Base-free, one-pot chemocatalytic conversion of glycerol to methyl lactate using supported gold catalysts

We report an efficient one-pot conversion of glycerol (GLY) to methyl lactate (MLACT) in methanol in good yields (73 % at 95 % GLY conversion) by using Au nanoparticles on commercially available ultra-stable zeolite-Y (USY) as the catalyst (160 °C, air, 47 bar pressure, 0.25 M GLY, GLY-to-Au mol ratio of 1407, 10 h). The best results were obtained with zeolite USY-600, a catalyst that has both Lewis and Brønsted sites. This methodology provides a direct chemo-catalytic route for the synthesis of MLACT from GLY. MLACT is stable under the reaction conditions, and the Au/USY catalyst was recycled without a decrease in the activity and selectivity. From glycerol to green building blocks and solvents! An efficient, base-free conversion of glycerol to methyl lactate in methanol is reported, achieving good yields (73 % at 95 % glycerol conversion) using Au/ultra-stable zeolite-Y (USY) as the catalyst and environmentally benign oxygen as the oxidant by combining two separate reaction steps efficiently in a one pot procedure. The Au/USY catalyst can be recycled without a decrease in the activity and selectivity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Elastic modulus study of gold thin film for use as an actuated membrane in a superconductive radio frequency (RF) microelectromechanical (MEM) switch

The objective of this research was to find Young's elastic modulus for thin gold films at room and cryogenic temperatures based on the flexional model which has not been previously attempted. Electrical Sonnet simulations and numerical methods using Abacus for the mechanical responses were employed for this purpose. A RF MEM shunt switch was designed and a fabrication process developed in house. The switch is composed of a superconducting YBa2 Cu3O7 coplanar waveguide structure with an Au bridge membrane suspended above an area of the center conductor covered with BaTiO3 dielectric. The Au membrane is actuated by the electrostatic attractive force acting between the transmission line and the membrane when voltage is applied. The value of the actuation force will greatly depend on the switch pull-down voltage and on the geometry and mechanical properties of the bridge material. Results show that the elastic modulus for Au thin film can be 484 times higher at cryogenic temperature than it is at room temperature. ^

Temperature dependence and characterization of gold thin film actuated membranes for radio frequency microelectromechanical switches

Over the last 10 years, the development and the understanding of the mechanical properties of thin film material have been essential for improving the reliability and lifetime in operation of microelectromechanical systems (MEMS). Although the properties of a bulk material might be well characterized, thin-film properties are considerably different from those of the bulk and it cannot be assumed that mechanical properties measured using bulk specimens will apply to the same materials when used as a thin film in MEMS. For many microelectronic thin films, the material properties depend strongly on the details of the deposition process and the growth conditions on its substrate. ^ The purpose of this dissertation is to determine the temperature dependence of a gold thin film membrane on the pull down voltage of a MEMS switch as the temperature is varied from room temperature (300 K) to cryogenic temperature (10 K). For this purpose, an RF MEMS shunt switch was designed and fabricated. The switch is composed of a gold coplanar waveguide structure with a gold bridge membrane suspended above an area of the center conductor which is covered by a dielectric (BaTiO3). The gold membrane is actuated by an electrostatic force acting between the transmission line and the membrane when voltage is applied. ^ Material characterization of the gold evaporated thin film membrane was obtained via AFM, SEM, TEM and X-ray diffraction analyses. A mathematical relation was used to estimate the pull down voltage of the switch at cryogenic temperature and results showed that the mathematical theory match the experimental values of the tested MEMS switches. ^

Vacuum brazing of alumina ceramic to titanium for biomedical implants using pure gold as the filler metal

