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).

The Ethical Gold series

A series of five articles, published over six months in 2010, which explained the key ethical issues relating to sourcing gold. The Ethical Gold Series was written for practising jewellers, industrial jewellery manufacturers and the wider design community. The Ethical Gold Series was published in the Benchpeg Newsletter, an online jewellery industry journal, which in 2010 had over 5,500 subscribers. The material for the articles was drawn from a year of ethnographic fieldwork in the UK jewellery sector, funded by the AHRC, and field visits to preserved, operating and proposed gold mining sites in Alaska, California, Sweden, Wales and Scotland. The ethnographic fieldwork included ‘ethical gold’ promotional events, private industry meetings and jewellery trade shows and meetings with jewellery manufacturers and retailers, assayers, gold refiners and traders and environmental and fair trade campaigners.

Containing precious metals: hallmarking, minting and the materiality of gold and silver in medieval and modern England.

This book chapter extends the argument constructed by Oakley in his conference paper ‘Containing gold: Institutional attempts to define and constrict the values of precious metal objects’ presented at ‘Itineraries of the Material’, a conference held at Goethe Universitaet, Frankfurt am Main in 2011. Oakley’s chapter investigates the social forces that define the identities, social pathways and physical movement of objects made of precious metal. It presents a case study in which constitutive substance rather than the conceptual object is the key driver behind the social trajectories of numerous artefacts and their reception by contemporary audiences. This supports the main contention of the book as a whole: the need to reconsider, and when necessary challenge, the dominance of the social biography of objects in the study of material culture. Oakley’s research used historical and ethnographic approaches, including three years’ of ethnographic field research in the jewellery industry. This included training as a precious metal assayer at the Birmingham Assay Office and observing the industry and public response to government proposals to abolish the hallmarking legislation. This fieldwork was augmented by archive, library and object collection research on the histories of assaying and goldsmithing. Oakley presents an analysis of the historical development and contemporary social relevance of hallmarking, a technological process that has never previously been subject to ethnographic study, yet is fundamental to one of the UK’s creative industries.

Moralising Gold Supply Chains

During the late twentieth century the supply chains for gold were considered by the majority of consumers (when they were considered at all) to be driven by simple commercial imperatives. That notion was shattered during the first decade of the twenty-first century by the appearance of ethical campaigns, led by advocates determined to present major players in the gold industry as morally reprehensible. The ‘No Dirty Gold’ campaign sought to shift the purchasing of gold onto a moral register, in order to challenge the activities of large mining corporations. It was followed by the Fairtrade Foundation’s ‘Fairtrade Gold’ initiative, which had aspirations to support subsistence mining communities at the expense of big business. By directly targeting a luxury material and playing on its inherent social ambiguities, campaigners hoped to thoroughly moralise the purchasing of gold objects. Dr Oakley’s presentation will examine the forces behind this developing social phenomenon, describe the trajectories of a selection of major campaigns, and consider the extent to which these have impacted on public attitudes, gold miners and the actions of consumers, producers and retailers of luxury goods.

Using an anisotropic semivariogram of acoustic backscatter intensity to determine the effects of river and tidal forces on the spatial structure of the Gold River delta

Senior thesis written for Oceanography 445

Churchill as Chancellor of the Exchequer (1924–9) and the return to the gold standard

The general election of 29 October 1924 saw Winston Churchill return to Parliament as Constitutionalist MP for Epping after two years in the political wilderness. It also saw Stanley Baldwin swept back to Number 10 on a Conservative landslide. Speculation about whether Baldwin would cement Churchill’s drift from the Liberal fold by offering him office surfaced during the election campaign. Churchill nevertheless thought ‘it very unlikely that I shall be invited to join the Government, as owing to the size of the majority it will probably be composed only of impeccable Conservatives’. [ 1 ] Because of his anti-socialist credentials, his ability to reassure wavering Liberals through his opposition to protectionism – dropped by Baldwin after its rejection in the 1923 general election – and concern he could prove a rallying point for backbench malcontents, there was however much to commend giving Churchill a post. To his surprise, Baldwin offered Churchill the long-coveted office of Chancellor of the Exchequer, briefly held by his father before his ill-conceived resignation in 1887. Having arranged a meeting with his Labour predecessor, Philip Snowden, about outstanding business the new Chancellor set to work. Marking his political transition, a few days later Churchill resigned from the National Liberal Club.

