Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution

The activation of oxygen molecules is an important issue in the gold-catalyzed partial oxidation of alcohols in aqueous solution. The complexity of the solution arising from a large number of solvent molecules makes it difficult to study the reaction in the system. In this work, O-2 activation on an Au catalyst is investigated using an effective approach to estimate the reaction barriers in the presence of solvent. Our calculations show that O-2 can be activated, undergoing OOH* in the presence of water molecules. The OOH* can readily be formed on Au(211) via four possible pathways with almost equivalent free energy barriers at the aqueous-solid interface: the direct or indirect activation of O-2 by surface hydrogen or the hydrolysis of O-2 following a Langmuir-Hinshelwood mechanism or an Eley-Rideal mechanism. Among them, the Eley-Rideal mechanism may be slightly more favorable due to the restriction of the low coverage of surface H on Au(211) in the other mechanisms. The results shed light on the importance of water molecules on the activation of oxygen in gold-catalyzed systems. Solvent is found to facilitate the oxygen activation process mainly by offering extra electrons and stabilizing the transition states. A correlation between the energy barrier and the negative charge of the reaction center is found. The activation barrier is substantially reduced by the aqueous environment, in which the first solvation shell plays the most important role in the barrier reduction. Our approach may be useful for estimating the reaction barriers in aqueous systems.

Structure and Catalytic Activity of Gold in Low-Temperature CO Oxidation

Structures and catalytic activities of Au thin films supported at anatase TiO(2)(101)) and a Au substrate are studied by using density functional theory calculations. The results show that O(2) can hardly adsorb at flat and stepped Au thin films, even supported by fully reduced TiO(2)(101) that can highly disperse Au atoms and offer strong electronic promotion. Interestingly, in both oxide-supported and pure Au. systems, wire-structured Au can adsorb both CO and O(2) rather strongly, and kinetic analysis suggests its high catalytic activity for low-temperature CO oxidation. The d-band center of Au at the catalytic site is determined to account for the unusual activity of the wire-structured film. A generalized structural model based on the wire-structured film is proposed for active Au, and possible support effects are discussed: Selected oxide surfaces can disperse Au atoms and stabilize the formation of a filmlike structure; they may also serve as a template for the preferential arrangement of Au atoms in a wire structure under low Au coverage.

Plasmon enhanced fluorescence studies from aligned gold nanorod arrays modified with SiO2 spacer layers

Here, we demonstrate that quasi self-standing Au nanorod arrays prepared with plasma polymerisation deposited SiO2 dielectric spacers support surface enhanced fluorescence (SEF) while maintaining high signal reproducibility. We show that it is possible to find a balance between enhanced radiative and non-radiative decay rates at which the fluorescent intensity is maximized. The SEF signal optimised with a 30 nm spacer layer thickness showed a 3.5-fold enhancement with a signal variance of <15% thereby keeping the integrity of the nanorod array. We also demonstrate the decreased importance of obtaining resonance conditions when localized surface plasmon resonance is positioned within the spectral region of Au interband transitions. Procedures for further increasing the SEF enhancement factor are also discussed.

Panning for Gold: The Standardizing Work of Filling “Autistic” Shells – Using institutional ethnography to explore textually mediated health relations in the diagnostic process of autism.

