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By Andreas Zielonka

To meet the increasing demands of the quality and long term stability of technical systems also the applied materials have to full fill higher standards. This is of special importance where the function of a whole system depends on the reliability of the used materials for example for connector systems in automotive, computer and other electronic equipment?s. In most cases for connector systems electro deposited top layers are applied. To improve the quality of the applied layers new electro deposited systems are developed. One important field of research are the development of composite materials as dispersion coatings and multilayer systems. Multilayers are systems with a high number of single inter-layers of different metals or alloys with the wide chance of the alloy composition. As gold is one of the most important contact material for high quality connector systems it is used as basis for the development of multilayer systems. For the electrodeposition of multilayers two different methods can be applied, the single and the dual plating process. As in the dual plating process two different electrolytes are used, the single plating process allows the formation of multilayers from one electrolyte. In the presented research results cobalt and nickel are used besides gold for the formation of the multilayers. The properties of the layers can be influenced in a wide range by the change of electrolyte composition and the process parameters as current density, current waveform, temperature, hydro-dynamic conditions at the electrode surface and by the number and thickness of the inter layers of the deposited materials. The paper describes the fundamentals of the electro deposition of multilayer systems. For the investigation of the properties of the multilayers different techniques are applied. One of the most important parameter are the thickness of the total layer and of the applied sublayers. The thickness of the sublayers can be varied between a few nanometers up to micrometers. The wear resistance, the contact resistance and the plug-in forces are measured as these parameters are important for the technical application of such layers. For the description of the structure composition and surface properties the sample where also investigated by scanning electron microscopy (SEM), energy dispersive x-ray-analyses (EDX) and glow discharge optical spectroscopy (GDOS). The paper shows that the deposition of gold based multilayers is possible and that the properties of such systems can be varied in a wide range what opens new fields of applications of such materials.

Oct 1, 2003

By Inga Tuzovskaya1i

Three types of gold species were observed for gold-zeolites, prepared by reduction of ionexchanged Au species in a series of zeolites: (i) Au3+cations, (ii) neutral Au0 n or charged Aus+ n clusters suggested to be inside the zeolite channels, (iii) Au nanoparticles with diameter varied from 2 through 20 nm located on the external surface of zeolite microcrystals. Contribution of the gold species formed in zeolite after the ion exchange was found to depend on zeolite type, acidity of zeolite, temperature of reduction and time of storage of the exchanged and reduced Au-containing zeolites. Au3+ ionic species and clusters Aun were formed after the ion-exchange procedure (in contrast with the familiar production of Agn in same zeolites). Gold nanoparticles were observed only as the result of reduction of the Au-exchanged forms at elevated temperatures due to reduction of Au3+ species and aggregation of clusters.

Oct 1, 2003

By Rodolfo Zanella

Au/TiO2 catalysts prepared by deposition-precipitation with NaOH (DPN) (~3 wt%) and urea (DPU) (~8 wt%) were tested in crotonaldehyde hydrogenation at atmospheric pressure. There is no differences in activity (mole.gAu -1 s-1) and selectivity between both DPU and DPN samples for a given activation treatment. This is due to the fact that DPU and DPN samples exhibit similar gold particle size distribution, although the gold loading in DPU is much higher that in DPN. The DPU samples were reduced under H2 at different temperatures (120-500 °C) or under air at 300 °C with various flow rates, to vary the average particle size within a large range, 1.7 to 8.7 nm. The selectivity to crotyl alcohol (selective hydrogenation of the carbonyl bond) is high, 60-70 %, and almost constant as a function of the particle size. The selectivity to crotyl alcohol is also constant for conversions between 10 and 50%. These results suggest that the adsorption mode of crotonaldehyde is of ?3 or ?4-type. In contrast, the TOF depends on the gold particle size, it drastically increases when the gold particle size is ~2 nm. Our results are in agreement with former studies that suggest that the gold atoms involved in the hydrogenation process are those of low coordination.

