A study of localised galvanic replacement of copper and silver films with gold using scanning electrochemical microscopy

Galvanic replacement represents a highly significant process for the fabrication of bimetallic materials, but to date its application has been limited to either modification of large area metal surfaces or nanoparticles in solution. Here, the localised surface modification of copper and silver substrates with gold through the galvanic replacement process is reported. This was achieved by generation of a localised flux of AuCl4− ions from a gold ultramicroelectrode tip which interacts with the unbiased substrate of interest. The extent of modification with gold can be controlled through the tip–substrate distance and electrolysis time.

Galvanic Replacement of Semiconductor Phase I CuTCNQ Microrods with KAuBr4 to Fabricate CuTCNQ/Au Nanocomposites with Photocatalytic Properties

In this study, the reaction of semiconductor microrods of phase I copper 7,7,8,8-tetracyanoquinodimethane (CuTCNQ) with KAuBr4 in acetonitrile is reported. It was found that the reaction is redox in nature and proceeds via a galvanic replacement mechanism in which the surface of CuTCNQ is replaced with metallic gold nanoparticles. Given the slight solubility of CuTCNQ in acetonitrile, two competing reactions, namely CuTCNQ dissolution and the redox reaction with KAuBr4, were found to operate in parallel. An increase in the surface coverage of CuTCNQ microrods with gold nanoparticles occurred with an increased KAuBr4 concentration in acetonitrile, which also inhibited CuTCNQ dissolution. The reaction progress with time was monitored using UV−visible, FT-IR, and Raman spectroscopy as well as XRD and EDX analysis, and SEM imaging. The CuTCNQ/Au nanocomposites were investigated for their photocatalytic properties, wherein the destruction of Congo red, an organic dye, by simulated solar light was found dependent on the surface coverage of gold nanoparticles on the CuTCNQ microrods. This method of decorating CuTCNQ may open the possibility of modifying this and other metal-TCNQ charge transfer complexes with a host of other metals which may have significant applications.

Synthesis of CuTCNQ/Au microrods by galvanic replacement of semiconducting phase I CuTCNQ with KAuBr4 in aqueous medium

The spontaneous reaction between microrods of an organic semiconductor molecule, copper 7,7,8,8-tetracyanoquinodimethane (CuTCNQ) with [AuBr4]− ions in an aqueous environment is reported. The reaction is found to be redox in nature which proceeds via a complex galvanic replacement mechanism, wherein the surface of the CuTCNQ microrods is replaced with metallic gold nanoparticles. Unlike previous reactions reported in acetonitrile, the galvanic replacement reaction in aqueous solution proceeds via an entirely different reaction mechanism, wherein a cyclical reaction mechanism involving continuous regeneration of CuTCNQ consumed during the galvanic replacement reaction occurs in parallel with the galvanic replacement reaction. This results in the driving force of the galvanic replacement reaction in aqueous medium being largely dependent on the availability of [AuBr4]− ions during the reaction. Therefore, this study highlights the importance of the choice of an appropriate solvent during galvanic replacement reactions, which can significantly impact upon the reaction mechanism. The reaction progress with respect to different gold salt concentration was monitored using Fourier transform infrared (FT-IR), Raman, and X-ray photoelectron spectroscopy (XPS), as well as XRD and EDX analysis, and SEM imaging. The CuTCNQ/Au nanocomposites were also investigated for their potential photocatalytic properties, wherein the destruction of the organic dye, Congo red, in a simulated solar light environment was found to be largely dependent on the degree of gold nanoparticle surface coverage. The approach reported here opens up new possibilities of decorating metal–organic charge transfer complexes with a host of metals, leading to potentially novel applications in catalysis and sensing.

A study of the galvanic replacement reaction at surfaces and the role of lateral charge propagation

The galvanic replacement of isolated nanostructures of copper and silver on conducting supports as well as continuous films of copper with gold is reported. The surface morphology was characterized by scanning electron microscopy and the replacement with gold was confirmed by EDX analysis. It was found that lateral charge propagation during the replacement reaction had a significant effect in all cases. For the isolated nanostructures the deposition of gold was observed not only at the sacrificial template but also at the surrounding unmodified areas of the conducting substrate. In the case of copper films the role of lateral charge propagation was also confirmed by connecting it to an ITO electrode through an external circuit upon which gold deposition was also observed to occur. Interestingly, by inhibiting the rate of charge propagation, through the introduction of a series resistor, the morphology of gold on the copper substrate could be changed from discrete surface decoration with cube like nanoparticles to a more porous rough surface.

