Deep desulfurization by selective adsorption of dibenzothiophenes on Ag+/SBA-15 and Ag+/SiO2

Silver (Ag+) salts adsorbed on amorphous silica or mesoporous SBA-15 extract dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-Me2DBT) from simulated, hydrotreated petroleum feedstocks.     

Efficient synthesis of aryl vinyl ethers exploiting 2,4,6-trivinylcyclotriboroxane as a vinylboronic acid equivalent

The synthesis of functionalized aryl vinyl ether derivatives can be readily achieved utilizing a room-temperature copper(II) acetate mediated coupling of substituted phenols with 2,4,6-trivinylcyclotriboroxane-pyridine complex in the presence of a suitable base. The scope of the procedure was demonstrated by the generation of an array of substituted aryl vinyl ethers. The reaction was seen to be tolerant of a diverse range of functional groups yielding products in high isolated yields. We have shown that one role of an amine base in the reaction sequence is the in situ generation of an amine coordinated boroxine ring. An X-ray crystal structure and low temperature (11)B NMR study of 2,4,6-trivinylcyclotriboroxane-pyridine complex demonstrated the nature of the tetracoordinate boron species, which may have a key role to play within the reaction sequence.     

The value of MRI in evaluating perirectal and pelvic disease

MRI of the perirectal region is facilitated by the superb soft tissue contrast, multiplanar imaging capability, lack of respiratory motion artifact and absence of clip artifact which can hamper visualization by CT scan. MRI provides distinct advantages over CT scanning without the need for ionizing radiation or the injection of intravenous contrast material. This study reviews the findings in 18 consecutive patients with a variety of perirectal pathologies including rectal carcinoma (3), gynecologic neoplasm (8), sacral lesions (2), pelvic arteriovenous malformations (2), inflammatory bowel disease (2), and a pelvic kidney (1). In the perirectal region, MR was useful to show normal tissue planes, benign processes which can mimic neoplasm, intrapelvic extension of malignancy and adenopathy.     

Delay dependence for the origin of the nonlinear derived transient evoked otoacoustic emission

In the guinea pig it has been shown that the nonlinear derived transient evoked otoacoustic emission (TEOAEnl) is comprised of significant amounts of intermodulation distortion energy. It is expected that intermodulation distortion arising from a nonlinear distortion mechanism will contribute to the overall TEOAE in a stimulus-level-dependent manner, being greatest when basilar-membrane vibration in response to a click stimulus is greatest; with decay of vibration of the basilar membrane subsequent to stimulation by a click, nonlinear interaction along the cochlear partition should reduce and so provide for a linear mechanism to dominate TEOAEnl generation, i.e., the contributions of each of these mechanisms should be delay dependent. To examine this delay dependence, TEOAEnl evoked by acoustic clicks of varying bandwidth were time-domain windowed using a recursive exponential filter in an attempt to separate two components with amplitude and phase properties consistent with different mechanisms of OAE generation. It was found that the part of the TEOAEnl occurring first in time can have a relatively constant amplitude and shallow phase slope, consistent with a nonlinear distortion mechanism. The latter part of the TEOAEnl has an amplitude microstructure and a phase response more consistent with a place-fixed mechanism.     

CpRu(CO)2(BF4) and [CpFe(CO)2(THF)]+ on mesoporous silica as adsorbents for the removal of dibenzothiophenes from hydrocarbon solutions

