Photo-Electron Spectroscopic Studies Of The Adsorption Of Organic-Molecules With Lone Pair Orbitals On Transition-Metal Surfaces

Ultraviolet and x-ray photoelectron spectroscopy have been employed to investigate the adsorption of methanol, ethanol, diethylether, acetaldehyde, acetone, methyl acetate and methylamine on surfaces of Fe, Ni and Cu. All these molecules adsorb molecularly at low temperatures (≤100 K). Lone pair orbitals of these molecules are stabilized on these metal surfaces (by 0·4–1·0eV) due to molecular chemisorption. The molecules generally undergo transformations as the temperature is raised to 120 K or above. The new species produced seems to depend on the metal surface. Some of the product species identified are methoxy species, formaldehyde and carbon monoxide in the case of methanol and methyl acetate, ethoxy species in the case of ethanol and 2-propanol in the case of acetone.

Adsorption of carbon monoxide on the surfaces of polycrystalline transition metals and alloys: electron energy loss and ultraviolet photoelectron spectral studies1

Adsorption of CO has been investigated on the surfaces of polycrystalline transition metals as well as alloys by employing electron energy loss spectroscopy (eels) and ultraviolet photoelectron spectroscopy (ups). CO adsorbs on polycrystalline transition metal surfaces with a multiplicity of sites, each being associated with a characteristic CO stretching frequency; the relative intensities vary with temperature as well as coverage. Whilst at low temperatures (80- 120 K), low coordination sites are stabilized, the higher coordination sites are stabilized at higher temperatures (270-300 K). Adsorption on surfaces of polycrystalline alloys gives characteristic stretching frequencies due to the constituent metal sites. Alloying, however, causes a shift in the stretching frequencies, indicating the effect of the band structure on the nature of adsorption. The up spectra provide confirmatory evidence for the existence of separate metal sites in the alloys as well as for the high-temperature and low-temperature phases of adsorbed CO.

Interaction of carbon monoxide with surfaces of metglasses

UPS and XPS studies indicate that carbon monoxide preferentially adsorbs dissociatively on the surfaces of the metallic glasses, Ni76B12Si12 and Fe40Ni38Mo4B18, suggesting that such metglasses could be potential catalysts for some of the reactions involving CO.

Study of solids and surfaces by photoacoustic spectroscopy

Photoacoustic spectroscopy has been employed to study the electronic spectra of a variety of solids. The systems studied include powders of intensely coloured dyes, amorphous chalcogenides and oxide gels besides polycrystalline samples of several oxide materials. Surface sensitivity of the technique has been examined by study of dye adsorption on oxide surfaces and determination of surface areas of active oxides. Acidic and basic sites on catalyst surfaces have also been estimated by this technique.

Photoacoustic spectroscopy of solids and surfaces

After briefly reviewing the theory and instrumentation, results from a variety of experiments carried out by the authors on the photoacoustic spectroscopy of solids and surfaces by employing an indigenous spectrometer are discussed in the light of the recent literature. Some of the important findings discussed are, phase angle spectroscopy, anomalous behaviour of monolayers, unusual frequency dependence in small cell volumes, spectra of a variety of solids including amorphous arsenic chalcogenides, photoacoustic detection of phase transitions and determination of surface areas and surface acidities of oxides. Recent developments such as piezoelectric photoacoustic spectroscopy, depth profiling and subsurface imaging are also presented.

Electron Spectroscopic Studies of Oxygen and Carbon Dioxide Adsorbed on Metal Surfaces

Adsorption of oxygen on Ni, Cu, Pd, Ag, and Au surfaces has been investigated by employing UV and X-ray photoelectron spectrscopy as well as electron energy loss spectroscopy (EELS). Molecularly chemisorbed (singlet) oxygen is found on Ni, Cu, Ag, and Au surfaces showing features such as stabilization of the rB* orbital, destabilization of the .nu orbital, higher O(1s) binding energy than the atomic species, and a band 2-3 eV below the Fermi level due to metal d-O(2p)u* interaction. 0-0 and metal-oxygen stretching frequencies have been observed in EELS. Physical adsorption of O2 is found to occur on Pd and Ni surfaces, only at high exposures in the latter case. Physical adsorption and multilayer condensation of CO, on metal surfaces are distinguished by characteristic relaxation shifts in UPS as well as O(1s) binding energies. Adsorption of CO on a Ni surface covered with presorbed atomic oxygen gives rise to C02.

The structure of turbulent boundary layers along mildly curved surfaces

This paper describes a detailed study of the structure of turbulence in boundary layers along mildly curved convex and concave surfaces. The surface curvature studied corresponds to δ/Rw = ± 0·01, δ being the boundary-layer thickness and Rw the radius of curvature of the wall, taken as positive for convex and negative for concave curvature. Measurements of turbulent energy balance, autocorrelations, auto- and cross-power spectra, amplitude probability distributions and conditional correlations are reported. It is observed that even mild curvature has very strong effects on the various aspects of the turbulent structure. For example, convex curvature suppresses the diffusion of turbulent energy away from the wall, reduces drastically the integral time scales and shifts the spectral distributions of turbulent energy and Reynolds shear stress towards high wavenumbers. Exactly opposite effects, though generally of a smaller magnitude, are produced by concave wall curvature. It is also found that curvature of either sign affects the v fluctuations more strongly than the u fluctuations and that curvature effects are more significant in the outer region of the boundary layer than in the region close to the wall. The data on the conditional correlations are used to study, in detail, the mechanism of turbulent transport in curved boundary layers. (Published Online April 12 2006)

Mean Flow Measurements in Turbulent Boundary Layers along Mildly Curved Surfaces

An experimental investigation of the mean flow characteristics of two-dimensional turbulent boundary layers over surfaces of mild longitudinal curvature is reported. The study covered both convex and concave walls of \d/Rw I « 0.013 (d being the boundary-layer thickness and Rw being the wall radius). It was found that, whereas the region close to the wall was not affected significantly by wall curvature, the outer region was very sensitive to even mild wall curvature. A detailed study of the wake region using present and other available data suggests a systematic effect of b/Rw on the wake structure. The paper also discusses in detail the effect of mild wall curvature on the boundary-layer development with particular emphasis on the difference in behavior of the boundary layer at short and long distances from the leading edge of the curved wall, an aspect which has not received sufficient attention in previous experimental investigations. An attempt has been made to explain this behavior from a consideration of the structure of turbulence in boundary layers over curved surfaces taken into account.

