Aerogel-coated metal nanoparticle colloids as novel entities for the synthesis of defined supported metal catalysts

Nanometer metal particles of tailored size (3-5 nm) and composition prepared via inverse microemulsion were encapsulated by ultrathin coatings (<2.5 nm) of inorganic porous aerogels covered with surface -OH groups. These composite materials formed metastable colloids in solvent(s), and the organic surfactant molecules were subsequently removed without leading to aggregation (the ethanolic colloid solution was shown to be stable against flocculation for at least weeks). We demonstrate that the totally inorganic-based composite colloids, after the removal of surfactant, can be anchored to conventional solid supports (gamma-alumina, carbons) upon mixing. Application of a high temperature resulted in the formation of strong covalent linkages between the colloids and the support because of the condensation of surface groups at the interface. Detailed characterizations (X-ray diffraction (XRD), pore analysis, transmission electron microscopy (TEM), CO chemisorption) and catalytic testing (butane combustion) showed that there was no significant metal aggregation from the fine metal particles individually coated with porous aerogel oxide. Most of these metal sites on the coated nanoparticles with and without support are fully accessible by small molecules hence giving extremely active metal catalysts. Thus, the product and technology described may be suitable to synthesize these precursor entities of defined metal sizes (as inks) for wash coat/impregnation applications in catalysis. The advantages of developing inorganic nanocomposite chemical precursors are also discussed.

Introducing assistive technologies (AT) into the existing homes of older people

The design of accessible environments, for use by all, is a legal requirement for all public buildings, under the Disability Discrimination Act 1995 (DDA, 1995) since October 1999 and the removal of all physical barriers becomes enforceable in 2004. Accessibility has transferred from being a social and moral issue to a legal requirement. The Research Group for Inclusive Environments at the University of Reading undertakes research to better understand methods to make the built environment more accessible. This paper presents the findings from the research project, Project Crystal, investigating the design of environments for better communication for deaf and hard of hearing people. At the last COBRA conference the preliminary findings from the pilot questionnaire were presented. During the year the questionnaire has been distributed more widely and a test environment has been used to investigate the effects the variables of lighting and colour have on people's ability to communicate. This paper will present some of the findings from the project, which is almost complete, and generalise on the effect wall surface design has on accessibility of an environment for people with a hearing impairment.

Teachers as researchers and teachers as software developers: how use-case analysis helps build better educational software

A series of government initiatives has raised both the profile of ICT in the curriculum and the expectation that high quality teaching and learning resources will be accessible across electronic networks. In order for e-learning resources such as websites to have the maximum educational impact, teachers need to be involved in their design and development. Use-case analysis provides a means of defining user requirements and other constraints in such a way that software developers can produce e-learning resources which reflect teachers' professional knowledge and support their classroom practice. It has some features in common with the participatory action research used to develop other aspects of classroom practice. Two case-studies are presented: one involves the development of an on-line resource centred on transcripts of original historical documents; the other describes how 'Learning how to Learn', a major, distributed research project funded under the ESRC Teaching and Learning Research Programme is using use-case analysis to develop web resources and services.

Effects of lactoperoxidase and hydrogen peroxide on rheological properties of yoghurt

The effects of activation of the lactoperoxidase (LPO) system by H2O2-NaSCN and hydrogen peroxide (H2O2) on the accessibility of sulphydryl groups (SH) in skimmed milk, and on the dynamic rheological properties of the resulting yoghurt were investigated. Four different concentrations of each reagent (20-80 mg H2O2-NaSCN/kg milk and 100-400 mg H2O2/kg milk) were compared. Clear negative correlations were noted between the accessibility of SH groups and both LPO activation rate and H2O2 concentration. Also the native PAGE pattern of the heat-treated samples showed that with increase in the H2O2-NaSCN and H2O2 concentrations, the level of interaction between beta-lactoglobulin (beta-Ig) and kappa-casein (K-CN) decreased. The complex modulus (G*) of skimmed milk yoghurts declined gradually with the decrease in the concentration of accessible SH groups accordingly. Tan delta values of yoghurt samples were found to be different from the control, but close to each other, indicating that protein interaction forces taking place in the formation of gel networks of treated yoghurts were different from the control.