One of the many promising applications of metal/ceramic joining is in biomedical implantable devices. This work is focused on vacuum brazing of C.P titanium to 96% alumina ceramic using pure gold as the filler metal. A novel method of brazing is developed where resistance heating of C.P titanium is done inside a thermal evaporator using a Ta heating electrode. The design of electrode is optimized using Ansys resistive heating simulations. The materials chosen in this study are biocompatible and have prior history in implantable devices approved by FDA. This research is part of Boston Retinal implant project to make a biocompatible implantable device (www.bostonretina.org). ^ Pure gold braze has been used in the construction of single terminal feedthrough in low density hermetic packages utilizing a single platinum pin brazed to an alumina or sapphire ceramic donut (brazed to a titanium case or ferrule for many years in implantable pacemakers. Pure gold (99.99%) brazing of 96% alumina ceramic with CP titanium has been performed and evaluated in this dissertation. Brazing has been done by using electrical resistance heating. The 96% alumina ceramic disk was manufactured by high temperature cofired ceramic (HTCC) processing while the Ti ferrule and gold performs were purchased from outside. Hermetic joints having leak rate of the order of 1.6 × 10-8 atm-cc/ sec on a helium leak detector were measured. ^ Alumina ceramics made by HTCC processing were centreless grounded utilizing 800 grit diamond wheel to provide a smooth surface for sputtering of a thin film of Nb. Since pure alumina demonstrates no adhesion or wetting to gold, an adhesion layer must be used on the alumina surface. Niobium (Nb), Tantalum (Ta) and Tungsten (W) were chosen for evaluation since all are refractory (less dissolution into molten gold), all form stable oxides (necessary for adhesion to alumina) and all are readily thin film deposited as metals. Wetting studies are also performed to determine the wetting angle of pure gold to Ti, Ta, Nb and W substrates. Nano tribological scratch testing of thin film of Nb (which demonstrated the best wetting properties towards gold) on polished 96% alumina ceramic is performed to determine the adhesion strength of thin film to the substrate. The wetting studies also determined the thickness of the intermetallic compounds layers formed between Ti and gold, reaction microstructure and the dissolution of the metal into the molten gold.^

A gold sol particle immunoassay for measurement of von willebrand factor using the CA-6000 analyzer

The diagnosis of Von Willebrand's disease (VWD) may sometimes be difficult because of the variability of the results obtained over time in individuals. Moreover, blood group, age, pregnancy and inflammatory stimuli influence the level of Von Willebrand Factor (VWF). The purpose of this thesis was to screen and characterize antibodies to Von Willebrand factor and to evaluate the most promising ones in a gold- Sol assay for VWF on the CA-6000 analyzer. Seven different lots of Anti-VWF antibodies, 3 polyclonal and 4 monoclonal Ab's were screened and evaluated. Two of these antibodies (Sunol R01358 and MAVWF-AP) were selected for preparation of a Gold coated antibody solution. The preliminary testing of these gold coated antibodies on CA-6000 Analyzer showed no immunoreactivity toward VWF for both individual and pooled plasma (from normal healthy donors). Although measurement of VWF for normal plasma with this technique was not demonstrated, these data will be valuable for future work on the design of sensitive and accurate automated sol Gold Immunoassays for the diagnosis of VWD.

Elastic modulus study of gold thin film for use as an actuated membrane in a superconductive radio frequency (RF) MicroElectroMechanical (MEM) switch

The objective of this research was to find Young's elastic modulus for thin gold films at room and cryogenic temperatures based on the flexional model which has not been previously attempted. Electrical Sonnet simulations and numerical methods using Abacus for the mechanical responses were employed for this purpose. A RF MEM shunt switch was designed and a fabrication process developed in house. The switch is composed of a superconducting YBa2Cu3O7 coplanar waveguide structure with an Au bridge membrane suspended above an area of the center conductor covered with BaTiO3 dielectric. The Au membrane is actuated by the electrostatic attractive force acting between the transmission line and the membrane when voltage is applied. The value of the actuation force will greatly depend on the switch pull-down voltage and on the geometry and mechanical properties of the bridge material. Results show that the elastic modulus for Au thin film can be 484 times higher at cryogenic temperature than it is at room temperature.

Selective gas phase hydrogenation of p-nitrobenzonitrile to p-aminobenzonitrile over zirconia supported gold

We acknowledge the contribution of Dr. N. Perret to this work. EPSRC support for free access to the TEM/SEM facility at the University of St. Andrews and financial support to Dr. X. Wang and Y. Hao through the Overseas Research Students Award Scheme (ORSAS) are also acknowledged.

Effect of support redox character on catalytic performance in the gas phase hydrogenation of benzaldehyde and nitrobenzene over supported gold

Peer reviewed

1960 Olympic three gold medal winner Wilma Rudolph with 14 year old daughter Djuana

General note: Title and date provided by Bettye Lane.

1960 gold medal Olympic champion skater Peggy Fleming

General note: Title and date provided by Bettye Lane.

