Phase-Transfer Catalysis in Segmented Flow in a Microchannel: Fluidic Control of Selectivity and Productivity

Precise control over the interfacial area of aqueous and organic slugs in segmented flow in a microchannel reactor provides an attractive means to optimize the yield and productivity of a phase-transfer-catalyzed reaction. Herein, we report the selective alkylation of phenylacetonitrile to the monoalkylated product in a microchannel of 250-mu m internal diameter operated in a continuous and solvent-free manner in the slug-flow regime. The conversion of phenylacetonitrile increased from 40% to 99% as a result of a 97% larger slug surface-to-volume ratio when the volumetric aqueous-to-organic phase flow ratio was raised from 1.0 to 6.1 at the same residence time. The larger surface-to-volume ratio significantly promoted catalyst phase transfer but decreased selectivity because of the simultaneous increase of the rate of the consecutive reaction to the dialkylated product. There exists all Optimum flow ratio with a maximum productivity. Conversion and selectivity in the microchannel reactor were both found to be significantly larger than in a stirred reactor.

Light emission from gold and silver thin films in a scanning tunneling microscope: role of contamination and interpretation of grain structure in photon maps

Scanning tunnelling microscope (STM) tip-induced light emission from Au and Ag has been studied. Thin film samples similar to100nm thick were prepared by thermal evaporation at 0.5nm/s onto a room-temperature glass substrate to produce grains of 20-50nm in lateral dimension at the surface. Light emission from the samples in the STM was quasi-simultaneously recorded with the topography, at 1.8V tip bias and 3-40nA current, alternating pixel by pixel at the same bias. Typically, a surface scan range of 150 nm x 150 nm was surveyed. Au, W and PtIr tips were used.

Wavelength Dependence of Raman Enhancement from Gold Nanorod Arrays: Quantitative Experiment and Modeling of a Hot Spot Dominated System

Surface-enhanced Raman scattering (SERS) spectra from molecules adsorbed on the surface of vertically aligned gold nanorod arrays exhibit a variation in enhancement factor (EF) as a function of excitation wavelength that displays little correlation with the elastic optical properties of the surface. The key to understanding this lack of correlation and to obtaining agreement between experimental and calculated EF spectra lies with consideration of randomly distributed, sub-10 nm gaps between nanorods forming the substrate. Intense fields in these enhancement “hot spots” make a dominant contribution to the Raman scattering and have a very different spectral profile to that of the elastic optical response. Detailed modeling of the electric field enhancement at both excitation and scattering wavelengths was used to quantitatively predict both the spectral profile and the magnitude of the observed EF.

TAP studies of CO oxidation over CuMnOX and Au/CuMnOX catalysts

The mechanism of CO oxidation reactions over undoped and gold-doped CuMnOX (Hopcalite) catalysts has been examined using a temporal analysis of products (TAP) reactor Gold doping has been found to increase the activity of the mixed oxide catalyst significantly however using consecutive pulsing TAP experiments the presence of gold was not found to affect the contribution of the Langmuir-Hinshelwood mechanism Conversely gold doping was found to promote the Mars van Krevelen mechanism Using CO and O-2 multi-pulse TAP experiments the gold was found to modify the catalyst surface such that it stores much more oxygen that is active for the CO oxidation The CO multi-pulse experiments indicated that two distinct types of active oxygen species were found to be involved in the CO oxidation One type was observed in a similar amount on both doped and undoped catalysts and was associated with mixed oxide while the second type was only found on the gold-doped catalyst and was therefore clearly associated with the presence of gold on the catalyst surface The latter was found to be much less active than the oxygen inherent to the oxide but was at a concentration of approximately 10 times larger leading to the enhanced activity observed on gold doping (C) 2010 Elsevier Inc All rights reserved

On the function of the internal cavity of histone deacetylase protein 8: R37 is a crucial residue for catalysis

Biochemical studies reveal that a conserved arginine residue (R37) at the centre of the 14 angstrom internal cavity of histone deacetylase (HDAC) 8 is important for catalysis and acetate affinity. Computational studies indicate that R37 forms multiple hydrogen bonding interactions with the backbone carbonyl oxygen atoms of two conserved glycine residues, G303 and G305, resulting in a 'closed' form of the channel. One possible rationale for these data is that water or product (acetate) transit through the catalytically crucial internal channel of HDAC8 is regulated by a gating interaction between G139 and G303 tethered in position by the conserved R37. (C) 2011 Elsevier Ltd. All rights reserved.

Combining bio- and chemo-catalysis: from enzymes to cells, from petroleum to biomass

In the future, biomass will continue to emerge as a viable source of chemicals. The development of new industries that utilize bio-renewables provides opportunities for innovation. For example, bio- and chemo-catalysts can be combined in 'one pot' to prepare chemicals of commercial value. This has been demonstrated using isolated enzymes and whole cells for a variety of chemical transformations. The one-pot approach has been successfully adopted to convert chemicals derived from biomass, and, in our opinion, it has an important role to play in the design of a more sustainable chemical industry. To implement new one-pot bio- and chemo-catalytic processes, issues of incompatibility must be overcome; the strategies for which are discussed in this opinion article.