Molecular recognition between functionalized gold nanoparticles and healable, supramolecular polymer blends – a route to property enhancement

A new, healable, supramolecular nanocomposite material has been developed and evaluated. The material comprises a blend of three components: a pyrene-functionalized polyamide, a polydiimide and pyrenefunctionalized gold nanoparticles (P-AuNPs). The polymeric components interact by forming well-defined p–p stacked complexes between p-electron rich pyrenyl residues and p-electron deficient polydiimide residues. Solution studies in the mixed solvent chloroform–hexafluoroisopropanol (6 : 1, v/v) show that mixing the three components (each of which is soluble in isolation), results in the precipitation of a supramolecular, polymer nanocomposite network. The precipitate thus formed can be re-dissolved on heating, with the thermoreversible dissolution/precipitation procedure repeatable over at least 5 cycles. Robust, self-supporting composite films containing up to 15 wt% P-AuNPs could be cast from 2,2,2- trichloroethanol. Addition of as little as 1.25 wt% P-AuNPs resulted in significantly enhanced mechanical properties compared to the supramolecular blend without nanoparticles. The nanocomposites showed a linear increase in both tensile moduli and ultimate tensile strength with increasing P-AuNP content. All compositions up to 10 wt% P-AuNPs exhibited essentially quantitative healing efficiencies. Control experiments on an analogous nanocomposite material containing dodecylamine-functionalized AuNPs (5 wt%) exhibited a tensile modulus approximately half that of the corresponding nanocomposite that incorporated 5 wt% pyrene functionalized-AuNPs, clearly demonstrating the importance of the designed interactions between the gold filler and the supramolecular polymer matrix.

Microchannel electrode interfaces to assess bladder afferent activity

By placing axons into polymeric micro-channels hosting embedded electrodes the extracellular amplitude of action potentials is greatly increased, allowing for robust recording and noise suppression. We are developing such an electrode interface to record electrical activity from bladder afferents to restore bladder control in patients suffering from spinal cord injury. Here we describe our microchannel electrode interface in terms of design, microfabrication and electrode characteristics and report on in vivo bladder function after implantation of teased dorsal rootlets within microchannels.

Electronic charge transfer between ceria surfaces and gold adatoms: a GGA+U investigation

We use density functional theory calculations with Hubbard corrections (DFT+U) to investigate electronic aspects of the interaction between ceria surfaces and gold atoms. Our results show that Au adatoms at the (111) surface of ceria can adopt Au0, Au+ or Au� electronic configurations depending on the adsorption site. The strongest adsorption sites are on top of the surface oxygen and in a bridge position between two surface oxygen atoms, and in both cases charge transfer from the gold atom to one of the Ce cations at the surface is involved. Adsorption at other sites, including the hollow sites of the surface, and an O–Ce bridging site, is weaker and does not involve charge transfer. Adsorption at an oxygen vacancy site is very strong and involves the formation of an Au� anion. We argue that the ability of gold atoms to stabilise oxygen vacancies at the ceria surface by moving into the vacancy site and attracting the excess electrons of the defect could be responsible for the enhanced reducibility of ceria surfaces in the presence of gold. Finally, we rationalise the differences in charge transfer behaviour from site to site in terms of the electrostatic potential at the surface and the coordination of the species.

Following the creation of active gold nanocatalysts from phosphine-stabilized molecular clusters

The phosphine-stabilised gold cluster [Au6(Ph2P-o-tolyl)6](NO3)2 is converted into an active nanocatalyst for the oxidation of benzyl alcohol through low-temperature peroxide-assisted removal of the phosphines, avoiding the high-temperature calcination process. The process was monitored using in-situ X-ray absorption spectroscopy, which revealed that after a certain period of the reaction with tertiary butyl hydrogen peroxide, the phosphine ligands are removed to form nanoparticles of gold which matches with the induction period seen in the catalytic reaction. Density functional theory calculations show that the energies required to remove the ligands from the [Au6Ln]2+ increase significantly with successive removal steps, suggesting that the process does not occur at once but sequentially. The calculations also reveal that ligand removal is accompanied by dramatic re-arrangements in the topology of the cluster core.

User's manual

'Typeform dialogues', as originally planned for publication, was an interactive CD-based screen interface presenting a comparative survey of typeform history and description. The CD was to be held inside a printed book that included two essays and a User’s Manual. Although 'Typeform dialogues' (CD+book) was not completed as planned, a PDF file was published containing the User’s Manual, together with background information about the interface and the project it was part of. The User's Manual presents all interface sections and features (using screen grabs) and explains their editorial rationale, design, and function.

