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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 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

By Mari Yamamoto

Controlled thermolysis of gold(I) complex, [Au(C13H27COO)(PPh3)], at 180 °C for 5 h under an N2 atmosphere affords the new type of monodispersed spherical gold nanoparticles capped by myristate and a small amount of PPh3 ligands (average diameter 23±1.5 nm), in spite of no use of solvent, reducing agent and stabilizer. Much attention has been paid to the preparation and structure determination of transition metal nanoparticles, because of their widespread use in technological applications.1 In general, the chemical reduction of metal salts and organometallic complexes2 by the use of reducing agent is carried out to prepare gold nanoparticles. In some cases, a large amount of solvent and stabilizers such as surfactants,3 polymers4 and ligands5 are used to prevent agglomeration of particles and control the particle size. For instance, Brust et al. reported a two-phase reduction of AuCl4 - by NaBH4 in the presence of dodecanethiol as stabilizer to prepare gold nanoparticles.6 On the other hand, O?Brien et al. recently reported an one-phase preparation of gold nanoparticles by the reduction of AuCl4 - by NaBH4 in the mixture of tri-n-octylphosphine oxide and octadecylamine which act as both solvent and stabilizer, but this procedure also needs reducing agent.7

Oct 1, 2003

By Hua-Zhong Yu

Gold is one of the most widely used substrate materials for self-assembly. Self-assembled monolayers (SAMs) prepared from alkanethiols and their derivatives on gold are the most reliable and well-studied systems to date, which have attracted much attention because of interest in two-dimensional molecular assemblies, and of their potential applications in molecular devices, sensors, and functionalized interfaces. Gold electrodes are also very important in microelectronics and electroanalytical chemistry. This work reports the characterization of a new type of gold substrates for self-assembly. The gold substrates are constructed from recordable compact disks (R-CDs) with simple and straightforward wet-chemical treatment, and can be made at desired sizes and shapes that satisfy different experimental needs. In particular, an easy, inexpensive, and reproducible method to prepare self-assembled monolayers (SAMs) on CD-R gold substrates after removing the protective polymer films with concentrated nitric acid was described.

Oct 1, 2003

By Kenji Koga

In order to derive the population distribution of gold nanoparticle morphologies as a function of size, highresolution electron microscopic (HREM) observations and structural analyses were done for over 4000 particles (3-18 nm) grown by an inert gas aggregation (IGA) source using helium. To obtain structural features threedimensionally and not to skip high-contrast images, twenty photos were taken for each particle by changing tilting angle of a specimen holder in combination with the through-focus procedure. For the reliable structural determinations, HREM images and their tilting sequences were directly compared with multislice-simulation results for icosahedral, decahedral and face-centered cubic morphologies, and finally the population distribution of each morphology was obtained as a function of size. In the present sample, icosahedral particles were dominantly populated over the whole observed size range and decahedral particles with non-spherical truncated bi-pyramid shape were secondly dominant. Even though a large number of sampling has been done, few crystalline particles were observed.

Oct 1, 2003

By Matthew S. Hall

Gold/iron oxide catalysts have been prepared and their catalytic performance evaluated for low temperature CO oxidation. The method and temperature used to dry the sample has a significant effect on their catalytic activity. Analysis by TEM revealed the catalysts contained Au particles, although catalysts with high and low activity did not always differ in their microstructure as evidenced by TEM. Catalysts were characterised using XPS and the difference between the Au(4d) and C(1s) binding energies measured; in general the greater the difference, the higher the catalytic activity of the material.

Oct 1, 2003

By Anna Maria Venezia

Bimetallic Au-Pd catalysts supported on amorphous silica-alumina (ASA) with vary amount of alumina (0, 8, 14, 28 and 100%) were prepared by the simultaneous reduction of palladium and gold precursors by ethanol in the presence of the polyvinylpyrrolidone (PVP). X-ray diffraction and X-ray photoelectron spectroscopy analyses indicated formation of alloyed Au-Pd particles. Ammonia temperature programmed desorption measurements were performed to monitor the acid strength and the amount of acid sites on the catalysts after their reduction with 10%H2/Ar at 573 K for 1h. The effect of the support acidity on the catalytic activity was investigated in the simultaneous hydrogenation (HYD) of toluene (T) and naphthalene (NP) in the presence of dibenzothiophene (DBT). Coke formation was also determined. Under the selected conditions (P = 5.0 MPa, T = 523 K, WHSV = 41.2 h-1), all the catalysts were resistant to poisoning with 113 ppm of S (as DBT). The hydrogenation activity of toluene and the HDS activity of DBT were found to correlate with the concentration of the medium strength acid sites. The enhancement of the HYD activity and the S- tolerance was related to modifications of the electronic properties of the metal atom upon interaction with the Brönsted acid sites and upon intermetallic interaction.

