Os(VIII)-catalysed oxidation of sulfides by sodium salt of N-chlorobenzenesulfonamide

Catalytic activity of Os(VIII) in the oxidation of some twenty organic sulfides with sodium salt of N-chlorobenzenesulfonamide (CAB) has been investigated in alkaline (pH8.7) t-butanol–water (1:1 v/v) medium. Significant retarding influence of [OH⁻] on the reactivity is exhibited. The catalysed reaction is strongly accelerated in the presence of Hg(II). Imperfections are observed in the linear Hammett relationship in the case of –NO₂ substituents.     

Raman spectroscopic investigation on the microenvironment of the liver tissues of Zebrafish (Danio rerio) due to titanium dioxide exposure

Nano titanium dioxide (nTiO₂), generally considered to be toxicologically inert, is manufactured in large quantities and extensively applied in consumer products. The small size and large surface area endow them with an active group or intrinsic toxicity. Advances in instrumentation are making Raman spectroscopy the tool of choice for an increasing number of (bio) chemical applications. One of the great advantages of this technique is its ability to provide information on the concentration, structure and interaction of biochemical molecules in their microenvironments within intact cells and tissues, non-destructively. Zebrafish (Danio rerio), one of the most important vertebrate model organisms used in developmental biology, are increasingly used in biomedical research, particularly as a model of human disease. In the present work, an attempt is made to study the effect of titanium dioxide, both nano and bulk, on the microenvironment of the liver tissues of Zebrafish using FT-Raman spectroscopy. The results of the present study suggest that TiO₂ exposure demonstrate a marked influence on the microenvironments of the liver tissues of Zebrafish. A shift to a higher wavenumber and an increase in the intensity of the band at ∼1087 cm⁻¹ in the TiO₂ exposed tissues suggest that some of the conformational changes resulting from the alkali recovery process takes place due to TiO₂ exposure. The decreased intensity ratio (I₃₂₂₀/I₃₄₀₀) observed in the titanium-exposed tissues suggests a decreased water domain size, which could be interpreted in terms of weaker hydrogen-bonded molecular species of water in the TiO₂ exposed tissues. The observed shift of COO⁻ bands to higher frequencies shows the disruption of salt bridges as a result of a change in the oppositely charged partners and due to the enhanced random coil conformation. The variation in the intensity ratio of the tyrosyl doublet (I₈₅₈/I₈₂₅) indicates variation in the hydrogen bonding of the phenolic hydroxyl group due to TiO₂ exposure. The results further suggest that the microenvironments are greatly altered due to titanium nano exposure when compared to titanium bulk. In conclusion, the results indicate that FT-Raman spectroscopy might be a useful tool for rapid assessment of nano particle biological interactions.     

The embedding of General Relativity in five dimensions

We argue that General Relativistic solutions can always be locally embedded in Ricci-flat 5-dimensional spaces. This is a direct consequence of a theorem of Campbell (given here for both a timelike and spacelike extra dimension, together with a special case of this theorem) which guarantees that anyn-dimensional Riemannian manifold can be locally embedded in an (n+1)-dimensional Ricci-flat Riemannian manifold. This is of great importance in establishing local generality for a proposal recently put forward and developed by Wesson and others, whereby vacuum (4+1)-dimensional field equations give rise to (3+1)-dimensional equations with sources. An important feature of Campbell's procedure is that it automatically guarantees the compatibility of Gauss-Codazzi equations and therefore allows the construction of embeddings to be in principle always possible. We employ this procedure to construct such embeddings in a number of simple cases.     

Towards a theory of macroscopic gravity

By averaging out Cartan's structure equations for a four-dimensional Riemannian space over space regions, the structure equations for the averaged space have been derived with the procedure being valid on an arbitrary Riemannian space. The averaged space is characterized by a metric, Riemannian and non-Rimannian curvature 2-forms, and correlation 2-, 3- and 4-forms, an affine deformation 1-form being due to the non-metricity of one of two connection 1-forms. Using the procedure for the space-time averaging of the Einstein equations produces the averaged ones with the terms of geometric correction by the correlation tensors. The equations of motion for averaged energy momentum, obtained by averaging out the contracted Bianchi identities, also include such terms. Considering the gravitational induction tensor to be the Riemannian curvature tensor (the non-Riemannian one is then the field tensor), a theorem is proved which relates the algebraic structure of the averaged microscopic metric to that of the induction tensor. It is shown that the averaged Einstein equations can be put in the form of the Einstein equations with the conserved macroscopic energy-momentum tensor of a definite structure including the correlation functions. By using the high-frequency approximation of Isaacson with second-order correction to the microscopic metric, the self-consistency and compatibility of the equations and relations obtained are shown. Macrovacuum turns out to be Ricci non-flat, the macrovacuum source being defined in terms of the correlation functions. In the high-frequency limit the equations are shown to become Isaacson's ones with the macrovauum source becoming Isaacson's stress tensor for gravitational waves.     

