Selective hydrogenation of citral with transition metal complexes in supercritical carbon dioxide

The activity and selectivity of the transition metal complexes formed from Ru, Rh, Pd and Ni with triphenylphosphine (TPP) have been investigated for hydrogenation of citral in supercritical carbon dioxide (scCO(2)). High activities are obtained with Ru/TPP and Pd/TPP catalysts, and the overall activity is in the order of Pd approximate to Ru > Rh > Ni. The Ru/TPP complex is highly selective to the formation of unsaturated alcohols of geraniol and nerol. In contrast, the Pd/TPP catalyst is more selective to partially saturated aldehydes of citronellal. Furthermore, the influence of several parameters such as CO2 and H-2 pressures, N-2 pressure and reaction time has been discussed. CO2 pressure has a significant impact on the product distribution, and the selectivity for geraniol and nerol can be enhanced from 27% to 75% with increasing CO2 pressure from 6 to 16 MPa, while the selectivity for citronellol decreases from 70% to 20%. Striking changes in the conversion and product distribution in scCO(2) could be interpreted with variations in the phase behavior and the molecular interaction between CO2 and the substrate in the gas phase and in the liquid phase.

Effects of zirconia phase on the synthesis of higher alcohols over zirconia and modified zirconia

The catalytic performances of ZrO2-based catalysts were evaluated for the synthesis of higher alcohols from synthesis gas. The crystal phase structures were characterized by X-ray diffraction (XRD) and UV Raman. The results indicated that ZrO2 and Pd modified ZrO2 catalysts were effective catalysts in the synthesis of ethanol or isobutanol, and their selectivities basically depended on the crystal phase of ZrO2 surface. The ZrO2 with surface tetragonal crystal phase exhibited a high activity to form ethanol, while the ZrO2 with surface monoclinic crystal phase exhibited a high activity to form isobutanol. Temperature-programmed desorption (TPD) experiment indicated that the high activity of isobutanol formation from synthesis gas over monoclinic zirconia was due probably to the strong Lewis acidity of Zr4+ cations and the strong Lewis basicity of O2- anions of coordinative unsaturated Zr4+-O2- pairs on the surface of monoclinic ZrO2. (C) 2003 Elsevier B.V. All rights reserved.

Fractal dimensions for unsaturated porous media

The analytical expressions of the fractal dimensions for wetting and non-wetting phases for unsaturated porous media are derived and are found to be a function of porosity, maximum and minimum pore sizes as well as saturation. There is no empirical constant in the proposed fractal dimensions. It is also found that the fractal dimensions increase with porosity of a medium and are meaningful only in a certain range of saturation S-w, i.e. S-w > S-min for wetting phase and S-w < S-max for non-wetting phase at a given porosity, based on real porous media for requirements from both fractal theory and experimental observations. The present analysis of the fractal dimensions is verified to be consistent with the existing experimental observations and it makes possible to analyze the transport properties such as permeability, thermal dispersion in unsaturated porous media by fractal theory and technique.

Work and energy equations and the principle of generalized effective stress for unsaturated soils

The effective stress principle has been efficiently applied to saturated soils in the soil mechanics and geotechnical engineering practice; however, its applicability to unsaturated soils is still under debate. The appropriate selection of stress state variables is essential for the construction of constitutive models for unsaturated soils. Owing to the complexity of unsaturated soils, it is difficult to determine the deformation and strength behaviors of unsaturated soils uniquely with the previous single-effective-stress variable theory and two-effective-stress-variable theory in all the situations. In this paper, based on the porous media theory, the specific expression of work is proposed, and the effective stress of unsaturated soils conjugated with the displacement of the soil skeleton is further derived. In the derived work and energy balance equations, the energy dissipation in unsaturated soils is taken into account. According to the derived work and energy balance equations, all of the three generalized stresses and the conjugated strains have effects on the deformation of unsaturated soils. For considering these effects, a principle of generalized effective stress to describe the behaviors of unsaturated soils is proposed. The proposed principle of generalized effective stress may reduce to the previous effective stress theory of single-stress variable or the two-stress variables under certain conditions. This principle provides a helpful reference for the development of constitutive models for unsaturated soils.

Sensitivity to alcohols of a planar waveguide ring resonator fabricated by a sol-gel method

A planar waveguide ring resonator was fabricated by organic-inorganic hybrid sol-gel materials; its sensitivity to ethanol vapor was experimentally investigated. It was found that dips in the transmission spectrum of the device shifted to longer wavelengths with increasing the ethanol concentration, and its sensitivity showed a linear relation with the ethanol concentration, showing a coefficient of 1.13 pm/ppm. In addition, the transmission loss of the ring resonator decreased with increasing the ethanol concentration. The measured characteristics suggest that the device may be considered as one of the candidates of alcohol vapor sensors. (c) 2006 Elsevier B.V. All rights reserved.

Structure and Electronic Properties of Saturated and Unsaturated Gallium Nitride Nanotubes

The atomic and electronic structures of saturated and unsaturated GaN nanotubes along the [001] direction with (100) lateral facets are studied using first-principles calculations. Atomic relaxation of nanotubes shows that appreciable distortion occurs in the unsaturated nanotubes. All the nanotubes considered, including saturated and unsaturated ones, exhibit semiconducting, with a direct band gap Surface states arisen from the 3-fold-coordinated N and Ga atoms at the lateral facets exist inside the bulklike band gap. When the nanotubes are saturated with hydrogen, these dangling bond bands are removed from the band gap, but the band gap decreases with increasing the wall thickness of the nanotubes.

Effects of molecular structures on the olfactory responses of phospholipid membranes to four alcohols

In order to understand the relationship between phospholipid molecular structures and their olfactory responses to odorants, we designed and synthesized four phosphatidylcholine analogues with different long hydrocarbon (CH) chains and selected three natural phospholipids with different head-groups. By using interdigital electrodes (IEs) as olfactory sensors (OSs), we measured the responses of the Ifs coated with these seven different lipid membranes to four alcohol vapors in a gas flow system. The Ifs voltage changes were recorded and the voltage-relative saturate vapor pressure (V-P/P degrees) curves were also plotted. It was found that with a methyl (-CH3) placed at the C-8 position in the 18-carbon chain, the olfactory responses could be improved about ten times and with conjugated double bonds (C=C) in the long chains, the sensitivity could be increased by 3 similar to 4 orders of magnitude. As to head-groups, choline is preferred over ethanolamine and serine in phospholipid structures in terms of high olfactory sensitivity: These results are expected to be useful in further designing and manufacturing lipid-mimicking OSs. (C) 1998 Elsevier Science Ireland Ltd. All rights reserved.

LIPID MICRORESISTOR AS MIMICKING OLFACTORY SENSOR - THE RULE OF THE RESPONSE OF LIPIDS TO C-1-C-4 ALCOHOLS

Phosphatidylcholine (PC) and six other PC-similar lipids are coated on interdigital electrodes, IEs, as sensitive membranes. Eight alcohols (C-1-C-4) are tested in a flow system at room temperature. It is found that all responses are log(response)-log(concentration) linear relations. These results agree with Steven's law in psychophysics. Moreover, the thresholds of the sensors are coincident with human olfactory thresholds. The authors have analysed the data of the lipid hypothesis suggested by Kurihara et al. We have found that this hypothesis is also in agreement with Steven's law. Lipid microresistors are real mimicking olfactory sensors. A definition of an olfactory sensor is suggested.