Oct 1, 2003

By Stephen J. Roberts

Gold catalysts were prepared on co-precipitated, calcined copper oxide - zinc oxide support by an inverse deposition-precipitation method. These catalysts were characterised by X-ray diffraction (XRD) and temperature-programmed reduction (TPR) and studied for CO oxidation activity at various catalyst calcination temperatures. TPR studies of the support material exhibited a double peak and shift to lower temperatures for the reduction of Cux+ to metallic copper, as opposed to the single reduction peak for pure CuO. This phenomenon is possibly caused by an interaction with the zinc oxide. The addition of gold to the support CuOZnO led to a further shift in copper reducibility to lower temperatures. Gold present in the initial uncalcined catalyst as Au3+ was auto-reduced to Au0 under various calcination temperatures. The Au3+ reduction peak was observed to shift to lower temperatures with increasing calcination temperature. The catalytic activity was found to pass through a minimum value with respect to calcination temperature. Catalysts with both gold in entirely the 3+ or metallic oxidation state were found to exhibit high activity. Furthermore, the catalysts were found to decrease in activity with decreasing Au3+ content up to an intermediate calcination temperature, afterwhich the activity increased sharply. Possibly at higher temperatures, a stronger Au-support interaction is formed, leading to a new active site.

Oct 1, 2003

By Susumu Tsubota

Three types of reference gold catalysts, i.e., 3wt%Au/TiO2 (Au-Ti: Type A), and 0.3wt%Au/Fe2O3 on alumina beads (AUS: Type B), and 5wt%Au/Fe2O3 (Au-Fe: Type C), were produced in a test plant scale by Sud-Chemie Catalysts Japan, INC. under the licensing of AIST. To evaluate the validity of the preparation methods and conditions used for the reference samples, elemental analyses by ICP, particle size measurements by TEM, and catalytic activity measurements for the oxidation of CO and H2 over these catalysts were made. Gold catalysts can be prepared in a large scale of ca 400g for the Au-Ti and Au-Fe catalysts, 5 kg for the AUS catalyst with good reproducibility. It was confirmed that they were available for useful as the reference gold catalysts of World Gold Council.

Oct 1, 2003

By Edward R. T. Tiekink

Metal complexes continue to find therapeutic applications for the treatment of a wide variety of human ailments. Amongst these, gold(I) thiolates are used to treat rheutmatoid arthritis but, usually in combination with other treatment or as a last resort. New therapeutic uses of gold, both as gold(I) and gold(III), are being sought, including against cancer, the focus of the present contribution. It will be demonstrated that certain gold(I) complexes show exciting cytotoxicity profiles, rivalling those of cisplatin and standard chemotherapeutic agents. More importantly, anti-tumour activity is demonstrated in vivo, albeit in a mouse model. The presentation will give a brief overview of ?metals in medicine? with a focus on gold and will summarise some recent advances in the development of goldbased anti-tumour agents.

Oct 1, 2003

By Laurence D. Burke

The electrocatalytic behaviour of gold in aqueous media is surprisingly complex and a novel view of gold electrode surfaces is proposed to explain the observed electrochemical responses. The metal surface is considered as a chemically (or redox) modified electrode, with equilibrated, low energy, surface gold atoms functioning as a relatively inert support and low coverage, high energy, protruding gold atoms (or minute clusters of same) functioning as electrocatalytic redox mediators. The protruding atoms are viewed as surface active sites and the complex electrocatalytic behaviour is attributed to the basic instability of the mediators, the diversity (and poor control) of same, and the acid/base (or hydrolysis) behaviour of the oxidized states of the mediators. It is assumed that major advances in the application of gold in the heterogeneous catalysis of gas phase reactions will be accompanied by similar advances in the use of gold in the electrocatalysis area; however, this will require considerable work of both a practical and theoretical nature.

