continuity 3 months later. Lastly, controlling for social desirability, relationship commitment status, and Time 1 adult attachment orientation scores, Time 1 dyadic perfectionism scores also uniquely predicted Time 2 relationship distress. Findings provide additional evidence that dyadic perfectionism is a risk factor for relationship dysfunction. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Individuality of understanding and assessment of sensory attributes of foods, in particular, tenderness of meat

This study examines the extent to which variations in consumers' sensory assessments of food arise from the inability to report accurately sensory perceptions, from confusion regarding the criteria by which to assess samples, or from differences in their oral breakdown of the products.

Twenty consumers assessed the tenderness of a range of 8 hot, freshly roasted meat samples using Time Intensity (TI). Overall a significant correlation was found between the maximum recorded intensity (Imax) of their TI curves and single sensory scores given by a trained panel. Correlation was significant for only 42% of the consumers individually. Significant correlations were found between the amount of masticatory muscle activity undertaken during chewing (measured using electromyography) and Imax for all but 2 of the consumers. Thus subjects' perceptions were accurately described by their chewing work, suggesting between subject differences in perception arose from differences in the way chewing work was applied to break down the samples. The sensory input from the masticatory muscles may represent the major determinant of perceived tenderness of meat.     

Is simplicity the key to engagement for children on the autism spectrum?

This article presents a conceptualisation of technologies as simple, ambient forms. By avoiding the tendency to solve problems and by being open to interaction that emerges through repetition and flow, we argue that technology can offer more for people than functionality. When the user is given freedom to discover control without burdensome cognitive demands and the fear of failure, even everyday technologies can arouse curiosity and thus reveal untapped ability. What is unique about our work is its therapeutic application as a medium for engaging the most hard to reach children on the autism spectrum. Our theoretical foundations are drawn from the human–computer interaction paradigm of tangible interaction. This is of interest to us as a framework for the study of the physical and sensory manipulation of information. For children with cognitive and developmental delays, discovering a close match between physical control and digital response has proved both rewarding and motivating. The significance of this is illustrated through a range of studies undertaken with children with autism spectrum disorders. These include a mixed group attending a holiday club, a study that introduced keyboard activities to children with poor receptive communication and a case study using an ordinary microphone. The research captures emergent, exploratory interaction with a software application called ReacTickles. The case study uses a specifically customised video coding technique to analyse idiosyncratic interactions that demonstrate the impact of simple, playful interaction on self-esteem and creativity.     

Modeling the tensile behavior of fiber bundles with irregular constituent fibers

In this article, the effect of fiber dimensional irregularities on the tensile behavior of fiber bundles is modeled with the finite element method. The fiber dimensional irregularities are simulated with sine waves of different magnitudes. The specific‐stress/strain curves of fiber bundles and their constituent single fibers are obtained and compared. The results indicate that fiber diameter irregularity along the fiber length has a significant effect on the tensile behavior of fiber bundles. For a bundle of uniform fibers of different diameters, all the constituent fibers will break simultaneously, regardless of the fiber diameter. Similarly, if fibers within a bundle have the same pattern and level of diameter irregularity along the fiber length, the fibers will break at the same time, also regardless of the difference in the average diameter of each fiber. In these cases, the specific‐stress/strain curve for the bundle overlaps with that of the constituent fibers. When a fiber bundle consists of single fibers with different levels of diameter irregularities, the specific‐stress/strain and load–elongation curves of the fiber bundle have a stepped or ladder shape. The fiber with the highest irregularity breaks first, even when the thinnest section of the fiber is still coarser than the diameter of a very thin but uniform fiber in the bundle. This study suggests that fiber diameter irregularity along the fiber length is a more important factor than the fiber diameter itself in determining the tensile behavior of a fiber bundle consisting of irregular fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2664–2668, 2004     

Poly(ethylene oxide)/Laponite nanocomposites via melt-compounding: effect of clay modification and matrix molar mass

The present study focuses on the preparation of poly(ethylene oxide) (PEO) nanocomposites based on the synthetic Laponite clay. The clay was added both in its pure form as well as organically modified with low molar mass poly(ethylene glycol) (PEG) components in order to enhance the compatibility between Laponite and PEO. Several PEG's with different end groups were used. Almost all of them were found to intercalate in the clay intergallery spacing. An order of intercalation efficiency could be established. The modified clays displayed a good thermal stability at the nanocomposite processing temperature.The nanocomposites based on the pure Laponite clay as well as the modified clays display an intercalated structure with a modest intergallery spacing. The ion-dipole modification with the PEG's was ineffective in improving the compatibility between PEO and the Laponite silicate layers. Their respective mechanical properties were found to be increased a little, which can be attributed to the low effective aspect ratio of the silicate platelets present in the nanocomposites. This is caused by the low initial aspect ratio of Laponite (w/t=25) and the limited basal spacing increase. The addition of clay does not result in nucleation of the PEO crystallisation. In contrast, the crystallisation was inhibited, resulting in decreased heat of fusions, especially for the pure Laponite nanocomposites. The nanocomposites based on the modified Laponites display a good thermal stability.     

Toughened electrospun nanofibers from crosslinked elastomer‐thermoplastic blends

A crosslink‐able elastomeric polyester urethane (PEU) was blended with a thermoplastic, polyacrylonitrile (PAN), and electrospun into nanofibers. The effects of the PEU/PAN ratio and the crosslinking reaction on the morphology and the tensile properties of the as‐spun fiber mats were investigated. With the same overall polymer concentration (9 wt %), the nanofiber containing higher composition of PEU shows a slight decrease in the average fiber diameter, but the tensile strength, the elongation at break and tensile modulus of the nanofiber mats are all improved. These tensile properties are further enhanced by slight crosslinking of the PEU component within the nanofibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

On the Relation of Job Insecurity,Job Autonomy,Innovative Work Behaviour and the Mediating Effect of Work Engagement

European policy is focusing on innovation as a way out of the economic crisis. At the same time, job insecurity is rising as Europe is still in crisis. In this paper, we examine whether job insecurity affects the innovative work behaviour of employees by focusing on the relation between job insecurity, job autonomy, work engagement and innovative work behaviour (IWB). Using employee level survey data, we use structural equation modelling to disentangle the relations between these variables. The partially mediated model shows the best fit with the data. This model shows that job insecurity and autonomy are both directly and indirectly, through work engagement, related with IWB. For autonomy these relations are positive, while they are negative (and smaller) for job insecurity. Moreover, a negative covariance is observed between job insecurity and autonomy.     

The Effects of Experience and Strategy on Visual Attention Allocation in an Automated Multiple-Task Environment

Operators and users interacting with computer environments often have to deal with multiple tasks at once, responding to each in series. Diagnostic automation, that is, automation that alerts users when and where to look, has been suggested to support the unique challenges of multiple task environments: activating tasks, switching between tasks, and tasks interfering with each other. Automation is not always reliable, however. Because of the common interaction with novel systems and the importance of training, the Simultaneous Task Environment Platform program—a multiple-task environment—was developed to understand the effects of experience on interaction with these automation-supported systems, as well as what strategies were developed. It was found that participants became more efficient with experience only when they interacted with higher reliability automation. Furthermore, the strategies participants developed focused on the differences between tasks and patterns across those tasks. Automated systems training should be sure to employ these findings.