Lateral charge propagation effects during the galvanic replacement of electrodeposited MTCNQ (M= Cu, Ag) microstructures with gold and its influence on catalysed electron transfer reactions

The galvanic replacement of isolated electrodeposited semiconducting CuTCNQ microstructures on a glassy carbon (GC) substrate with gold is investigated. It is found that anisotropic metal nanoparticles are formed which are not solely confined to the redox active sites on the semiconducting materials but are also observed on the GC substrate which occurs via a lateral charge propagation mechanism. We also demonstrate that this galvanic replacement approach can be used for the formation of isolated AgTCNQ/Au microwire composites which occurs via an analogous mechanism. The resultant MTCNQ/Au (M = Cu, Ag) composite materials are characterized by Raman, spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and investigated for their catalytic properties for the reduction of ferricyanide ions with thiosulphate ions in aqueous solution. Significantly it is demonstrated that gold loading, nanoparticle shape and in particular the MTCNQ–Au interface are important factors that influence the reaction rate. It is shown that there is a synergistic effect at the CuTCNQ/Au composite when compared to AgTCNQ/Au at similar gold loadings.

Multi-criteria optimization of group replacement schedules for distributed water pipeline assets

This thesis presents a multi-criteria optimisation study of group replacement schedules for water pipelines, which is a capital-intensive and service critical decision. A new mathematical model was developed, which minimises total replacement costs while maintaining a satisfactory level of services. The research outcomes are expected to enrich the body of knowledge of multi-criteria decision optimisation, where group scheduling is required. The model has the potential to optimise replacement planning for other types of linear asset networks resulting in bottom-line benefits for end users and communities. The results of a real case study show that the new model can effectively reduced the total costs and service interruptions.

Clinical and radiographic outcomes of acetabular impaction grafting without cage reinforcement for revision hip replacement : a minimum ten-year follow-up study

Impaction bone grafting for reconstitution of bone stock in revision hip surgery has been used for nearly 30 years. We used this technique, in combination with a cemented acetabular component, in the acetabula of 304 hips in 292 patients revised for aseptic loosening between 1995 and 2001. The only additional supports used were stainless steel meshes placed against the medial wall or laterally around the acetabular rim to contain the graft. All Paprosky grades of defect were included. Clinical and radiographic outcomes were collected in surviving patients at a minimum of 10 years following the index operation. Mean follow-up was 12.4 years (SD 1.5; range 10.0-16.0). Kaplan-Meier survivorship with revision for aseptic loosening as the endpoint was 85.9% (95% CI 81.0 to 90.8%) at 13.5 years. Clinical scores for pain relief remained satisfactory, and there was no difference in clinical scores between cups that appeared stable and those that appeared loose radiographically.

Replacement of healthcare-associated MRSA by community-associated MRSA in Queensland : confirmation by genotyping

Objective To describe the changing prevalence of healthcare- and community-associated MRSA. Methods Susceptibility phenotypes of MRSA were observed from 2000 to 2012 using routine susceptibility data. Phenotypic definitions of major clones were validated by genotyping isolates from a nested period prevalence survey in 2011. Results The predominant healthcare-associated (AUS-2/3 like) MRSA phenotype decreased from 42 to 14 isolates per million occasions of service in outpatients (P < 0.0001) and from 650 to 75 isolates per million accrued patient days in inpatients (P 0.0005), while the respective rates of the healthcare-related EMRSA-15 like phenotype increased from 1 to 19 in outpatients (P < 0.0001) and from 11 to 83 in inpatients (P < 0.0001) and those of the community-associated MRSA phenotype increased from 17 to 296 in outpatients (P < 0.0001) and from 71 to 486 in inpatients (P < 0.0001). When compared with single nucleotide polymorphism genotyping the AUS-2/3 like phenotype had a sensitivity and positive predictive value (PPV) for CC239 of 1 and 0.791 respectively, while the EMRSA-15 like phenotype had a sensitivity and PPV for CC22 of 0.903 and 0.774. PVL-positive CA-MRSA, predominantly ST93 and CC30, accounted for 60.8% of MRSA, while PVL-negative CA-MRSA, mainly CC5 and CC1, accounted for 21.4%. Conclusions The initially dominant healthcare-associated MRSA clone has been progressively replaced, mainly by four community-associated lineages.