Is there a gold social seal? The financial effects of additions to and deletions from social stock indices

This study investigates the financial effects of additions to and deletions from the most well-known social stock index: the MSCI KLD 400. Our study makes use of the unique setting that index reconstitution provides and allows us to bypass possible issues of endogeneity that commonly plague empirical studies of the link between corporate social and financial performance. By examining not only short-term returns but also trading activity, earnings per share, and long-term performance of stocks that are involved in these events, we bring forward evidence of a ‘social index effect’ where unethical transgressions are penalized more heavily than responsibility is rewarded. We find that the addition of a stock to the index does not lead to material changes in its market price, whereas deletions are accompanied by negative cumulative abnormal returns. Trading volumes for deleted stocks are significantly increased on the event date, while the operational performances of the respective firms deteriorate after their deletion from the social index.

Self-assembly of a Model Peptide incorporating a Hexa-Histidine sequence attached to an Oligo-Alanine sequence, and binding to Gold NTA/Nickel nanoparticles

Amyloid fibrils are formed by a model surfactant-like peptide (Ala)10-(His)6 containing a hexahistidine tag. This peptide undergoes a remarkable two-step self-assembly process with two distinct critical aggregation concentrations (cac’s), probed by fluorescence techniques. A micromolar range cac is ascribed to the formation of prefibrillar structures, whereas a millimolar range cac is associated with the formation of well-defined but more compact fibrils. We examine the labeling of these model tagged amyloid fibrils using Ni-NTA functionalized gold nanoparticles (Nanogold). Successful labeling is demonstrated via electron microscopy imaging. The specificity of tagging does not disrupt the β-sheet structure of the peptide fibrils. Binding of fibrils and Nanogold is found to influence the circular dichroism associated with the gold nanoparticle plasmon absorption band. These results highlight a new approach to the fabrication of functionalized amyloid fibrils and the creation of peptide/nanoparticle hybrid materials.

Polymer protected gold nanoparticles: synthesis, characterization and application in catalysis

This review discusses the stabilization of gold nanoparticles (AuNPs) by nonionic, anionic, cationic and amphoteric polymers. The protocols used for synthesis of AuNPs in aqueous and organic solvents are described. Size, shape and morphology of AuNPs are characterized by various physicochemical methods. Application aspects of polymer-protected AuNPs in catalysis are outlined.

A land cover map of Latin America and the Caribbean in the framework of the SERENA project

Land cover maps at different resolutions and mapping extents contribute to modeling and support decision making processes. Because land cover affects and is affected by climate change, it is listed among the 13 terrestrial essential climate variables. This paper describes the generation of a land cover map for Latin America and the Caribbean (LAC) for the year 2008. It was developed in the framework of the project Latin American Network for Monitoring and Studying of Natural Resources (SERENA), which has been developed within the GOFC-GOLD Latin American network of remote sensing and forest fires (RedLaTIF). The SERENA land cover map for LAC integrates: 1) the local expertise of SERENA network members to generate the training and validation data, 2) a methodology for land cover mapping based on decision trees using MODIS time series, and 3) class membership estimates to account for pixel heterogeneity issues. The discrete SERENA land cover product, derived from class memberships, yields an overall accuracy of 84% and includes an additional layer representing the estimated per-pixel confidence. The study demonstrates in detail the use of class memberships to better estimate the area of scarce classes with a scattered spatial distribution. The land cover map is already available as a printed wall map and will be released in digital format in the near future. The SERENA land cover map was produced with a legend and classification strategy similar to that used by the North American Land Change Monitoring System (NALCMS) to generate a land cover map of the North American continent, that will allow to combine both maps to generate consistent data across America facilitating continental monitoring and modeling

Validation of the NANA (Novel Assessment of Nutrition and Ageing) touch screen system for use at home by older adults

