Effect of catalyst on regioselectivity and vinyl/H exchange on silicon in the hydrosilylation of vinyl-siloxanes by T8 hydrogen silsesquioxane

We have recently reported the synthesis of octopus molecules of defined shape and size with molecular weights well into the thousands. These octopus molecules were made by placing eight pendant groups symmetrically about a central silsesquioxane core via the H₂PtCl₆ catalyzed hydrosilylation of 1-alkenes as well as vinyl- and allyl-siloxanes by T₈ hydrogen silsesquioxane, (HSiO₃₂)₈. The chemistry of addition was studied and it was found that while the addition of the 1-alkenes to T₈ was regioprecise with only -addition being observed, both - and -addition occurred with vinyl-siloxane. In addition, H-vinyl exchange on silicon was observed to occur with addition of vinyl-siloxane to T₈. In the current studies, the effect of the hydrosilylation catalyst. homogeneous and heterogeneous, on the regioselectivity of addition and on the extent of exchange on silicon was evaluated. It was found that the heterogeneous catalysts Pt–C, sulfided Pt–C, and Rh–C required higher temperature and longer times to get complete reaction than the homogeneous catalysts. H₂PtCl₆ and the tetramethyldivinyldisiloxane complex of Pt. Pd supported catalysts were not effective catalysts for this hydrosilylation. The extent of exchange on silicon and the degree of the second mode of addition occurring were higher with the heterogenous catalysts and may be a result of the higher reaction temperatures.     

Free fatty acid inhibition of the insulin induction of glucose-6-phosphate dehydrogenase in rat hepatocyte monolayers

Rat hepatocytes in monolayer culture were utilized to determine if the decrease in glucose-6-phosphate dehydrogenase (G6PD) activity resulting from the ingestion of fat can be mimicked by the addition of fatty acids to a chemically, hormonally defined medium. G6PD activity in cultured hepatocytes was induced several-fold by insulin. Dexamethasone or T3 did not amplify the insulin induction of G6PD. Glucose alone increased G6PD activity in cultured hepatocytes from fasted donors by nearly 500%. Insulin in combination with glucose induced G6PD an additional two-fold. The increase in G6PD activity caused by glucose was greater in hepatocytes isolated from 72 hr-fasted rats as compared to fed donor rats. Such a response was reminiscent of the “overshoot” phenomenon in which G6PD activity is induced well above the normal level by fasting-refeeding rats a high glucose diet. Addition of linoleate to the medium resulted in a significant suppression of insulin’s ability to induce G6PD, but linoleate had no effect on the induction of G6PD activity by glucose alone. A shift to the right in the insulin-response curve for the induction of G6PD also was detected for the induction of malic enzyme and acetyl-CoA carboxylase. Arachidonate (0.25 mM) was a significantly more effective inhibitor of the insulin action than linoleate was. Apparently rat hepatocytes in monolayer culture can be utilized as a model to investigate the molecular mechanism by which fatty acids inhibit the production of lipogenic enzymes. In part, this mechanism of fatty acid inhibition involves desensitization of hepatocytes to the lipogenic action of insulin.     

Comparison of single and coastal superphosphate for subterranean clover on phosphorus leaching soils

Coastal superphosphate, a partially acidulated rock phosphate (PARP), is being considered as an alternative fertilizer to single superphosphate for pastures in high rainfall (> 800 mm annual average) areas of south-western Australia. The effectiveness of single and coastal superphosphate, as P fertilizers, was measured in two field experiments using dry herbage yield of subterranean clover (Trifolium subterraneum). The experiments were started in April 1990 and were terminated at the end of 1993. In the years after P applications, soil samples were collected each January to measure Colwell soil-test P, which was related to plant yields measured later on that year, to provide soil P test calibrations.Relative to freshly-applied single superphosphate, the effectiveness of freshly-applied coastal superphosphate and the residues of previously-applied single and coastal superphosphate were less effective in some years (from 3% as effective to equally effective), and up to 100% more effective in other years. This large range in effectiveness values in different years is attributed to different climatic conditions. Soil P test calibrations were different for soils treated with single or coastal superphosphate. The calibrations were also different for different yield assessments (harvests) in the same year, and in different years. Consequently soil P testing can only provide a very crude estimate of the current P status of the soils.     

Estimation of the concentration of donatable hydrogen in a coal solvent by n.m.r.

¹H and ¹³C nuclear magnetic resonance (n.m.r.) spectroscopies have been used to study the changes in composition of a hydrogenated anthracene oil solvent that occur during extraction of a UK bituminous coal. It has been shown that the principal hydrogen donor groups in the solvent are hydroaromatic and naphthenic rings in hydroaromatic species. Good agreement was achieved between the concentration of donatable hydrogen estimated from n.m.r., and the amount of hydrogen transferred from the solvent during exhaustive extraction.     