The complexes, CpRu(CO)2(BF4) and [CpFe(CO)2(eta2-2-methylpropene)][BF4], react with dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-Me2DBT) to give [CpRu(CO)2(DBT)][BF4] and [CpFe(CO)2(4,6-Me2DBT)][BF4], whose structures were established by X-ray diffraction studies. The same types of products are obtained when dibenzothiophenes react with CpRu(CO)2(BF4) and [CpFe(CO)2(THF)][BF4] that are adsorbed on the mesoporous silica SBA-15. DRIFT and XPS studies indicate that CpRu(CO)2(BF4) and [CpRu(CO)2(DBT)][BF4] are adsorbed on the SBA-15 by hydrogen-bonding of the BF4- anions to surface Si-O-H groups. CpRu(CO)2(BF4)/SBA-15 removes 99% of the DBT in a 45% toluene/55% hexanes simulated petroleum feedstock. This solid phase extractant is less successful for sterically-hindered 4,6-Me2DBT, as only 72% of it is removed. The results show that CpRu(CO)2(BF4) can be immobilized by adsorption on mesoporous silica and that it reacts with dibenzothiophenes in the adsorbed form, CpRu(CO)2(BF4)/SBA-15, in much the same way that it reacts in solution.     

Optical and photocatalytic properties of nanocrystalline TiO2 synthesised by solid-state chemical reaction

Nanoparticulate TiO₂ is of interest for a variety of technological applications, including optically transparent UV-filters and photocatalysts for the destruction of chemical waste. The successful use of nanoparticulate TiO₂ in such applications requires an understanding of how the synthesis conditions effect the optical and photocatalytic properties. In this study, we have investigated the effect of heat treatment temperature on the properties of nanoparticulate TiO₂ powders that were synthesised by solid-state chemical reaction of anhydrous TiOSO₄ with Na₂CO₃. It was found that the photocatalytic activity increased with the heat treatment temperature up to a maximum at 600 °C and thereafter declined. In contrast, the optical transparency decreased monotonically with the heat treatment temperature. These results indicate that solid-state chemical reaction can be used to prepare powders of nanoparticulate TiO₂ with properties that are optimised for use as either optically transparent UV-filters or photocatalysts.     

Using filament stretching rheometry to predict strand formation and “processability” in adhesives and other non-Newtonian fluids

The spinning of polymeric fibers, the processing of numerous foodstuffs and the peel and tack characteristics of adhesives are all associated with the formation, stability and, ultimately, the longevity of thin fluid `strands'. This tendency to form strands is usually described in terms of the tackiness of the fluid or by heuristic concepts such as `stringiness' (Lakrout et al. J Adhesion 1999). The dynamics of such processes are complicated due to spatially and temporally non-homogeneous growth of extensional stresses, the action of capillary forces and the evaporation of volatile solvents. We describe the development and application of a simple instrument referred to as a microfilament rheometer (MFR) that can be used to readily differentiate between the dynamical response of different pressure-sensitive adhesive fluid formulations. The device relies on a quantitative observation of the rate of extensional thinning or `necking' of a thin viscous or viscoelastic fluid filament in which the solvent is free to evaporate across the free surface. This high-resolution measurement of the radial profile provides a direct indication of the ultimate time to break up of the fluid filament. This critical time is a sensitive function of the rheological properties of the fluid and the mass transfer characteristics of the solvent, and can be conveniently reported in terms of a new dimensionless quantity we refer to as a processability parameter P. We demonstrate the usefulness of this technique by presenting our results in the form of a case study in which we measure the visco-elasto-capillary thinning of slender liquid filaments for a number of different commercial polymer/solvent formulations and relate this to the reported processing performance of the materials. We also compare the MFR observations with the prediction of a simple 1D theory derived from the governing equations that model the capillary thinning of an adhesive filament. Received: 22 December 1999/Accepted: 4 January 2000     

The impact of the natural sciences on archaeology

This article reviews some of the applications of physics to the solution of archaeological problems. The use of magnetic, resistivity and electromagnetic surveying techniques for the location of buried features is described. Various methods of age determination are outlined while the problems associated with radiocarbon dating of organic material and thermoluminescent dating of pottery are discussed in detail. The techniques, including petrological examination, chemical analysis and isotopic analysis, employed in the physical examination of archaeological artefacts are described. Examples of the application of these techniques in establishing the source of the raw materials used in pottery, metal and stone implements and in elucidating the techniques of manufacture of pottery and metal objects are also given.