Averaging out the Einstein equations

A general scheme to average out an arbitrary 4-dimensional Riemannian space and to construct the geometry of the averaged space is proposed. It is shown that the averaged manifold has a metric and two equi-affine symmetric connections. The geometry of the space is characterized by the tensors of Riemannian and non-Riemannian curvatures, an affine deformation tensor being the result of non-metricity of one of the connections. To average out the differential Bianchi identities, correlation 2-form, 3-form and 4-form are introduced and the differential relations on these correlations tensors are derived, the relations being integrable on an arbitrary averaged manifold. Upon assuming a splitting rule for the average of the product including a covariantly constant tensor, an averaging out of the Einstein equations has been carried out which brings additional terms with the correlation tensors into them. As shown by averaging out the contracted Bianchi identities, the equations of motion for the averaged energy-momentum tensor do also include the geometric correction terms. Considering the gravitational induction tensor to be the Riemannian curvature tensor (then the non-Riemannian one is the macroscopic gravitational field), a theorem that relates the algebraic structure of the averaged microscopic metric with that of the induction tensor is proved. Due to the theorem the same field operator as in the Einstein equations is manifestly extracted from the averaged ones. Physical interpretation and application of the relations and equations obtained to treat macroscopic gravity are discussed.     

Averaged Lagrangians and MacCallum-Taub's limit in macroscopic gravity

The derivation of MacCallum-Taub's averaged high-frequency Lagrangian [1] is analysed with special attention paid to the assumptions made along the derivation. It is shown that averaged high-frequency Lagrangians of the same form as MacCallum-Taub's Lagrangian can be derived by applying the Brill-Hartle and macroscopic gravity averaging schemes. A procedure for the derivation of a Lagrangian of macroscopic gravity (an averaged Hilbert action) is proposed and its high-frequency limit (namely, its high-frequency perturbation expansion up to the second order terms in perturbations, which is referred to as MacCallum-Taub's limit) is calculated. There is disagreement [2] in the expressions for MacCallum-Taub's averaged high-frequency Lagrangian and the high-frequency limit of the macroscopic gravity Lagrangian. Possible reasons for such disagreement are analysed. The origin of the difference is shown to consist in using the propagation equation for perturbations, i.e. the linearized Ricci tensor vanishes, during the derivation (averaging) carried out in [1]. A new derivation of an averaged high-frequency Lagrangian without assuming the propagation equation to hold and by taking into account the proper correlation functions is given. The newly derived expression is shown to coincide with MacCallum-Taub's limit of the macroscopic gravity Lagrangian, which resolves the disagreement.     

Direct equilibration of soil water for delta(18)O analysis and its application to tracer studies

Current methods for stable oxygen isotopic (delta (18)O) analysis of soil water rely on separation of water from the soil matrix before analysis. These separation procedures are not only time consuming and require relatively large samples of soil, but also have been shown to introduce a large potential source of error. Current research at Queen's University Belfast is focused on using direct equilibration of CO(2) with the pore water to eliminate this extraction step using the automated Multiprep system and a Micromass Prism III isotope ratio mass spectrometer (IRMS). The findings of this research indicate the method is less time consuming, more reliable, and reproducible to within accepted limits (+/-0.1% per thousand delta (18)O). In this study the direct equilibration method is used to analyse delta (18)O tracer profiles in the unsaturated zone of field soils, concurrently with chloride tracer profiles, which can be used to assess infiltration rates and mechanisms through the unsaturated zone. Copyright 1999 John Wiley & Sons, Ltd.     

Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

The study of the changes in the thermal properties of <Emphasis Type="Italic">Labeo rohita</Emphasis> bones due to arsenic exposure

The paper presents the changes in the thermal properties of control, arsenic exposed and DMSA treated Labeo rohita bones by using thermo analytical techniques. The result shows that the mass loss due to the thermal decomposition occurs in three distinct steps due to loss of water, organic and inorganic materials. The arsenic exposed bones present a different thermal behaviour compared to the control bones. The residue masses are increased due to arsenic exposure, while the DMSA treatment reduces the residue mass level. These thermal characteristics can be used as a qualitative method to check the metal accumulation in samples.