Mechanisms of G protein activation via the D-2 dopamine receptor: evidence for persistent receptor/G protein interaction after agonist stimulation

Background and purpose: The aim of this report is to study mechanisms of G protein activation by agonists. Experimental approach: The association and dissociation of guanosine 5'-O-(3-[S-35] thio) triphosphate ([S-35] GTP gamma S) binding at G proteins in membranes of CHO cells stably transfected with the human dopamine D-2short receptor was studied in the presence of a range of agonists. Key results: Binding of [S-35] GTPgS was dissociable in the absence of agonist and dissociation was accelerated both in rate and extent by dopamine, an effect which was blocked by the dopamine D-2 receptor antagonist raclopride and by suramin, which inhibits receptor/G protein interaction. A range of agonists of varying efficacy increased the rate of dissociation of [S-35] GTPgS binding, with the more efficacious agonists resulting in faster dissociation. Agonists were able to dissociate about 70% of the pre-bound [S-35] GTPgS, leaving a component which may not be accessible to the agonist-bound receptor. The dissociable component of the [S-35] GTPgS binding was reduced with longer association times and increased [S-35] GTPgS concentrations. Conclusions and implications: These data are consistent with [S-35] GTPgS binding being initially to receptor-linked G proteins and then to G proteins which have separated from the agonist bound receptor. Under the conditions used typically for [S-35] GTPgS binding assays, therefore, much of the agonist-receptor complex remains in proximity to G proteins after they have been activated by agonist.

The representation of delayed intentions: a prospective subject-performed task?

To-be-enacted material is more accessible in tests of recognition and lexical decision than material not intended for action (T. Goschke J. Kuhl, 1993; R. L. Marsh, J. L. Hicks, & M. L. Bink, 1998). This finding has been attributed to the superior status of intention-related information. The current article explores an alternative (action-superiority) account that draws parallels between the intended enactment effect (IEE) and the subject-performed task effect. Using 2 paradigms, the authors observed faster recognition latencies for both enacted and to-be-enacted material. It is crucial to note that there was no evidence of an IEE for items that had already been executed during encoding. The IEE was also eliminated when motor processing was prevented after verbal encoding. These findings suggest an overlap between overt and intended enactment and indicate that motor information may be activated for verbal material in preparation for subsequent execution.

Aging and the accessibility of performed and to-be-performed actions

In young adults information designated for future enactment is more readily accessible from memory than information not intended for enactment (e.g. Goschke & Kuhl, 1993). We examined whether this advantage for to-be-enacted material is reduced in older adults and thus whether attenuated action accessibility could underlie age-associated declines in prospective remembering. Young and older adults showed an equivalent increase in accessibility (faster recognition latencies) for to-be-enacted items over items intended for verbal report. Both age groups also showed increased accessibility for actions performed at encoding compared with verbally encoded items. Moreover, these effects were non-additive, suggesting similarities in the representation of completed and to-be-completed actions.

Motor brain regions are involved in the encoding of delayed intentions: a fMRI study

In studies of prospective memory, recall of the content of delayed intentions is normally excellent, probably because they contain actions that have to be enacted at a later time. Action words encoded for later enactment are more accessible from memory than those encoded for later verbal report [Freeman, J.E., and Ellis, J.A. 2003a. The representation of delayed intentions: A prospective subject-performed task? Journal of Experimental Psychology: Learning, Memory, and Cognition, 29, 976-992.]. As this higher assessibility is lost when the intended actions have to be enacted during encoding, or when a motor interference task is introduced concurrent to intention encoding, Freeman and Ellis suggested that the advantage of to-be-enacted actions is due to additional preparatory motor operations during encoding. Accordingly, in a fMRI study with 10 healthy young participants, we investigated whether motor brain regions are differentially activated during verbal encoding of actions for later enactment with the right hand in contrast to verbal encoding of actions for later verbal report. We included an additional condition of verbal encoding of abstract verbs for later verbal report to investigate whether the semantic motor information inherent in action verbs in contrast to abstract verbs activates motor brain regions different from those involved in the verbal encoding of actions for later enactment. Differential activation for the verbal encoding of to-be-enacted actions in contrast to to-be-reported actions was found in brain regions known to be involved in covert motor preparation for hand movements, i.e. the postcentral gyrus, the precuneus, the dorsal and ventral premotor cortex, the posterior middle temporal gyrus and the inferior parietal lobule. There was no overlap between these brain regions and those differentially activated during the verbal encoding of actions in contrast to abstract verbs for later verbal report. Consequently, the results of this fMRI study suggest the presence of preparatory motor operations during the encoding of delayed intentions requiring a future motor response, which cannot be attributed to semantic information inherent to action verbs. (c) 2006 Elsevier B.V. All rights reserved.

Visual eye disease simulator

Visually impaired people have a very different view of the world such that seemingly simple environments as viewed by a ‘normally’ sighted people can be difficult for people with visual impairments to access and move around. This is a problem that can be hard to fully comprehend by people with ‘normal vision’ even when guidelines for inclusive design are available. This paper investigates ways in which image processing techniques can be used to simulate the characteristics of a number of common visual impairments in order to provide, planners, designers and architects, with a visual representation of how people with visual impairments view their environment, thereby promoting greater understanding of the issues, the creation of more accessible buildings and public spaces and increased accessibility for visually impaired people in everyday situations.