Oct 1, 2003

By Golaleh Riahi

An original method is used to obtain stable nanoparticles of gold-based mono- and bimetallic systems supported on an acidic zeolite. This approach has been applied to PtHY (1wt% Pt) and to bimetallic Pt-AuHY containing 1% of platinum to which is added the amount of gold required to give Au/Pt molar ratios of 20,40,60 and 80%. Metal clusters of Au or Pt-AuHY are formed inside the supercages of the zeolite framework by the thermal reduction of cations by the ligands (en = H2N-CH2-CH2-NH2) under inert gas flow at a temperature depending on the metal. The use of acidic zeolites favours the dispersion of the metal and the thermal stability of the particles. This stability is explained by chemical anchoring of metal clusters by the Brønsted sites of the support. Several techniques have proved that for a molar ratio of 20% metal particles of Pt-AuHY are bimetallic. The segregation of Pt and Au starts for molar ratio =?40%. The catalysts tested on the methylcyclopentane hydroconversion reaction reveal that the addition of gold to platinum leads to an increase in the activity and an improvement in the selectivity for isomerization of the skeleton (cyclohexane and benzene) to the detriment of hydrogenolysis. Similar results were obtained for the dodecane isomerisation to isododecane. These catalysts were also tested in CO, propene and propane oxidation. The activity of fresh catalysts is rather low. It increases after their pretreatment in oxygen or hydrogen atmosphere. In propene oxidation in the reaction mixture O2 ? H2, beside total oxidation of propene to CO2, also propene hydrogenation was observed, particularly at low temperatures. The presence of Au enhances the hydrogenation properties: high selectivities (> 90%) to propane and high propane yields on PtAu HY are observed up to ~150oC, whereas for Pt HY catalyst the selectivity and yield to C3H8 decreases rapidly with the temperature beginning from ~100oC.

Oct 1, 2003

By Masami Nakamoto

Controlled thermolysis of gold(I) thiolate complex, [C14H29(CH3)3N][Au(SC12H25)2], at 180 °C for 5 h under an N2 atmosphere produces novel gold nanoparticles passivated by alkyl groups derived from the precursor complex, the TEM photograph of which shows spherical particles with average diameter 26 nm. Since Brust et al. reported the two-phase reduction of AuCl4 - by NaBH4 to afford monodispersed gold nanoparticles passivated by alkanethiolate ligands (1), plenty of preparative investigations on gold nanoparticles (2,3) and its surface modification (3,4) have appeared, because of their potential applications in microelectronics (5). However, those preparative methods generally involve the reduction of AuCl4 - by reducing agent NaBH4 in the presence of suitable organic stabilizers such as alkanethiol (1-4), phosphane (5), quarternary ammonium salts (6), surfactants (7) or polymers (8). On the other hand, O?Brien et al. recently reported the preparation of organically capped gold nanoparticles at 190 °C, where tri-n-octylphosphine oxide and/or n-octadecylamine are used both as a reaction medium and as a passivating ligand (6), but this procedure also needs NaBH4 as reducing agent. Our strategy of novel preparative method of gold nanoparticles is the combination of reductive elimination of thiolate ligands and simultaneous attachment of organic moiety on the growing nuclei. Gold(I) thiolate complexes with ammonium cations were useful for our preparative method. We now report the controlled thermolysis of gold(I) thiolate complexes, [R(CH3)3N][Au(SC12H25)2] and [R(CH3)3N][Au(SC6H4-p-R?)2] (R= C14H29, C12H25; R?= C8H17, CH3), under an N2 atmosphere, where the powder of gold(I) thiolate complexes completely melts to afford the precursor liquid and then the liquid gradually decomposes. In spite of no use of reducing agent and solvent, reduction reaction is thermochemically induced to afford novel gold nanoparticles passivated by alkyl groups rather than by alkanethiolate ligands. Figure 1a shows a typical transmission electron microscopy (TEM) image of gold nanoparticles prepared by thermolysis of [C14H29(CH3)3N][Au(SC12H25)2] at 180 °C for 5 h, indicating a controlled growth of spherical gold nanoparticles. As shown in Fig. 1b, these spherical gold nanoparticles display the size distribution ranging from 5 to 50 nm. Although the particle size is larger than that of thiol-derivatized gold nanoparticles (less than 5 nm) prepared by NaBH4 reduction (1-3), the aggregation of gold nuclei is smoothly regulated and the growth of core gold is limited to be 26 nm in average diameter in spite of thermal procedure.