Prospective measurement of nutrition, cognition, and physical activity in later life would facilitate early detection of detrimental change and early intervention but is hard to achieve in community settings. Technology can simplify the task and facilitate daily data collection. The Novel Assessment of Nutrition and Ageing (NANA) toolkit was developed to provide a holistic picture of an individual's function including diet, cognition and activity levels. This study aimed to validate the NANA toolkit for data collection in the community. Forty participants aged 65 years and over trialled the NANA toolkit in their homes for three 7-day periods at four-week intervals. Data collected using the NANA toolkit were compared with standard measures of diet (four-day food diary), cognitive ability (processing speed) and physical activity (self-report). Bland–Altman analysis of dietary intake (energy, carbohydrates, protein fat) found a good relationship with the food diary and cognitive processing speed and physical activity (hours) were significantly correlated with their standard counterparts. The NANA toolkit enables daily reporting of data that would otherwise be collected sporadically while reducing demands on participants; older adults can complete the daily reporting at home without a researcher being present; and it enables prospective investigation of several domains at once

Shifting sand, shifting livelihoods? Reflections on a coastal gold rush in Ghana

Artisanal and small-scale mining (ASM) is often characterised as rush-type activity undertaken by people looking to ‘get-rich quick’. An alternative view posits ASM as poverty-driven activity which provides a valuable source of employment to a rural population where agriculture has failed to provide an adequate income. Against this dichotomy, this article critically reviews the short-lived, but high profile, gold rush which occurred on the beaches of Elmina, a fishing town in Ghana’s Central Region. At its peak, more than 1000 people, including local fishermen and career miners from the Western Region and Eastern Region of the country, were mining on the beaches. Drawing on interviews with miners and local business owners, the analysis explores the dynamics of the rush and its implications for understanding the ASM sector in Ghana. The discussion highlights the challenges associated with managing resources in dynamic and heterogeneous contexts, reconciling separate and conflicting sectoral priorities and the need to go beyond simplified and dualistic representations of the sector.

Tensile bond strength of cast commercially pure titanium and cast gold-alloy posts and cores cemented with two luting agents

Statement of problem. In vitro studies on the retentive strengths of various cements used to retain posts have reported conflicting results. Purpose. The purpose of this study was to compare the tensile strength of commercially pure titanium and type III cast gold-alloy posts and cores cemented with zinc phosphate or resin cement. Material and methods. Forty-two extracted human canines were endoclontically treated. The root preparations were accomplished using Largo reamers (10 mm in depth and 1.7 mm in diameter). Acrylic resin patterns for the posts and cores were made, and specimens were cast in commercially pure titanium and in type III gold alloy (n=7). Fourteen titanium cast posts and cores were submitted to surface treatment with Kroll acid solution and to scanning electron microscopy (SEM), before and after acid etching. The groups (n=7) were cemented with zinc phosphate cement or resin cement (Panavia F). Tensile strengths were measured in a universal testing machine at a crosshead speed of 0.5 mm/min. The results (Kgf) were statistically analyzed by 2-way ANCIVA (alpha=.05). Results. The 2-way ANOVA indicated that there were no significant differences among the groups tested. Retentive means for zinc phosphate and Panavia F cements were statistically similar. The bond strength was not Influenced by the alloy, the luting material, or the etching treatment. SEM analysis indicated that the etched surfaces were smoother than those that did not receive surface treatment, but this fact did not influence the results. Conclusions. Commercially pure titanium cast posts and cores cemented with zinc phosphate and resin cements demonstrated similar mean tensile retentive values. Retentive values were also similar to mean values recorded for cast gold-alloy posts and cores cemented with zinc phosphate cement and resin cements.

Accuracy of Periapical Radiography and Cone-Beam Computed Tomography Scans in Diagnosing Apical Periodontitis Using Histopathological Findings as a Gold Standard

Introduction: The aim of this study was to evaluate the accuracy of two imaging methods in diagnosing apical periodontitis (AP) using histopathological findings as a gold standard. Methods: The periapex of 83 treated or untreated roots of dogs` teeth was examined using periapical radiography (PR), cone-beam computed tomography (CBCT) scans, and histology. Sensitivity, specificity, predictive values, and accuracy of PR and CBCT diagnosis were calculated. Results: PR detected AP in 71% of roots, a CBCT scan detected AP in 84%, and AP was histologically diagnosed in 93% (p = 0.001). Overall, sensitivity was 0.77 and 0.91 for PR and CBCT, respectively. Specificity was 1 for both. Negative predictive value was 0.25 and 0.46 for PR and CBCT, respectively. Positive predictive value was 1 for both. Diagnostic accuracy (true positives + true negatives) was 0.78 and 0.92 for PR and CBCT (p = 0.028), respectively. Conclusion: A CBCT scan was more sensitive in detecting AP compared with PR, which was more likely to miss AP when it was still present. (J Endod 2009;35:1009-1012)