Sonogashira coupling on an extended gold surface in vacuo: reaction of phenylacetylene with iodobenzene on Au(111)

Temperature-programmed reaction measurements supported by scanning tunneling microscopy have shown that phenylacetylene and iodobenzene react on smooth Au(111) under vacuum conditions to yield biphenyl and diphenyldiacetylene, the result of homocoupling of the reactant molecules. They also produce diphenylacetylene, the result of Sonogashira cross-coupling, prototypical of a class of reactions that are of paramount importance in synthetic organic chemistry and whose mechanism remains controversial. Roughened Au(111) is completely inert toward all three reactions, indicating that the availability of crystallographically well-defined adsorption sites is crucially important. High-resolution X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy show that the reactants are initially present as intact, essentially flat-lying molecules and that the temperature threshold for Sonogashira coupling coincides with that for C−I bond scission in the iodobenzene reactant. The fractional-order kinetics and low temperature associated with desorption of the Sonogashira product suggest that the reaction occurs at the boundaries of islands of adsorbed reactants and that its appearance in the gas phase is rate-limited by the surface reaction. These findings demonstrate unambiguously and for the first time that this heterogeneous cross-coupling chemistry is an intrinsic property of extended, metallic pure gold surfaces: no other species, including solvent molecules, basic or charged (ionic) species are necessary to mediate the process.

Abatement of mercury pollution in the small-scale gold mining industry: Restructuring the policy and research agendas

This paper critiques contemporary research and policy approaches taken toward the analysis and abatement of mercury pollution in the small-scale gold mining sector. Unmonitored releases of mercury from gold amalgamation have caused considerable environmental contamination and human health complications in rural reaches of sub-Saharan Africa, Latin America and Asia. Whilst these problems have caught the attention of the scientific community over the past 15-20 years, the research that has since been undertaken has failed to identify appropriate mitigation measures, and has done little to advance understanding of why contamination persists. Moreover, the strategies used to educate operators about the impacts of acute mercury exposure, and the technologies implemented to prevent farther pollution, have been marginally effective at best. The mercury pollution problem will not be resolved until governments and donor agencies commit to carrying out research aimed at improving understanding of the dynamics of small scale gold mining communities. Acquisition of this knowledge is the key to designing and implementing appropriate support and abatement measures. (c) 2005 Elsevier B.V. All rights reserved.

'Fair trade gold': Antecedents, prospects and challenges

This paper critically examines the challenges with, and impacts of, adopting the models in place for fair trade agriculture in the artisanal gold mining sector. Over the past two years, an NGO-led 'fair trade gold' movement has surfaced, its crystallization fuelled by a burgeoning body of evidence that points to impoverished artisanal miners in developing countries receiving low payments for their gold, as well as working in hazardous and unsanitary conditions. Proponents of fair trade gold contest that increased interaction between artisanal miners and Western jewellers could facilitate the former receiving fairer prices for gold, accessing support services, and ultimately, improving their quality of life. In the case of sub-Saharan Africa, however, the gold being mined on an artisanal scale does not supply Western retailers as perhaps believed; it is rather an important source of foreign exchange, which host governments employ buyers to collect for their coffers. It is maintained here that if the underlying purpose of fair trade is to improve the livelihoods and well-being of subsistence producers in developing countries, then the models that have proved so successful in alleviating the hardships of agro-producers of 'tropical' commodities such as coffee, tea, bananas and cocoa, should be adapted to artisanal gold mining in sub-Saharan Africa. Campaigns promoting 'fair trade gold' in the region should view host governments, and not Western retailers, as the 'end consumer', and focus on improving governance at the grassroots, organizing informal operators into working cooperatives, and addressing complications with purchasing arrangements - all of which would go a long way toward improving the livelihoods of subsistence artisanal miners. A case study of Noyem, Ghana, the location of a sprawling illegal gold mining community, is presented, which magnifies these challenges further and provides perspective on how they can be overcome. (c) 2007 Elsevier Ltd. All rights reserved.

Improving awareness of mercury pollution in small-scale gold mining communities: Challenges and ways forward in rural Ghana

This paper critiques the approach taken by the Ghanaian Government to address mercury pollution in the artisanal and small-scale gold mining sector. Unmonitored releases of mercury-used in the gold-amalgamation process-have caused numerous environmental complications throughout rural Ghana. Certain policy, technological and educational initiatives taken to address the mounting problem, however, have proved marginally effective at best, having been designed and implemented without careful analysis of mine community dynamics, the organization of activities, operators' needs and local geological conditions. Marked improvements can only be achieved in this area through increased government-initiated dialogue with the now-ostracized illegal galamsey mining community; introducing simple, cost-effective techniques for the reduction of mercury emissions; and effecting government-sponsored participatory training exercises as mediums for communicating information about appropriate technologies and the environment. (c) 2006 Elsevier Inc. All rights reserved.