Oct 1, 2003

By Toshiharu Teranishi

When we apply the Au nanoparticle superlattices to the future nanooptical and nanoelectronic devices, the control of not only the particle size but also the interparticle spacing and symmetry of superlattice are the essential problems to be overcome. First, we developed a novel synthetic procedure to precisely control the particle size of alkanethiol-protected Au nanoparticles in the range from 1.5 to 9.7 nm by the heat-treatment of the small Au nanoparticles in the solid state. Absorption and nonlinear optical properties of alkanethiol-protected Au nanoparticle superlattices were then elucidated. On the other hand, the hexagonal close-packed (hcp) 2D superlattices of small Au nanoparticles with the interparticle spacings from 1.9 to 3.6 nm were successfully prepared by using newly-synthesized ligand for single electron tunneling devices. Finally, various symmetric superlattices, such as chain (2-fold), quasi-honeycomb (3-fold), square (4-fold), etc., of Au nanoparticles could be produced by making use of interligand interactions or some templates.

Oct 1, 2003

By Fernando Canales

In the last decade a great dealt of attention has been paid to the chemistry of polynuclear gold derivatives with a central heteroatom, not only from the experimental and structural but also from the theoretical standpoint (1). Interesting hypercoordinated species of the type [C(AuPR3)5]+, [C(AuPR3)6]2+, [N(AuPR3)5]2+, [P(AuPR3)5]2+ and [P(AuPR3)6]3+ have been described (2), apart from other complexes with more conventional stoichiometry, and all have in common the presence of gold-gold interactions of ca. 3 Å. Usually, the chemistry of the first row elements of the p-block is known to follow classical rules of bonding, and only in cases of extreme electron-deficiency has the traditional electron count to be reconsidered to account for special types of molecular or solid state structures. Many of these heteroatomcentered complexes are electron-deficient and the gold-gold interactions provide a significant contribution to their stability. The attraction between these closed-shell systems has recently captured the attention in inorganic and organometallic chemistry (1). P. Pyykkö has summarized the available theoretical and experimental evidence of intra- and inter-molecular interactions between heavy metal atoms, such as Au(I) (3). In general, when heavy metals are involved in such interaction, the closed-shell attractions are of metallophilic or van der Waals type, as has been found for d8, d10 coinage-metals, and d10s2 centers. Experimental evidence for the aurophilic Au(I)???Au(I) attraction is available from crystallography, NMR and Raman spectroscopies, and optical spectroscopic measurements of the interaction strength (4). It is manifested in molecular conformations with relatively close Au???Au interactions of ca. 3 Å, whose strength has been estimated at ca. 25-50 kJ/mol (5). These attractions are weaker than most covalent or ionic bonds, but stronger than other van der Waals bonds and comparable in strength to typical hydrogen bonds. The phenomenon cannot be satisfactorily explained by classical theories such as hybridization (3). From a theoretical point of view, the attractions close to equilibrium distances are caused by dispersive interactions together with relativistic effects (6). The attractive contributions are dominated by pair-excitations from the heavy metal, such as gold, strengthened by relativistic effects. In all the cases where there are inter- or intramolecular metal-metal attractions, the correlation effects are essential; if they are omitted, at the Hartree-Fock (HF) level, repulsive interactions are obtained (6). Hence, it is necessary to use at least second-order Møller-Plesset level (MP2) methods for the dispersive forces, which are included in the electronic correlation effects (7).

Oct 1, 2003

By Elma van der Lingen

Gold is considered the most inert of all metallic elements, but the metal can show catalytic activity when prepared by specific techniques. Preparation techniques being used to prepare gold catalysts systems mainly involve precipitation methods incorporating gold compounds or complexes. This paper introduces a totally different method for the preparation of gold-based heterogeneous catalysts that can be used for oxidation and reduction reactions, as well as electrocatalysts. The method involves alloying of gold with a less noble metal, such as aluminium, to form a gold-containing intermetallic precursor. AuAl2 was produced by melting gold and aluminium together in a vacuum arc furnace under a protective atmosphere. The aluminium is then dissolved from the AuAl2 precursor by means of NaOH to produce a highly porous gold structure. The paper also reports on a method of incorporating transition metal oxide(s) with the porous gold to form an active heterogeneous catalyst. Promoter elements can also be melted with AuAl2 to improve catalytic activity. Alloying has the advantage that the promoter element can be in contact on atomic level with the gold. In-situ xray photoelectron spectroscopy (XPS) studies have also been done on the porous gold catalysts to further clarify the CO oxidation mechanism on gold-based catalysts.