Oct 1, 2003

By Gary Pattrick

A new class of spongy Au catalysts is studied for the selective catalytic reduction of NOx by propene under leanburn conditions. The spongy catalyst is an unsupported powdered Au that consists of micrometer particles (~5 microns) that have nanometer scale (~10 nm) internal skeletal structures. The effects of alloying 1 ? 50 atom % platinum group metals (M= Pt, Pd, Rh) and 5 wt% first row transition metals (M = Ti, Mn, Fe, Co) were studied. Even low additions of PGMs (1 at.%) cause significant shifts to lower temperature regions of activity and the largest shift is obtained for Rh. For Rh this is interpreted as a strong synergistic interaction between Rh and Au. Possibly related to the Rh effect, Co is the only other metal studied that lowers the temperature of NOx reduction. The other first row transition metals inhibit the reduction reaction.

Oct 1, 2003

By Jolanta Olkowska-Oetzel

Reactions of gold?phosphino complexes [(AuX)(PR3)] (X= Cl, Br, I; R = organic rest) with Se(SiMe3)2 lead to the formation of gold complexes with chalcogenide bridges. The reaction of the complex Ph3PAuCl and tBuSe(SiMe3) gives the cluster [Au5Se2(PPh3)4]Cl 1. The in situ preparation of the complex [(AuCl)2dpph] (dpph = Ph2P(CH2)6PPh2) by reaction of dpph with Me2SAuCl, and subsequent reaction with Se(SiMe3)2 leads to the formation of [(Au3Se)2(dpph)3]Cl2 2. Reactions of the gold(I) complex [(AuCl)2dpppe], (dpppe = Ph2P(CH2)5PPh2) with Se(SiMe3)2 and InCl3 in different molar ratios lead to the formation of [Au10Se4(dpppe)4]InCl5 3 and [Au4(SeInCl3)2(dpppe)2] 4. The reaction of [(AuCl)2dpph] with Te(SiMe3)2 and GaCl3 produces the isostructural cluster compound [Au4(TeGaCl3)2(dpph)2] 5. From the reaction of Se(SiMe3)2 with [(AuCl)2dppe] (dppe = Ph2P(CH2)2PPh2) and InCl3 [Au8Se4In(dppe)4](InCl4)3 6 can be isolated. The structures of 1 - 6 were determined by X?ray diffraction.

Oct 1, 2003

By Fabian Mohr

The methyl substituted binuclear cyclometallated gold(I) complexes [Au2(?-n-MeC6H3PPh2)2] [n = 4, 5 and 6] all undergo oxidative addition reactions with halogens and, in the case of the 4- and 5-methyl substituted analogues, with dibenzoyl peroxide to give metal-metal bonded digold(II) complexes [Au2X2(?-C6H3-n-MePPh2)2]. The 4- and 5-methyl substituted digold(II) compounds on warming or exposure to light undergo carbon-carbon coupling reactions to give gold(I) complexes containing the corresponding 2,2'-n,n'-biphenylyldiphenylphosphines. The 6- methyl substituted digold(II) complexes rapidly isomerise above ca. -20° C to binuclear heterovalent gold(I)/gold(III) compounds [XAu(?-2-Ph2PC6H3-6-Me)AuX{?2-(6-MeC6H3-2-PPh2)}], containing a fourmembered cyclometallated ring on a gold(III) centre. Surprisingly, no carbon-carbon coupling could be induced for any of the 6-methyl substituted compounds, even under forcing conditions. This difference in reactivity of the 6- methyl derivative, compared to that of the 5-methyl and unsubstituted analogues was studied by ab initio calculations using a series of model compounds. The results are in excellent agreement with the experimental findings and suggest that the key-step in the C-C coupling reaction is the partial opening of the Au(III)-P bond in one of the transition states. In the 6-methyl system this transition state is energetically inaccessible and hence no C-C coupling occurs.

Oct 1, 2003

By Gaby Steinbach

A novel synthesis is described for the preparation of supported gold catalysts for low-temperature CO oxidation. The novel route is a variation of the inverse co-precipitation method and requires amphoteric metal hydroxides, with zinc and aluminium hydroxides chosen. Catalysts were prepared by inverse co-precipitation (ICPa) and by the novel route (ICPb) and tested for CO oxidation at 60ºC. Preliminary results showed the novel route to be superior to ICPa; the catalysts prepared by ICPb showed higher catalytic activities. The effect on catalytic activity of parameters such as pH, calcination temperature, washing of precursor and calcined catalysts and ageing was investigated. A preparation pH of 9 and a Zn to Al mass ratio of 3 proved to be optimal. It was possible to remove residual chloride by washing thereby enhancing catalyst performance. Ageing and Mg citrate addition were also shown to improve catalyst performance. Characterization of the catalysts revealed that better activities were obtained when the support was more crystalline and had a higher surface area. The presence of carbonate-containing species in the support decreased catalytic activity. 197Au Mössbauer Spectroscopy revealed the presence of Au3+ when catalysts were heat-treated at temperatures of 200ºC and below. Catalysts calcined at 400º had 75% of the gold present as Au0, with the remaining gold present as Au3+.