Health reform practices in Canada and elsewhere have restructured the purpose and use of diagnostic labels and the processes of naming such labels. Diagnoses are no longer only a means to tell doctors and patients what may be wrong and indicate potential courses of treatment; some diagnoses activate specialized services and supports for persons with a disability and those who provide care for them. In British Columbia, a standardized process of diagnosis with the outcome of an autism spectrum disorder gives access to government provided health care and educational services and supports. Such processes enter individuals into a complex of text mediated relations, regulated by the principles of evidence-based medicine. However, the diagnosis of autism in children is notoriously uncertain. Because of this ambiguity, standardizing the diagnostic process creates a hurdle in gaining help and support for parents who have children with problems that could lead to a diagnosis on the autism spectrum. Such processes and their organizing relations are problematized, explored and explicated below. Grounded in the epistemological and ontological shift offered by Dorothy E. Smith (1987; 1990a; 1999; 2005), this article reports on the findings of an institutional ethnographic study that explored the diagnostic process of autism in British Columbia. More specifically, this article focuses on the processes involved in going from mothers talking from their experience about their childrens problems to the formalized and standardized, and thus “virtually” produced, diagnoses that may or may not give access to services and supports in different systems of care. Two psychologists, a developmental pediatrician, a social worker – members of a specialized multidisciplinary assessment team – and several mothers of children with a diagnosis on the autism spectrum were interviewed. The implications of standardizing the diagnosis process of a disability that is not clear-cut and has funding attached are discussed. This ethnography also provides a glimpse of the implications of current and ongoing reforms in the state-supported health care system in British Columbia, and more generally in Canada, for people’s everyday doings.

Exploiting Human Resource Requirements to Infer Human Movement Patterns for Use in Modelling Disease Transmission Systems: An Example from Eastern Province, Zambia

In this research, an agent-based model (ABM) was developed to generate human movement routes between homes and water resources in a rural setting, given commonly available geospatial datasets on population distribution, land cover and landscape resources. ABMs are an object-oriented computational approach to modelling a system, focusing on the interactions of autonomous agents, and aiming to assess the impact of these agents and their interactions on the system as a whole. An A* pathfinding algorithm was implemented to produce walking routes, given data on the terrain in the area. A* is an extension of Dijkstra's algorithm with an enhanced time performance through the use of heuristics. In this example, it was possible to impute daily activity movement patterns to the water resource for all villages in a 75 km long study transect across the Luangwa Valley, Zambia, and the simulated human movements were statistically similar to empirical observations on travel times to the water resource (Chi-squared, 95% confidence interval). This indicates that it is possible to produce realistic data regarding human movements without costly measurement as is commonly achieved, for example, through GPS, or retrospective or real-time diaries. The approach is transferable between different geographical locations, and the product can be useful in providing an insight into human movement patterns, and therefore has use in many human exposure-related applications, specifically epidemiological research in rural areas, where spatial heterogeneity in the disease landscape, and space-time proximity of individuals, can play a crucial role in disease spread.

Imaging and radiation effects of gold nanoparticles in tumour cells

Gold nanoparticle radiosensitization represents a novel technique in enhancement of ionising radiation dose and its effect on biological systems. Variation between theoretical predictions and experimental measurement is significant enough that the mechanism leading to an increase in cell killing and DNA damage is still not clear. We present the first experimental results that take into account both the measured biodistribution of gold nanoparticles at the cellular level and the range of the product electrons responsible for energy deposition. Combining synchrotron-generated monoenergetic X-rays, intracellular gold particle imaging and DNA damage assays, has enabled a DNA damage model to be generated that includes the production of intermediate electrons. We can therefore show for the first time good agreement between the prediction of biological outcomes from both the Local Effect Model and a DNA damage model with experimentally observed cell killing and DNA damage induction via the combination of X-rays and GNPs. However, the requirement of two distinct models as indicated by this mechanistic study, one for short-term DNA damage and another for cell survival, indicates that, at least for nanoparticle enhancement, it is not safe to equate the lethal lesions invoked in the local effect model with DNA damage events.

Free-roaming dogs control activities in one Italian province (2000-2013): Is the implemented approach effective?