Alternatives to cyanide in the gold mining industry: what prospects for the future

This paper reviews a series of alternative lixiviant systems for the recovery of gold from ores and concentrates. For over 100 years, cyanide has been the leach reagent of choice in gold mining because of its high gold recoveries, robustness and relatively low costs. The environmental damages resulting from its mismanagement, however, have initiated widespread research aimed at identifying and developing less toxic leaching agents. The most widely-researched alternative lixiviants for gold ores are examined in this paper, but it is evident that none has yet made any significant inroad into the dominant position of cyanide as the reagent of choice at the vast majority of gold mines worldwide. (c) 2005 Published by Elsevier Ltd.

Gold mining in Ghana's forest reserves: a report on the current debate

This paper examines the debate surrounding a recent decision made by the Ghanaian government to permit gold exploration - and potentially, mining - in 'protected' forest reserves. In 2001, four mining companies were awarded mineral exploration concessions in forested regions of the country, and have since put forward applications to mine for gold. Notwithstanding the sharp divide in opinion on the issue, the continued uncertainty surrounding the implications of the proposed activities makes further research on the ground imperative in the short term. Work aiming to elicit indigenous perspectives on the projects, as well as research that facilitates dialogue between and/or among stakeholder parties, should be prioritized.

Mercury: An agent of poverty in Ghana's small-scale gold-mining sector?

There is consensus worldwide that the artisanal and small-scale mining (ASM) sector is comprised of individuals who are trapped in a vicious cycle of poverty, lacking the necessary financial and technological means to improve their standards of living. Minimal work, however, has been undertaken to identify the very factors behind miners' plight, which inevitably vary from country to country. This paper uses a case study of Ghana to argue that an increased dependence upon mercury for amalgamation In artisanal gold-mining communities is one such-albeit overlooked-"agent of poverty". There is mounting empirical evidence which suggests that dealings with the monoponistic middlemen who supply mercury, purchases of costly medicines to remedy ailments caused by mercury poisoning, and a lack of appropriate safeguards and alternatives to amalgamation, are preventing gold miners from improving their practices and livelihoods. The solution to the problem lies in breaking this cycle of dependency, which can be achieved by providing miners with robust support services, mercury-free technologies and education. (c) 2006 Elsevier Ltd. All rights reserved.

Challenges with minimising mercury pollution in the small-scale gold mining sector: Experiences from the Guianas

This paper examines the barriers to mitigating mercury pollution at small-scale gold mines in the Guianas (Guyana, French Guiana and Suriname), and prescribes recommendations for overcoming these obstacles. Whilst considerable attention has been paid to analysing the environmental impacts of operations in the region, minimal research has been undertaken to identify appropriate policy and educational initiatives for addressing the mounting mercury problem. Findings from recent fieldwork and selected interviews with operators from Guyanese and Surinamese gold mining regions reveal that legislative incapacity, the region's varied industry policy stances, various technological problems, and low environmental awareness on the part of communities are impeding efforts to facilitate improved mercury management at small-scale gold mines in the Guianas. Marked improvements can be achieved, however, if legislation, particularly that pertaining to mercury, is harmonised in the region; educational seminars continue to be held in important mining districts; and additional outlets for disseminating environmental equipment and mercury-free technologies are provided.

Anthraquinone catalysis in the glucose-driven reduction of indigo to leuco-indigo

Anthraquinone immobilised onto the surface of indigo microcrystals enhances the reductive dissolution of indigo to leuco-indigo. Indigo reduction is driven by glucose in aqueous NaOH and a vibrating gold disc electrode is employed to monitor the increasing leuco-indigo concentration with time. Anthraquinone introduces a strong catalytic effect which is explained by invoking a molecular "wedge effect'' during co-intercalation of Na+ and anthraquinone into the layered indigo crystal structure. The glucose-driven indigo reduction, which is in effective in 0.1 M NaOH at 65 degrees C, becomes facile and goes to completion in the presence of anthraquinone catalyst. Electron microscopy of indigo crystals before and after reductive dissolution confirms a delamination mechanism initiated at the edges of the plate-like indigo crystals. Catalysis occurs when the anthraquinone-indigo mixture reaches a molar ratio of 1:400 (at 65 degrees C; corresponding to 3 mu M anthraquinone) with excess of anthraquinone having virtually no effect. A strong temperature effect ( with a composite E-A approximate to 120 kJ mol(-1)) is observed for the reductive dissolution in the presence of anthraquinone. The molar ratio and temperature effects are both consistent with the heterogeneous nature of the anthraquinone catalysis in the aqueous reaction mixture.

Electrochemical determination of plant-derived leuco-indigo after chemical reduction by glucose

Electrochemical determination of redox active dye species is demonstrated in indigo samples contaminated with high levels of organic and inorganic impurities. The use of a hydrodynamic electrode system based on a vibrating probe (250 Hz, 200 mu m lateral amplitude) allows time-independent diffusion controlled signals to be enhanced and reliable concentration data to be obtained under steady state conditions at relatively fast scan rates up to 4 V s-1In this work the indigo content of a complex plant-derived indigo sample (dye content typically 30%) is determined after indigo is reduced by addition of glucose in aqueous 0.2 M NaOH. The soluble leuco-indigo is measured by its oxidation response at a vibrating electrode. The vibrating electrode, which consisted of a laterally vibrating 500 mu m diameter gold disc, is calibrated with Fe(CN)(6) 3-/4- in 0.1 M KCl and employed for indigo determination at 55, 65, and 75 C in 0.2 M NaOH. Determinations of the indigo content of 25 different samples of plant-derived indigo are compared with those obtained by conventional spectrophotometry. This comparison suggests a significant improvement by the electrochemical method, which appears to be less sensitive to impurities.