Oct 1, 2003

By József L. Margitfalvi

Different Au/MgO catalysts modified with Mn, and Fe were prepared by precipitation-deposition. The catalysts were characterized by XRD, FTIR, Temperature Programmed Reduction (TPR) and CO chemisorption and were tested in CO oxidation in the temperature range of 243-523 K. The catalytic tests using both Temperature Programmed Oxidation (TPO) technique and time on stream (TOS) experiments revealed the high activity of catalysts prepared. In TPO experiments the modification by Mn significantly increased the activity above 300 K, however in the subambient temperature range the activity decreased considerably. Catalysts modified by iron did not show any decrease in the activity below 300 K, while the activity at high temperature increased significantly. Catalysts modified by Mn, Fe showed higher activity, selectivity and stability in preferential CO oxidation, carried out in the presence of hydrogen than the unmodified Au/MgO catalysts. Results of in situ FTIR spectroscopy on both the base Au/MgO and the iron modified catalyst unambiguously revealed the formation of ionic gold in the presence of CO/O2 mixture. The formation of this species was strongly hindered in catalyst modified by manganese. Results obtained strongly support the need for the formation of "metal ion - metal nanocluster" ensemble sites. These sites are involved in the activation of the CO molecule prior to its reaction with atomic oxygen. It is suggested that at subambient temperature these ensemble sites contain mainly ionic forms of gold, while at higher temperature iron or manganese ions are involved in CO activation.

Oct 1, 2003

By Lizelle Glaner

An investigation was carried out by Mintek to investigate the influence of additions of gold to ?Fecraloy?, alloys based on Fe-Cr-Al. The aim was to try and improve the oxidation resistance of the ?Fecraloy? alloys at elevated temperatures over extended periods of time. The ?Fecraloy? alloys are very oxidation resistant alloys already employed in industry as substrates for metallic catalysts in auto-catalyst systems for high performance cars. Since their life and durability is limited by the slow, but steady, oxidation of the substrates, any change in the growth or stability of the oxides could be an improvement.

Oct 1, 2003

By Peter Claus

In the last years, supported gold catalysts with particle sizes smaller than 10 nm have attracted a lot of attention. While gold bulk metal is rather inert in chemical reactions and, thus, is of low interest for catalysis, highly dispersed gold particles supported on oxides as TiO2 or ZrO2 show surprisingly high activities in some reactions important for the chemical industry. The oxidation of carbon monoxide at low temperatures is mainly used as model reaction to study the unusual properties of gold catalysts [1]. On the other hand, to evaluate the catalytic potential of gold, other chemical reactions which allow to control also the selectivity have to be considered. The selective hydrogenation of ???-unsaturated aldehydes to allylic alcohols is of both commercial relevance (e.g. in fine chemical and pharmaceutical intermediate production) and specific scientific interest [2]. Note that thermodynamics favors hydrogenation of the C=C over the C=O group (stronger negative free reaction enthalpy of 35 kJ/mol), and for kinetic reasons the C=C bond is more reactive than the C=O group. Thus, in the presence of most of the conventional hydrogenation catalysts, based on Pt, Rh or Pd, -unsaturated aldehydes such as acrolein and crotonaldehyde are hydrogenated predominantly to the saturated aldehydes and only to a minor extent to unsaturated alcohols. Therefore, it is desirable to find catalysts which are able to control the intramolecular selectivity by hydrogenation preferentially the C=O group while keeping the olefinic double bond intact (Fig. 1).