Control strategies to prevent total hip replacement-related infections : a systematic review and mixed treatment comparison

OBJECTIVE: To synthesise the available evidence and estimate the comparative efficacy of control strategies to prevent total hip replacement (THR)-related surgical site infections (SSIs) using a mixed treatment comparison. DESIGN: Systematic review and mixed treatment comparison. SETTING: Hospital and other healthcare settings. PARTICIPANTS: Patients undergoing THR. PRIMARY AND SECONDARY OUTCOME MEASURES: The number of THR-related SSIs occurring following the surgical operation. RESULTS: 12 studies involving 123 788 THRs and 9 infection control strategies were identified. The strategy of 'systemic antibiotics+antibiotic-impregnated cement+conventional ventilation' significantly reduced the risk of THR-related SSI compared with the referent strategy (no systemic antibiotics+plain cement+conventional ventilation), OR 0.13 (95% credible interval (CrI) 0.03-0.35), and had the highest probability (47-64%) and highest median rank of being the most effective strategy. There was some evidence to suggest that 'systemic antibiotics+antibiotic-impregnated cement+laminar airflow' could potentially increase infection risk compared with 'systemic antibiotics+antibiotic-impregnated cement+conventional ventilation', 1.96 (95% CrI 0.52-5.37). There was no high-quality evidence that antibiotic-impregnated cement without systemic antibiotic prophylaxis was effective in reducing infection compared with plain cement with systemic antibiotics, 1.28 (95% CrI 0.38-3.38). CONCLUSIONS: We found no convincing evidence in favour of the use of laminar airflow over conventional ventilation for prevention of THR-related SSIs, yet laminar airflow is costly and widely used. Antibiotic-impregnated cement without systemic antibiotics may not be effective in reducing THR-related SSIs. The combination with the highest confidence for reducing SSIs was 'systemic antibiotics+antibiotic-impregnated cement+conventional ventilation'. Our evidence synthesis underscores the need to review current guidelines based on the available evidence, and to conduct further high-quality double-blind randomised controlled trials to better inform the current clinical guidelines and practice for prevention of THR-related SSIs.

Department of Social Services Options Paper : Options for Replacement Arrangements Following the Abolition of the Australian Charities and Not-for-profits Commission : Response

Submission in response to government options paper regarding arrangements for regulation of charities following abolition of the Australian Charities and Not-for-profits Commission.

Better cars or older cars?: Assessing CO2 emission reduction potential of passenger vehicle replacement programs

The primary motivation for the vehicle replacement schemes that were implemented in many countries was to encourage the purchase of new cars. The basic assumption of these schemes was that these acquisitions would benefit both the economy and the environment as older and less fuel-efficient cars were scrapped and replaced with more fuel-efficient models. In this article, we present a new environmental impact assessment method for assessing the effectiveness of scrappage schemes for reducing CO2 emissions taking into account the rebound effect, driving behavior for older versus new cars and entire lifecycle emissions for during the manufacturing processes of new cars. The assessment of the Japanese scrappage scheme shows that CO2 emissions would only decrease if users of the scheme retained their new gasoline passenger vehicles for at least 4.7 years. When vehicle replacements were restricted to hybrid cars, the reduction in CO2 achieved by the scheme would be 6-8.5 times higher than the emissions resulting from a scheme involving standard, gasoline passenger vehicles. Cost-benefit analysis, based on the emission reduction potential, showed that the scheme was very costly. Sensitivity analysis showed that the Japanese government failed to determine the optimum, or target, car age for scrapping old cars in the scheme. Specifically, scrapping cars aged 13 years and over did not maximize the environmental benefits of the scheme. Consequently, modifying this policy to include a reduction in new car subsidies, focused funding for fuel-efficient cars, and modifying the target car age, would increase environmental benefits. © 2013 Elsevier Ltd.

Distribution of fitness in populations of dengue viruses

Genetically diverse RNA viruses like dengue viruses (DENVs)segregate into multiple, genetically distinct, lineages that temporally arise and disappear on a regular basis. Lineage turnover may occur through multiple processes such as, stochastic or due to variations in fitness. To determine the variation of fitness, we measured the distribution of fitness within DENV populations and correlated it with lineage extinction and replacement. The fitness of most members within a population proved lower than the aggregate fitness of populations from which they were drawn, but lineage replacement events were not associated with changes in the distribution of fitness. These data provide insights into variations in fitness of DENV populations, extending our understanding of the complexity between members of individual populations.