In Italy, standards for the management of free-roaming dogs (FRDs) are defined by regional norms, generating a high variability of approaches around the country. Despite efforts carried out by the competent authorities, FRDs are still a reality impacting upon animal health and welfare and public costs. A similar scenario can be found in many other Mediterranean and Balkan counties. Here we present 14 years of data (2000–2013) retrieved from the admission dog registry of a public shelter (PS) responsible for the collection of stray dogs from one Italian province. The aim of this retrospective study was to describe the local FRD population, identifying its source and to evaluate the effectiveness of the actions implemented by the local authorities. In the investigated period, 7,475 dogs were admitted to the PS. Despite the intense sterilisation plan (mean 381.7 sterilisations per year), the overall number of dogs entering PS did not decrease consistently across the years. Results highlighted a lack of responsibility of owners by failing to sterilise and identify their dogs and allowing intact animals to roam free, therefore producing uncontrolled and unwanted litters. The current dog population management strategy, based on both sheltering and capture-neuter-release programmes, is insufficient to tackle the straying phenomenon. Educational and sterilisation programmes should be an integral part of a successfully implemented FRD control plan. Our results provide further insight on free-roaming dog population dynamics and control systems, and may have important implications for many other local contexts across Europe trying to overcome the straying phenomenon.

Gold nanoparticle surface functionalization: mixed monolayer versus hetero bifunctional peg linker

To create a clinically relevant gold nanoparticle (AuNP) treatment, the surface must be functionalized with multiple ligands such as drugs, antifouling agents and targeting moieties. However, attaching several ligands of differing chemistries and lengths, while ensuring they all retain their biological functionality remains a challenge. This review compares the two most widely employed methods of surface co-functionalization, namely mixed monolayers and hetero-bifunctional linkers. While there are numerous in vitro studies successfully utilizing both surface arrangements, there is little consensus regarding their relative merits. Animal and preclinical studies have demonstrated the effectiveness of mixed monolayer functionalization and while some promising in vitro results have been reported for PEG linker capped AuNPs, any potential benefits of the approach are not yet fully understood.

A comparison of gold nanoparticle surface co-functionalization approaches using Polyethylene Glycol (PEG) and the effect on stability, non-specific protein adsorption and internalization

To create clinically useful gold nanoparticle (AuNP) based cancer therapeutics it is necessary to co-functionalize the AuNP surface with a range of moieties; e.g. Polyethylene Glycol (PEG), peptides and drugs. AuNPs can be functionalized by creating either a mixed monolayer by attaching all the moieties directly to the surface using thiol chemistry, or by binding groups to the surface by means of a bifunctional polyethylene glycol (PEG) linker. The linker methodology has the potential to enhance bioavailability and the amount of functional agent that can be attached. While there is a large body of published work using both surface arrangements independently, the impact of attachment methodology on stability, non-specific protein adsorption and cellular uptake is not well understood, with no published studies directly comparing the two most frequently employed approaches. This paper compares the two methodologies by synthesizing and characterizing PEG and Receptor Mediated Endocytosis (RME) peptide co-functionalized AuNPs prepared using both the mixed monolayer and linker approaches. Successful attachment of both PEG and RME peptide using the two methods was confirmed using Dynamic Light Scattering, Fourier Transform Infrared Spectroscopy and gel electrophoresis. It was observed that while the 'as synthesized' citrate capped AuNPs agglomerated under physiological salt conditions, all the mixed monolayer and PEG linker capped samples remained stable at 1M NaCl, and were stable in PBS over extended periods. While it was noted that both functionalization methods inhibited non-specific protein attachment, the mixed monolayer samples did show some changes in gel electrophoresis migration profile after incubation with fetal calf serum. PEG renders the AuNP stable in-vivo however, studies with MDA-MB-231 and MCF 10A cell lines indicated that functionalization with PEG, blocks cellular uptake. It was observed that co-functionalization with RME peptide using both the mixed monolayer and PEG linker methods greatly enhanced cellular internalization compared to PEG capped AuNPs.

In Troubles and Darkness:Black Red Gold

This is an essay including annotated critical editions documenting the history of reception of this song since 1848. Published in the Liederlexikon for the AHRC and DFG funded project 'The History of Reception of the Songs of the 1848 Revolution' (2009-2013).