Winston Churchill as Chancellor of the Exchequer (1924-9) and the Return to the Gold Standard

This revisits Churchill's decision, as Chancellor of the Exchequer 1924-29, to restore the Gold Standard in 1925. This is considered within the wider context of the overall aims of Churchill's policies, including his efforts to: tackle Anglo-American economic and financial relations in the aftermath of the Great War; address budgetary pressures; widen the tax base through innovations such as the Betting Duty; spread the social burden of taxes; and revive the economy, not least through his de-rating scheme.

Twentieth Century Modern Architecture and the Countryside: Ludwig Mies van der Rohe's design for a country gold clubhouse for the Krefeld Golf Club Association

This paper investigates relationships between modernity and monumentality in the architecture of Ludwig Mies van der Rohe. In his Modern Architecture, the critic and historian Kenneth Frampton separated Mies’ work into two historical periods, 1921-1933 and 1933-1967; the first he entitled ‘Mies van der Rohe and the significance of fact,’ the second ‘Mies van der Rohe and the monumentalisation of technique.’ The two historical periods correspond to two different geopolitical phases of Mies’ career, the first in Weimar Germany the second in the United States. By looking at a number of designs and texts made by Mies in the 1930’s and 1940’s, this essay questions the validity of separating Mies’ architecture into such clear-cut categories, where each one can enjoy a seeming independence from the other. The fulcrum for the discussion is Mies’ design of 1930 for a country golf clubhouse for the industrial town of Krefeld in north-western Germany. Our attention to the golf clubhouse design was prompted by the recent installation (2013), in which a 1-1 model of the design, made primarily from plywood, was erected in a field close the the site of Mies' original proposal.

Gold, power, protest: Digital and social media and protests against large-scale mining projects in Colombia

Colombia’s Internet connectivity has increased immensely. Colombia has also ‘opened for business’, leading to an influx of extractive projects to which social movements object heavily. Studies on the role of digital media in political mobilisation in developing countries are still scarce. Using surveys, interviews, and reviews of literature, policy papers, website and social media content, this study examines the role of digital and social media in social movement organisations and asks how increased digital connectivity can help spread knowledge and mobilise mining protests. Results show that the use of new media in Colombia is hindered by socioeconomic constraints, fear of oppression, the constraints of keyboard activism and strong hierarchical power structures within social movements. Hence, effects on political mobilisation are still limited. Social media do not spontaneously produce non-hierarchical knowledge structures. Attention to both internal and external knowledge sharing is therefore conditional to optimising digital and social media use.

Electroanalysis of urinary L-dopa using tyrosinase immobilized on gold nanoelectrode ensembles

The performance of an amperometric biosensor constructed by associating tyrosinase (Tyr) enzyme with the advantages of a 3D gold nanoelectrode ensemble (GNEE) is evaluated in a flow-injection analysis (FIA) system for the analysis of l-dopa. GNEEs were fabricated by electroless deposition of the metal within the pores of polycarbonate track-etched membranes. A simple solvent etching procedure based on the solubility of polycarbonate membranes is adopted for the fabrication of the 3D GNEE. Afterward, enzyme was immobilized onto preformed self-assembled monolayers of cysteamine on the 3D GNEEs (GNEE-Tyr) via cross-linking with glutaraldehyde. The experimental conditions of the FIA system, such as the detection potential (−0.200 V vs. Ag/AgCl) and flow rates (1.0 mL min−1) were optimized. Analytical responses for l-dopa were obtained in a wide concentration range between 1 × 10−8 mol L−1 and 1 × 10−2 mol L−1. The limit of quantification was found to be 1 × 10−8 mol L−1 with a resultant % RSD of 7.23% (n = 5). The limit of detection was found to be 1 × 10−9 mol L−1 (S/N = 3). The common interfering compounds, namely glucose (10 mmol L−1), ascorbic acid (10 mmol L−1), and urea (10 mmol L−1), were studied. The recovery of l-dopa (1 × 10−7 mol L−1) from spiked urine samples was found to be 96%. Therefore, the developed method is adequate to be applied in the clinical analysis.

