Mechanism in homogeneous catalysis; NMR as a prime mover

An overview of the contribution of NMR to the development of our understanding of homogeneous catalysis is presented, with an emphasis on work from the author’s research group.     

Computational analysis of native and modified oligofructosides

This paper presents a quantum chemical calculation of native (2–7 fructoside residues) and chemically modified (2–4 fructoside residues) levan molecule models. A levan modification was carried out by oxidation and the following reduction or hyrdazonation of the fructoside rings. The conformational particularity and reaction ability was studied for the native and for the modified levan molecules.     

Noise-impact estimates per FTA and APTA criteria

In a recent paper, light-rail line noise exposures were predicted both in terms of maximum pass-by sound levels for comparison to APTA criteria and day-night average sound levels for comparison to FTA criteria. For the local land uses and ambient noise conditions of the project, the distances for the unmitigated pass-by noise exposures to attenuate to the APTA and FTA criteria limits were estimated and the numbers of included dwellings counted. The results found that the FTA impact-onset (i.e., “some-impact”) criterion curve yielded significantly greater noise exposed areas while the APTA criteria yielded results between those of the FTA “some”- and “severe”-impact curves. However, those results only applied to the specific project under evaluation. This paper attempts to extend and generalize the comparison by parametric computation of exposed areas using both the FTA and APTA procedures. Predicted exposures in this paper are compared as a function of background ambient sound levels, type of land use impacted, numbers of daytime and nighttime operations, and train pass-by maximum sound levels. At very low background ambient sound levels, FTA tended to predict the greatest exposure, while in very noisy environments, APTA predicted more exposure. APTA predicted more exposure with low numbers of daily and/or nighttime operations, and FTA predicted more exposure with high numbers, but the comparative exposures were strongly dependent upon background ambient sound level and land use. For train pass-by maximum sound levels, APTA tended to show more exposure for very quiet pass-bys and to be intermediate to FTA/some and FTA/severe for noisier events—with the comparative exposures strongly dependent upon background ambient and land use.     

Mechanism of formation of highly conductive layer on ZnO crystal surface

The mechanism of formation of a thin highly conductive layer, which is known to be present on ZnO surface, has been proposed. This process has been assumed to consist in accumulation of mobile shallow donors at crystal surface due to their drift in band-bending electric field caused by adsorbed oxygen. Experimental results that confirm this mechanism have been obtained.     

A study of the atmospheric lead pollution in Seville, Spain. Influence of meteorology and traffic, and relationship with other traffic-generated pollutants

A study of the atmospheric pollution by suspended particulate lead in the city of Seville, Spain, was carried out during the period between March 1983 and February 1984. The results obtained from seven sampling stations allowed us to study the site to site variations; there are two locations with average annual concentrations higher than 2 micrograms X m-3. In one station, the meteorological and traffic effects and relationship with other traffic-related pollutants, were investigated. The regression analyses performed on the average monthly data have shown an inverse correlation with wind speed and temperature and a direct correlation with carbon monoxide and smoke concentrations, but no significant correlation was found with the lead deposition levels.     

Stopping rule for variable selection using stepwise discriminant analysis

Summary In general, when characterizing samples, such as ceramic samples or other types of samples, for first time by means of chemical elements, the analyst measures a large number of variables, many of which may not be very informative. In fact, some may even be unrelated to the issue at hand and blur the picture instead of making it clearer. In subsequent studies the analyst may wish to measure fewer variables for several reasons, such as being very time consuming; in cases where measurement time is important, such as on-line monitoring; in order to reduce cost or effort; etc. Therefore, the hope is to determine those variables that are most relevant without losing essential information and to remove the less productive information. The problem is how to perform this in an objective way and to capture crucial information using a multivariate analysis. This paper aims to describe and illustrate a stopping rule for the identification of redundant variables, and the selection of variable subsets, preserving multivariate data structure using stepwise discriminant analysis, selecting those variables that are in some senses adequate for discrimination purposes. One illustrative example using data sets obtained via INAA of ceramic samples from two archaeological sites is provided.     

A microspectroscopic study of the electronic homogeneity of ordered and disordered Sr2FeMoO6

Disordered Sr₂FeMoO₆ shows a drastic reduction in saturation magnetization compared to highly ordered samples, moreover magnetization as a function of the temperature for different disordered samples shows qualitatively different behaviours. We investigate the origin of such diversity by performing spatially resolved photoemission spectroscopy on various disordered samples. Our results establish that e_xtensive electronic inhomogeneity, arising most probably from an underlying chemical inhomogeneity in disordered samples, is responsible for the observed magnetic inhomogeneity. It is further pointed out that these inhomogeneities are connected with composition fluctuations of the type Sr₂Fe_1+x Mo_1-x O₆ with Fe-rich (x > 0) and Mo-rich (x < 0) regions. Dedicated to Prof J Gopalakrishnan on his 62nd birthday.