Oct 1, 2003

By Aalbert Zwijnenburg

One of problems connected with the use of gold/titania-based catalyst systems is the low yield in propene oxide (up to 2 wt %). It is shown that the low propene oxide yield is due to product inhibition. New options for propene epoxidation with hydrogen and oxygen are discussed. INTRODUCTION The direct gas-phase synthesis of propene oxide (PO), by the use of molecular oxygen, is still aimed for. Agbased catalysis is in principle possible, but selectivity at present is not promising. Highly dispersed gold on titanium containing catalysts show an extraordinary selectivity in the oxidation of propene to the corresponding epoxide (> 99 %), using a combination of H2 and O2 as oxidation mixture [1]. Additional studies of the epoxidation reaction have indicated several drawbacks of the Au/TiO2 catalyst. Firstly, the low conversion (1- 2 %) obtained under typical reaction conditions (atmospheric pressure, 323 - 423 K) cannot be increased by increasing the reaction temperature, because this leads to extensive by-product formation. Secondly, the low efficiency of hydrogen (relatively large amounts of water are formed) is hard to prevent. Finally, significant deactivation of Au/TiO2 catalysts within several hours on stream has been observed. Deactivation can be almost completely prevented by using dispersed TiO2 supports, such as TiO2/SiO2 and Titanium-Silicalite-1 (TS-1) [2]. In recent literature [2,3] a hydroperoxide-like intermediate has been proposed to be responsible for the selective epoxidation. This oxidising species is said to be formed over gold and subsequently used for epoxidation over the Ti-containing support. The support is responsible for the slow desorption of PO. One of the problems for future industrial application might be the low yield in propene oxide. Furthermore, the presence of minor amounts of by-products, not detected on lab-scale catalyst testing, might complicate the separation unit in an industrial process. The reason for the low PO yield over Au/TiO2-based catalysts will be discussed in this paper. Temperature Programmed Desorption (TPD) and micro-flow experiments have been carried out to study PO desorption and catalyst performance, respectively. A catalytic cycle is proposed together with its consequences for the maximum yield in PO. Finally, several process and catalyst options are discussed in view of potential future industrial application.

Oct 1, 2003

By Michael Bowker

Au/TiO2 catalysts were prepared by incipient wetness impregnation and tested for the room temperature photocatalytic reforming of methanol in aqueous solution. These catalysts proved to be more active, on a molar basis, than Pd/TiO2. The dependence on loading of gold was different from that of palladium, showing a double maximum in yield at 0.1 and 2 wt. % with low rate below 0.01% and above 10%. A model is proposed for the reaction involving band gap excitation of titania electrons which are used to oxidise the methanol via adsorbed CO. With palladium, photoreforming of CO and water can be achieved, but this is much less effective on gold, presumably due to the much weaker bonding of CO on Au.