Anodic adsorptive stripping voltammetric determination of atrazine in spiked soil samples with a gold microelectrode

Microwave-assisted solvent extraction was combined with anodic adsorptive stripping voltammetry at a gold microelectrode to extract and quantify the herbicide atrazine in spiked soil samples. A systematic study of the experimental parameters affecting the stripping response was carried out by square-wave voltammetry. The voltammetric procedure is based on controlled adsorptive accumulation of atrazine at the potential of 0.35V (versus Ag/AgCl) in the presence of Britton–Robinson buffer pH (2.0). The limit of detection obtained for a 30 sec collection time was 4.3x10-7 mol L-1. Recovery experiments, at the 1µgg-1 level of spiking, gave good results for the global procedure, and the values found were comparable to those obtained by HPLC.

Determination of ametryn in soils via microwave-assisted solvent extraction coupled to anodic stripping voltammetry with a gold ultramicroelectrode

An extraction-anodic adsorptive stripping voltammetric procedure using microwave-assisted solvent extraction and a gold ultramicroelectrode was developed for determining the pesticide ametryn in soil samples. The method is based on the use of acetonitrile as extraction solvent and on controlled adsorptive accumulation of the herbicide at the potential of 0.50 V (vs. Ag/AgCl) in the presence of Britton-Robinson buffer (pH 3.3). Soil sample extracts were analysed directly after drying and redissolution with the supporting electrolyte but without other pre-treatment. The limit of detection obtained for a 10 s collection time was 0.021 µg g-1. Recovery experiments for the global procedure, at the 0.500 µg g-1 level, gave satisfactory mean and standard deviation results which were comparable to those obtained by HPLC with UV detection.

Detection of Arah1 (a major peanut allergen) in food using an electrochemical gold nanoparticle-coated screen-printed immunosensor

A gold nanoparticle-coated screen-printed carbon electrode was used as the transducer in the development of an electrochemical immunosensor for Ara h 1 (a major peanut allergen) detection in food samples. Gold nanoparticles (average diameter=32 nm) were electrochemically generated on the surface of screen-printed carbon electrodes. Two monoclonal antibodies were used in a sandwich-type immunoassay and the antibody–antigen interaction was electrochemically detected through stripping analysis of enzymatically (using alkaline phosphatase) deposited silver. The total time of the optimized immunoassay was 3 h 50 min. The developed immunosensor allowed the quantification of Ara h 1 between 12.6 and 2000 ng/ml, with a limit of detection of 3.8 ng/ml, and provided precise (RSD <8.7%) and accurate (recovery >96.6%) results. The immunosensor was successfully applied to the analysis of complex food matrices (cookies and chocolate), being able to detect Ara h 1 in samples containing 0.1% of peanut.

Using artificial neural networks to generate trading signals for crude oil, copper and gold futures

In this thesis, a feed-forward, back-propagating Artificial Neural Network using the gradient descent algorithm is developed to forecast the directional movement of daily returns for WTI, gold and copper futures. Out-of-sample back-test results vary, with some predictive abilities for copper futures but none for either WTI or gold. The best statistically significant hit rate achieved was 57% for copper with an absolute return Sharpe Ratio of 1.25 and a benchmarked Information Ratio of 2.11.