A peer-to-peer approach to content dissemination and search in collaborative networks

There are three key driving forces behind the development of Internet Content Management Systems (CMS) - a desire to manage the explosion of content, a desire to provide structure and meaning to content in order to make it accessible, and a desire to work collaboratively to manipulate content in some meaningful way. Yet the traditional CMS has been unable to meet the latter of these requirements, often failing to provide sufficient tools for collaboration in a distributed context. Peer-to-Peer (P2P) systems are networks in which every node is an equal participant (whether transmitting data, exchanging content, or invoking services) and there is an absence of any centralised administrative or coordinating authorities. P2P systems are inherently more scalable than equivalent client-server implementations as they tend to use resources at the edge of the network much more effectively. This paper details the rationale and design of a P2P middleware for collaborative content management.

Simplifying Bode's maximum available feedback design

Bode's method for obtaining 'maximum obtainable feedback' is a good example of a nontrivial feedback system design technique, but it is largely overlooked. This paper shows how the associated mathematics can be simplified and linear elements used in its implementation, so as to make it accessible for teaching to undergraduates.

Developments in block copolymer science and technology

Focuses on recent advances in research on block copolymers, covering chemistry (synthesis), physics (phase behaviors, rheology, modeling), and applications (melts and solutions). Written by a team of internationally respected scientists from industry and academia, this text compiles and reviews the expanse of research that has taken place over the last five years into one accessible resource. Ian Hamley is the world-leading scientist in the field of block copolymer research Presents the recent advances in the area, covering chemistry, physics and applications. Provides a broad coverage from synthesis to fundamental physics through to applications Examines the potential of block copolymers in nanotechnology as self-assembling soft materials

Heterosite effects in novel heteronuclear clusters [OS2Ru(CO)(11)(PPh3)] and Os2Ru(CO)(10)(2-acetylpyridine-N-isopropylimine)]

A new synthetic route towards the mixed-metal cluster [OS2Ru(CO)(12)] is described together with the syntheses of its PPh3 and iPr-AcPy (iPr-AcPy = 2-acetylpyridine-N-isopropylimine) derivatives. The molecular structures of the novel clusters [Os2Ru(CO)(11)(PPh3)] and [Os2Ru(CO)(10)(iPr-AcPy)] were determined on the basis of crystalline solid solutions of the Os2Ru and corresponding Os-3 species. The structures reveal that coordination of the Lewis bases occurs exclusively at the ruthenium site of [Os2Ru(CO)(12)], which is in agreement with density functional theory (DFT) calculations on several structural isomers of these compounds. According to the time-dependent DFT results, the lowest optically accessible excited state of [Os2Ru(CO)(10)(iPr-AcPy)] has a prevailing sigma(Ru-Os-2)pi*(iPr-AcPy) character, with a partial sigma sigma*(Ru-Os-2) contribution. In weakly coordinating 2-chlorobutane, the excited state has a lifetime tau = 10.4 +/- 1.2 ps and produces biradicals considerably faster than observed for [Os-3(CO)10(iPr-AcPy) (tau = 25.3 +/- 0.7ps)]. In coordinating acetonitrile, the excited state of [Os2Ru(CO)(10)(iPr-AcPy)] decays mono-exponentially with a lifetime tau = 2.1 +/- 0.2 ps. In contrast to [Os-3(CO)(10)(iPr-AcPy)] that forms biradicals as the main primary photoproduct even in strongly coordinating solvents, zwitterion formation from the solvated lowest excited state is observed for the heterometallic cluster. This is concluded from time-resolved absorption studies in the microsecond time domain. Due to the lower tendency of the coordinatively unsaturated Ru+(CO)(2)(iPr-AcPy-/0) moiety to bind a Lewis base, the heteronuclear biradical and zwitterionic photoproducts live significantly shorter than their triosmium counterparts. The influence of the weaker Os-2-Ru(iPr-AcPy) bond on the redox reactivity is clearly reflected in very reactive radical anions formed upon electrochemical reduction of [Os2Ru(CO)(10)(iPr-AcPy)]. The dimer [-OS(CO)(4)-Os(CO)(4)-Ru(CO)(2)(iPr-AcPy)](2)(2-) is the only IR-detectable intermediate reduction product. The dinuclear complex [Os-2(CO)(8)](2-) and insoluble [Ru(CO)(2)(iPr-AcPy)](n), are the ultimate reduction products, proving fragmentation of the OS2Ru core.