Oct 1, 2003

By Peter J. Barnard

Mitochondria play a key role in the regulation of apoptosis (cell death) and in diseases characterised by abnormal apoptotic responses such as cancer. Mitochondrial membrane permeabilisation (MMP), regulated by the mitochondrial permeability transition pore complex, is widely accepted as being central to the process of cell death. As a result there has been considerable recent interest in targeting mitochondrial cell death pathways in the development of new chemotherapeutic agents.(1) There is potential to overcome the two overriding problems in cancer chemotherapy?the common occurrence of drug-resistant tumour cells and the lack of selectivity of cancer drugs in differentiating between tumour cells and normal tissues. Significantly, carcinoma cells have an elevated mitochondrial membrane potential relative to normal cells and lipophilic cations are concentrated within mitochondria in response to mitochondrial membrane potentials. There is potential for the selective targeting to tumour cells with compounds having optimal lipophilic-hydrophilic character. Research stemming from the early 1980?s points to two distinct classes of Au(I) phosphine antitumour agents where an antimitochondrial mode of action has been implicated: (i) neutral linear two-coordinate Au(I) complexes such as triethylphosphinegold(I) chloride and the tetraacetylthioglucose gold(I) phosphine complex, Auranofin; (ii) cationic tetrahedral bis-chelated Au(I) phosphine complexes related to [Au(dppe)2]+.(2) Recently it has been reported that Auranofin, at submicromolar concentrations, induces MMP observed as mitochondrial swelling and dissipation of membrane potential.(3, 4) Both events are completely inhibited by cyclosporin-A, the specific inhibitor of MMP. The permeability changes were shown to occur at concentrations associated with the selective inhibition of mitochondrial thioredoxin reductase.(3) Auranofin is a potent and specific inhibitor of this enzyme due to Au(I) binding to the active-site selenol group.(5) The redox state of mitochondrial thiols may be critical in the control of MMP.(3) In general, swelling is stimulated by thiol blocking or oxidising agents and is prevented by thiol reducing agents.(1) Mitochondrial thioredoxin reductase may play an import role in the redox control of the permeability of mitochondrial membranes.(3) Our interest is in investigating the antitumour potential of Au(I) phosphine compounds using a number of different approaches. In recent work we have evaluated a series of hydrophilic analogs of [Au(dppe)2]+ containing pyridylphosphine ligands which have demonstrated greater tumour selectivity than the parent compound. To investigate the possible antimitochondrial mode of action we are studying the effect of [Au(dppe)2]+ and related compounds on isolated rat liver mitochondria. To assess whether the lipophiliccationic nature of the compounds determines the antitumour activity, we have synthesized a series of novel Au(I) complexes based on heterocyclic carbene rather than phosphine ligands. The similar chemistry and structural features of the two classes of complexes allow us to assess whether the phosphine ligands are essential for the antitumour properties.

Oct 1, 2003

By Ronald L. Bruening

IBC has developed a cost effective MRT process for the selective extraction and recovery of gold, copper, and a mixture of other base metals from mine leach cyanide solutions. This is a two-stage system in which the gold is first recovered selectively as a high purity salt. The copper is then recovered separately as a sulfate salt. The other base metals are then collected as a cyano anion concentrate. Three different SuperLig® materials are used. The first stage can be used alone on gold leach solutions where copper and other base metals are not a problem. The two or three stage system is used when the base metals build up in the leach solution, resulting in increased costs. The cyanide or cyanide/cyano anion concentrate can be recycled back to the leach solution until the build-up of other salts, etc. becomes too high, or this too can be controlled with a percentage bleed stream.

Oct 1, 2003

By K. Wongpreedee

Recovery and recrystallization of Au wire can degrade strength and alter conductivity properties during exposure to elevated temperature. Au Deformation Processed Metal Metal Composites (Au DMMC's) are being developed for electronic applications requiring high conductivity and high strength. This paper discusses the relationships between microstructure, strength, and resistivity of Au DMMC's. It also presents the results of a recent study on the elevated temperature stability of Au DMMC's of several compositions. Au-7 vol %Ag, Au-14 vol %Ag, and Au-vol 7%Pt DMMC samples were prepared by a powder metallurgy technique. All specimens were processed into wire by extrusion, swaging, and drawing. The smallest final diameter of these wires was 120 ?m. Thermal stability was analyzed by electrical resistivity measurements to determine the relation between transformation rates and time at elevated temperature. The extensive deformation used to produce these composites reshaped the initially equi-axed powder into filaments that are 30 to 100 nm in diameter and 16 to 180 mm in length. The small filament diameter confers high strength on the composite. The high conductivity can be explained by electrons flowing parallel to the filamentary microstructure aligned with the wire axis. Using the Avrami and Arrhenius equation relationships, it is possible to predict the times and temperatures needed to achieve various degrees of homogenization. The Au DMMC's were found to have good thermal stability compared to conventional coldworked Au interconnection wires. Although these composites will revert to solid solutions if exposed to high temperatures for prolonged time periods, their relative stability is sufficient to allow them to maintain their twophase microstructure during the anticipated lifetime temperature profiles of many products.