High activity supported gold catalysts by incipient wetness impregnation

It is generally thought that catalysts produced by incipient wetness impregnation (IW) are very poor for low temperature CO oxidation, and that it is necessary to use methods such as deposition-precipitation (DP) to make high activity materials. The former is true, indeed such IW catalysts are poor, and we present reactor data, XPS and TEM analysis which show that this is due to the very negative effect of the chloride anion involved in the preparation, which results in poisoning and excessive sintering of the Au particles. With the DP method, the chloride is largely removed during the preparation and so poisoning and sintering are avoided. However, we show here that, contrary to previous considerations, high activity catalysts can indeed be prepared by the incipient wetness method, if care is taken to remove the chloride ion during the process. This is achieved by using the double impregnation method (DIM). In this a double impregnation of chloroauric acid and a base are made to precipitate out gold hydroxide within the pores of the catalyst, followed by limited washing. This results in a much more active catalyst, which is active for CO oxidation at ambient temperature. The results for DIM and DP are compared, and it is proposed that the DIM method may represent an environmentally and economically more favorable route to high activity gold catalyst production. (C) 2007 Elsevier B.V. All rights reserved.

Serum proteomic abnormality predating screen detection of ovarian cancer

Ovarian cancer is characterized by vague, non-specific symptoms, advanced stage at diagnosis and poor overall survival. A nested case control study was undertaken on stored serial serum samples from women who developed ovarian cancer and healthy controls (matched for serum processing and storage conditions as well as attributes such as age) in a pilot randomized controlled trial of ovarian cancer screening. The unique feature of this study is that the women were screened for up to 7 years. The serum samples underwent prefractionation using a reversed-phase batch extraction protocol prior to MALDI-TOF MS data acquisition. Our exploratory analysis shows that combining a single MS peak with CA125 allows statistically significant discrimination at the 5% level between cases and controls up to 12 months in advance of the original diagnosis of ovarian cancer. Such combinations work much better than a single peak or CA125 alone. This paper demonstrates that mass spectra from the low molecular weight serum proteome carry information useful for early detection of ovarian cancer. The next step is to identify the specific biomarkers that make early detection possible.

A study of co-precipitated bimetallic gold catalysts for water-gas shift reaction

Synthesis, testing and characterisation of bimetallic gold, Au-M on ceria as catalysts were carried out for low temperature water-gas shift reaction (WGS). Amongst the entire screened catalysts 3 wt% (AU-Pt)/CeO2 displayed the best WGS activity than the monometallic promotors, giving the light-off curve at the lowest temperature in the range 100-300 degrees C. (Au-Pd)/CeO2 also achieved the same activity but at a higher temperature. It was also found that WGS activity was strongly correlated with the surface reducibility which in turn depended on the modified local electronic band structure of promoted ceria. These results clearly suggest that the key role of bimetallic promoter may involve in facilitating the creation of defective reduced surface by exerting its local electronic effect on ceria to form the surface germinal -OH groups in water which act as active sites for enhanced WGS activity. (C) 2008 Elsevier B.V. All rights reserved.

The syntheses, structures and redox properties of phosphine-gold(I) and triruthenium-carbonyl cluster derivatives of tolans

The syntheses of several ethynyl-gold(I) phosphine substituted tolans (1,2-diaryl acetylenes) of general form [Au(C=CC6H4C=CC6H4X)(PPh3)] are described [X = Me (2a), OMe (2b), CO2Me (2c), NO2 (2d), CN (2e)]. These complexes react readily with [Ru-3(CO) 10(mu-dppm)] to give the heterometallic clusters [Ru3(mu-AuPPh3)(mu-eta(1), eta(2)-C2C6H4C, CC6H4X)(CO)(7)(mu-dppm)] (3a-e). The crystallographically determined molecular structures of 2b, 2d, 2e and 3a-e are reported here, that of 2a having been described on a previous occasion. Structural, spectroscopic and electrochemical studies were conducted and have revealed little electronic interaction between the remote substituent and the organometallic end-caps. (C) 2007 Elsevier B. V. All rights reserved.

Low temperature CO oxidation on supported and unsupported gold compounds

Several simple gold compounds and their physical mixtures with TiO2 Were tested for low temperature CO oxidation. No true catalytic activity was found for gold precursors on their own, although both Au2O3 and Au(OH)(3) react well with CO even at room temperature in a non-catalytic manner. Despite that catalytic activity was obtained by physically mixing Au(OH)(3) or Au2O3 with TiO2 and the results further emphasise the importance of a good contact between the gold and the support for good CO oxidation activity. (c) 2005 Published by Elsevier.