A parameter characterizing plowing nature of surfaces close to Gaussian

A non-dimensional parameter descriptive of the plowing nature of surfaces is proposed for the case of sliding between a soft and a relatively hard metallic pair. From a set of potential parameters which can be descriptive of the phenomenon, dimensionless groups are formulated and the influence of each one of them is analyzed. A non-dimensional parameter involving the root-mean square deviation (R-q) and the centroidal frequency (F-mean) deducted from the power-spectrum is found to have a high degree of correlation (as high as 0.93) with the coefficient of friction obtained in sliding experiments under lubricated condition.

Domains in complex surfaces with non-compact automorphism groups

Let X be an arbitrary complex surface and D a domain in X that has a non-compact group of holomorphic automorphisms. A characterization of those domains D that admit a smooth, weakly pseudoconvex, finite type boundary orbit accumulation point is obtained.

Visual Analysis of Biomolecular Surfaces

Surface models of biomolecules have become crucially important for the study and understanding of interaction between biomolecules and their environment. We argue for the need for a detailed understanding of biomolecular surfaces by describing several applications in computational and structural biology. We review methods used to model, represent, characterize, and visualize biomolecular surfaces focusing on the role that geometry and topology play in identifying features on the surface. These methods enable the development of efficient computational and visualization tools for studying the function of biomolecules.

Pollinator limitation and the effect of breeding systems on plant reproduction in forest fragments

Reproduction of plants in fragmented habitats may be limited because of lower diversity or abundance of pollinators, and/or variation in local plant density. We assessed natural fruit set and pollinator limitation in ten species of woody plants in natural and restored fragments in the Pondicherry region of southern India, to see whether breeding system of plants (self-compatible and self-incompatible) affected fruit set. We tested whether the number of flowering individuals in the fragments affected the fruit set and further examined the adult and sapling densities of self-compatible (SC) and self-incompatible (SI) species. We measured the natural level of fruit set and pollinator limitation (calculated as the difference in fruit set between hand cross-pollinated and naturally pollinated flowers). Our results demonstrate that there was a higher level of pollinator limitation and hence lower levels of natural fruit set in self-incompatible species as compared to self-compatible species. However, the hand cross-pollinated flowers in SC and SI species produced similar levels of fruit set,further indicating that lower fruit set was due to pollinator limitation and not due to lack of cross-compatible individuals in the fragments. There was no significant relation between number of flowering individuals and the levels of natural fruit set, except for two species Derris ovalifolia, Ixora pavetta. In these species the natural fruit set decreased with increasing population size, again indicating pollinator limitation. The adult and sapling densities in self-compatible species were significantly higher than inself-incompatible species. These findings indicate that the low reproductive output in self-incompatible species may eventually lead to lower population sizes. Restoration of pollinator services along with plant species in fragmented habitats is important for the long-term conservation of biodiversity. (C) 2009 Elsevier Masson SAS. All rights reserved.

Interrelations of micro-organisms and mulberry II. Phyllosphere microflora and nitrogen fixation in leaf and root surfaces

The mulberry leaves were shown to harbour substantial populations of bacteria, streptomycetes, yeasts, and moulds. Azotobacter and Beijerinckia were observed to contribute to nearly 5 to 10 per cent of the bacterial population. When grown in water culture under sterile conditions, Azotobacter inoculation on the leaf or root surface was found to increase plant growth, dry wt, and nitrogen content of the mulberry. The beneficial effect of Azotobacter was largely influenced by the presence of a carbon source in the plant nutrient solution. The root inoculation in comparison to leaf application was found to confer greater benefits to the growing plant. The presence of carbohydrates and amino acids in the leaf leachates of mulberry was shown. The mutual beneficial nature of the association of the plant and Azotobacter has been brought to light.

Adhesion of Acidithiobacillus ferrooxidans to mineral surfaces

Direct contact mechanism in bioleaching implies prior mineral adhesion of Acidithiobacillus ferrooxidans and subsequent enzymatic attack.Prior bacterial adaptation to sulfide mineral substrates influences bacterial ferrous ion oxidation rates. It is highly beneficial to understand major biooxidation mechanisms with reference to solution- and mineral-grown cells in order to optimize bioleaching reactions. For A. ferrooxidans grown in the presence of solid substrates such as sulfur, pyrite and chalcopyrite, bacterial adhesion is required for its enzymatic machinery to come into close contact for mineral dissolution.But when grown in solution substrate such as ferrous ions and thiosulfate, such an adhesion machinery is not required for substrate utilization. Proteinaceous compounds were observed on the surface of sulfur-grown cells. Such an induction of relatively hydrophobic proteins and down regulation of exposed polysaccharides leads to changes in cell surface chemistry. Sulfur-grown and pyrite- and chalcopyrite-grown bacterial cells were found to be more efficient in the bioleaching of chalcopyrite than those grown in the presence of ferrous ions and thiosulfate. (C) 2010 Elsevier B.V. All rights reserved.