Oct 1, 2003

By Chih-Huey Lin

The Au/?-Al2O3 catalyst prepared by AuCl3 impregnation is subjected to the influence of residual chlorine after an oven drying. A post-impregnation NH4OH treatment was able to eliminate chlorine, and to reduce the cluster size of Au moiety. However, the CO oxidation activity was not increased by this post-impregnation NH4OH treatment. This suggests that certain metal-support interaction (MSI) is the determining factor for the activity of Au catalysts. Thermal treatment under H2, O2 or He was attempted to increase MSI of the prepared catalyst with or without the post-impregnation NH4OH treatment. No significant activity enhancement was found but the TPD analysis suggests that a H2 treatment has a higher chance to induce MSI.

Oct 1, 2003

By Simon P. Fricker

Gold drugs have been used for the treatment of rheumatoid arthritis since the mid 20th century as disease-modifying antirheumatic drugs (DMARD) class. Methotrexate is often the preferred DMARD, and with the advent of new therapies gold drugs are now used infrequently. Since the introduction of auranofin in 1985 there has been no new clinically approved gold drug. In spite of this apparent lack of progress there has been a great deal of interest in the use of gold compounds for cancer therapy and early promising indications were achieved with a gold phosphine complex [Au(dppe)2]Cl. This compound was not entered for clinical trials, however, due to problems with cardiotoxicity highlighted during pre-clinical toxicology studies. Gold(III) is isoelectronic (d8) with platinum(II) and likewise forms square planar complexes. It is therefore tempting to speculate that such complexes would have similar antitumor activity to cisplatin. In order to stabilise the gold(III) oxidation cycloaurated complexes were synthesised with a single mononegative bidentate ligand, damp, (2-[(dimethylamino)methyl]phenyl), and two monodentate anionic ligands e.g. Cl or acetate. The damp ligand forms part of a five-membered chelate ring. The monodentate ligands are readily hydrolysed and are available for substitution. These compounds had limited anti-tumor activity in in vivo against human tumor xenografts. Mechanistic studies indicated that these compounds had a different mechanism of action to cisplatin. An alternative molecular target for these compounds is biologically important thiol-containing molecules such as the cysteine protease cathepsin B. Modifications were made to the Au(III) damp structure to give compounds with a six-membered chelate ring. These compounds were shown to be inhibitors of cathepsin B. Compounds were also tested for cytotoxicity against a panel of human tumor cell lines. Three compounds were selected for further evaluation against a human colon tumor xenograft. The compounds showed modest anti-tumor activity but with no marked improvement over the parent Au(III)damp complexes. Initial indications are that Au(III) compounds targeted against disease-specific thiol-containing biological molecules have potential as drugs, particularly for cancer. However, further work is required to produce a target-specific drug with a suitable pharmacological activity and toxicity profile.

Oct 1, 2003

By Rodolfo Zanella

Au/TiO2 catalysts were prepared by deposition-precipitation using NaOH (DPN) (~3 wt % Au) and urea (DPU) (~8 wt % Au), and calcined at various temperatures between 100 and 400 °C. They were characterized by UV-Visible, XANES, EXAFS and TEM. Their activity were tested in the reaction of CO oxidation at 5°C. After preparation, the gold species are in the oxidic state III. They begin to transform into metallic gold under air at ~100 °C for DPN and ~150 °C for DPU. At 200 °C, all the gold is metallic for the two preparation methods. The particle size increases from 1.5 to 3.5 nm with the calcination temperature. The catalytic activity for CO oxidation increases with the percentage of metallic gold, and it is maximum at 200°C for both types of samples. The activities (per mole of Au) are the same for the two types of catalysts. At higher temperatures, the catalytic activity drops. The decrease of activity is mainly due to a change of particle shape with the calcination temperature rather than to the increase of the particle size. At a calcination temperature of 200°C, the particles present small facets with rounded parts, and their outer surface contains a large proportion of low coordinated sites (steps and corners) while at high temperature of calcination, they are truncated octahedra with smooth facets.

Oct 1, 2003