Viking Age gold and silver from Irish crannogs and other watery places

It has been observed that Viking Age gold finds in Scandinavia and Britain are frequently associated with watery environments and may represent ritual or votive depositions. There is also evidence, literary and archaeological, for the ritual deposition of some silver hoards in the Viking world. This paper considers the evidence of those Viking Age gold and silver hoards and single finds from Ireland that derive from watery locations, including crannogs and their environs. It is noted that all recorded gold hoards, with one exception, have an apparent association with water or watery places and thus conform to the patterns noted elsewhere. Most of the crannog finds, which are invariably of silver, are from the midland region, and it is noted that a high proportion of them contain ingots and hack-silver and are thus most probably economic rather than ritual in function. It is suggested that these types of hoards evidence a close economic relationship between the Hiberno-Scandinavians of Dublin and the Southern Uí Néill rulers of this area. Some of the remaining silver hoards—from bogs, rivers, lakes, small islands and shorelines—which vary in terms of their contents, with both complete ornaments and hack-silver being represented, may have been ritually deposited, but this is difficult to establish with any degree of certainty. A general discussion of ritual hoarding is presented, and it is concluded that this practice may have been more commonplace than has generally been accepted to date and that some, at least, of the ‘watery’ finds from Ireland were indeed deposited in a ritual context.

Towards thiol functionalization of vanadium pentoxide nanotubes using gold nanoparticles

Template-directed synthesis is a promising route to realize vanadate-based 1-D nanostructures, an example of which is the formation of vanadium pentoxide nanotubes and associated nanostructures. In this work, we report the interchange of long-chained alkyl amines with alkyl thiols. This reaction was followed using gold nanoparticles prepared by the Chemical Liquid Deposition (CLD) method with an average diameter of ∼0.9 nm and a stability of ∼85 days. V2 O5 nanotubes (VOx-NTs) with lengths of ∼2 μm and internal hollow diameters of 20-100 nm were synthesized and functionalized in a Au-acetone colloid with a nominal concentration of ∼ 4 × 1 0- 3 mol dm-3. The interchange reaction with dodecylamine is found only to occur in polar solvents and incorporation of the gold nanoparticles is not observed in the presence of n-decane.

Writing self-assembled monolayers with Cs: Optimization of atomic nanolithography imaging using self-assembled monolayers on gold substrates

We report the results of a study into the factors controlling the quality of nanolithographic imaging. Self-assembled monolayer (SAM) coverage, subsequent postetch pattern definition, and minimum feature size all depend on the quality of the Au substrate used in material mask atomic nanolithographic experiments. We find that sputtered Au substrates yield much smoother surfaces and a higher density of {111}-oriented grains than evaporated Au surfaces. Phase imaging with an atomic force microscope shows that the quality and percentage coverage of SAM adsorption are much greater for sputtered Au surfaces. Exposure of the self-assembled monolayer to an optically cooled atomic Cs beam traversing a two-dimensional array of submicron material masks mounted a few microns above the self-assembled monolayer surface allowed determination of the minimum average Cs dose (2 Cs atoms per self-assembled monolayer molecule) to write the monolayer. Suitable wet etching, with etch rates of 2.2 nm min-1, results in optimized pattern definition. Utilizing these optimizations, material mask features as small as 230 nm in diameter with a fractional depth gradient of 0.820 nm were realized.

The nature of alkanethiol self-assembled monolayer adsorption on sputtered gold substrates

A detailed study of the self-assembly and coverage by 1-nonanethiol of sputtered Au surfaces using molecular resolution atomic force microscopy (AFM) and scanning tunneling microscopy (STM) is presented. The monolayer self-assembles on a smooth Au surface composed predominantly of {111} oriented grains. The domains of the alkanethiol monolayer are observed with sizes typically of 5-25 nm, and multiple molecular domains can exist within one Au grain. STM imaging shows that the (4 × 2) superlattice structure is observed as a (3 × 2√3) structure when imaged under noncontact AFM conditions. The 1-nonanethiol molecules reside in the threefold hollow sites of the Au{111} lattice and aligned along its lattice vectors. The self-assembled monolayer (SAM) contains many nonuniformities such as pinholes, domain boundaries, and monatomic depressions which are present in the Au surface prior to SAM adsorption. The detailed observations demonstrate limitations to the application of 1-nonanethiol as a resist in atomic nanolithography experiments to feature sizes of ∼20 nm.