Oct 1, 2003

By V. Caps

Gold has been often used as an alloying component in order to increase or modify the catalytic properties of an active metal. For example, in the hydroconversion of methylcyclopentane, Riahi et al [1] shown that the addition of gold to palladium or platinum enhances the activity which becomes greater than that of the pure metals whereas the selectivity towards products resulting from ring expansion increases. Molenbroek et al [2] presented a detailed study on Ni-Au catalysts which exhibit activity for steam reforming and have been proved to be more resistant toward carbon formation than the pure Ni catalysts. Blocking of highly reactive Ni edge and kink sites by Au atoms is assumed to be the reason for the increased robustness of the Ni-Au catalyst. Nevertheless, the own catalytic properties of pure gold have been almost ignored up to the pioneering work of Haruta et al [3] which demonstrates the high activity of gold for CO oxidation at low temperatures. Other reactions such as WGS reaction, propylene epoxidation or benzene total oxidation have then been shown to be catalyzed by gold [4]. This discovery induced the publication of papers devoted to analyze the different factors controlling the activity of gold catalysts. Among them the most relevant appears to be the gold particle size, the nature of the support [5] and the preparation methods [6]. Clearly distinguish between support and size effect is not straightforward. Indeed, the calcination step often needed to synthesize supported catalysts on different supports, leads to different particle sizes showing that particle size and support are interdependent. To circumvent this difficulty, Au-based supported catalysts have been synthesized by using laser vaporization and low energy cluster beam deposition. The as prepared catalysts have then been characterized and tested in CO oxidation reaction.

Oct 1, 2003

By Michael Hopp

The beginning of the electroforming technology dates itself on the beginning of the industrial revolution 1800 to 1820 approximately. Basis was the existence of electricity in order to be able to drive the electro-form-process. With the development of the electroforming, big names of the science-history, like Michael Faraday (1791? 1867), Sir Humphry Davy (1778?1829), Max Schlöter (1878?1946), Werner von Siemens (1816?1892), and many others. Already about 1840, the first monograph originated to electroforming (38). While in the first years the electro-forming most extensive only to the coating of art - or other usefulness-objects was used. At the beginning of the 20th century the formation of objects from pure metals became more and more, later also from alloys to application. One of the first bigger electroforming factory, the ?Württembergische Metallwarenfabrik? was working 1894 in Geislingen / Steige, Germany. In the industrial application, the electroforming-technology is to be imagined away for miscellaneous coatingtasks and the form-body-preparation no longer today (18). A little bit confusing is the german name ?galvano-technology?. It based on the Italian physiologist and naturalist Luigi Galvani (1737 ? 1798). This technically seen is however wrong, right, the name is electroforming. The physical bases were founded mainly by Michael Faraday and Sir Humphry Davy.

Oct 1, 2003

By Shinji Shirakawa

The gold wire bonding technology is widely used for electrically connecting aluminum pads on IC devices to external terminal of semiconductor. In 1960?s, the tensile strength of gold bonding wire was about 100 MPa only. However, recently the wire with 300 MPa in strength has been developed. Since the gold bonding wire was started to use for IC package in early 1960?, the many types of gold bonding wire has been developing continuously in order to meet market?s needs, such as high density, small size and thin type of IC packages. Moreover, electronic equipments were used in automobile applications and also demanded good reliability under severe temperature environment. Thus Au-Pd alloy wire has been introduced instead of the wire with 4N(99.99wt%) purity gold to provide excellent reliability in Au-Al bond interface. The phenomena at Au-Al interface in the high temperature storage have been already explained by several studies as follows. There are five phases of inter metallic compound (IMC) between gold and aluminum. Just after bond gold ball on aluminum pad, Au5Al2 phase was formed and occupied almost all of IMC area. During high temperature storage test, Au5Al2 phase transformed to Au4Al phase, then this phase was corroded by Bromide (Br) ion that was isolated from molding resin. Thus the reliability between Au and Al degraded. In case of Au-Pd alloy wire, the concentrated palladium phase (Au-Pd-Al) was formed at the interface between Au alloy ball and Al pad. The Au-Pd-Al phase prevented from transforming between Au and Al, therefore Au5Al2 phase was hard to transform to Au4Al phase. Consequently the reliability at the interface between Au alloy ball and Al pad was less degradation. However, in recent study using several advanced analysis technique, Au4Al phase was found at the interface between Au alloy ball and Al pad same as the case of conventional gold wire (4N purity gold bonding wire). It was suggested that the formation of concentrated palladium phase (Au-Pd-Al) related the excellent reliability at ball bonding process.

Oct 1, 2003

By Donka H. Andreeva

Gold catalysts based on different supports, titania, zirconia, ceria and mesoporous titania and zirconia, nonpromoted and promoted by vanadia in the reaction of complete benzene oxidation have been studied. XRD, HRTEM, TPR, Raman and ESR spectroscopy were applied for the characterization of the catalysts. The influence of gold on the reduction behavior, state and structure of vanadia on the surface was studied, as well as the role of supports nature on the properties and catalytic activity. A strong synergistic effect between gold and vanadia was observed for the all studied catalysts with an exception of the catalysts supported on mesoporous zirconia. In the last case the catalysts containing gold and gold-vanadia exhibit high and equal catalytic activity. The catalysts on ceria show highest and stable catalytic activity in the studied reaction among the all studied catalysts.

Oct 1, 2003