Effect of Zwitterionic Surfactants on Interparticle Forces, Rheology, and Particle Packing of Silicon Nitride Slurries

Phosphocholine (PC) zwitterionic surfactants, with different hydrocarbon chain lengths (C₆C₆PC to C₉C₉PC), were absorbed on the surface of silicon nitride near the isoelectric point (pH 6). Adsorption of the surfactants changed the lateral and normal surface forces, the rheology, and the consolidation behavior of the particles. The normal force between two silicon nitride surfaces as a function of separation and the lateral (friction) forces were measured using an atomic force microscope (AFM). These measurements indicated that surfactant adsorption reduced the magnitude of the long-range attractive van der Waals force and produced a repulsive short-range force. Although the adsorbed layers provided a barrier to particle contact, they could be ejected with a critical force that increased with the hydrocarbon chain length. The effect of an adsorbed layer on the viscosity and consolidation of slurries was also measured. The viscosity of all slurries decreased with increasing shear rate, indicative of attractive particle networks. The highest viscosity was observed for slurries formulated at the isoelectric point without added surfactant. Much lower viscosities were observed when the surfactant concentration was greater than the critical micelle concentration (cmc). A relative density of 0.46 was obtained via pressure filtration at 4 MPa without a surfactant, and between 0.46 to 0.59 (C₆C₆PC to C₉C₉PC, respectively) for surfactant concentrations greater than the cmc. Comparing force measurements with rheology and packing density provides a basis for discussing the role of interparticle forces in ceramic powder processing via colloidal routes.     

Deformation Bands in Ceria-Stabilized Tetragonal Zirconia/Alumina : II, Stress-Induced Aging at Room Temperature

A stress-induced aging phenomenon is observed to occur at room temperature in deformation bands introduced into a 8.5 mol% ceria-stabilized tetragonal zirconia/alumina (CeTZP/A1₂O₃) composite by flexural loading. The aging occurs with time after unloading and in laboratory air. Over a period of 100 days, the concentration of monoclinic zirconia within a deformation band increases and, in addition, the wedge-shaped deformation band grows with time. Accompanying these two changes are an increase in the tensile stress in the remaining tetragonal zirconia within the deformation band and a consequential increase in the overall compressive stress within the band. The average value of the monoclinic concentration within the deformation band is found to increase parabolically with time, suggesting the mechanism responsible for the observed aging is diffusion limited. Away from the deformation bands, no aging is observed to occur, suggesting aging is stress dependent. Although a water-vapor-mediated mechanism cannot be ruled out, it is proposed that the observed aging is in fact due to a tensile stress assisted chemical reduction of Ce⁴⁺ to Ce³⁺ whose rate is controlled by the indiffusion of oxygen vacancies driven by the tensile stress gradient. It is further proposed that the deformation band grows with time, since the region ahead of the band is under tension and hence subject to an enhanced rate of reduction     

Aromatic bisphenol A-based elastomers via hydrosilylation chemistry

The preparation of highly aromatic elastomers from a bisphenol A-based divinyl-terminated resin and polymerization with various aromatic silane containing compounds utilizing a room temperature hydrosilylation reaction is demonstrated. The polymers exhibit high thermal and oxidative stability with 5% weight losses around 430 and 350°C and char yields ranging from 35% to 40%. The thermosets maintained their elastomeric properties with good hardness and mechanical properties as measured by elongation measurements. The toughness of the thermosets was not improved with the inclusion of aromatic moieties but the hardness did appear to increase with the addition of more aromatic groups.     

Optics clustered to output unique solutions: a multi-laser facility for combined single molecule and ensemble microscopy

Optics clustered to output unique solutions (OCTOPUS) is a microscopy platform that combines single molecule and ensemble imaging methodologies. A novel aspect of OCTOPUS is its laser excitation system, which consists of a central core of interlocked continuous wave and pulsed laser sources, launched into optical fibres and linked via laser combiners. Fibres are plugged into wall-mounted patch panels that reach microscopy end-stations in adjacent rooms. This allows multiple tailor-made combinations of laser colours and time characteristics to be shared by different end-stations minimising the need for laser duplications. This setup brings significant benefits in terms of cost effectiveness, ease of operation, and user safety. The modular nature of OCTOPUS also facilitates the addition of new techniques as required, allowing the use of existing lasers in new microscopes while retaining the ability to run the established parts of the facility. To date, techniques interlinked are multi-photon/multicolour confocal fluorescence lifetime imaging for several modalities of fluorescence resonance energy transfer (FRET) and time-resolved anisotropy, total internal reflection fluorescence, single molecule imaging of single pair FRET, single molecule fluorescence polarisation, particle tracking, and optical tweezers. Here, we use a well-studied system, the epidermal growth factor receptor network, to illustrate how OCTOPUS can aid in the investigation of complex biological phenomena.     

Analyzing clusters of class characteristics in OO applications

The transition from Java 1.4 to Java 1.5 has provided the programmer with more flexibility due to the inclusion of several new language constructs, such as parameterized types. This transition is expected to increase the number of class clusters exhibiting different combinations of class characteristics. In this paper we investigate how the number and distribution of clusters are expected to change during this transition. We present the results of an empirical study were we analyzed applications written in both Java 1.4 and 1.5. In addition, we show how the variability of the combinations of class characteristics may affect the testing of class members.     

Verification of evolving software via component substitutability analysis

This paper presents an automated and compositional procedure to solve the substitutability problem in the context of evolving software systems. Our solution contributes two techniques for checking correctness of software upgrades: (1) a technique based on simultaneous use of over-and under-approximations obtained via existential and universal abstractions; (2) a dynamic assume-guarantee reasoning algorithm—previously generated component assumptions are reused and altered on-the-fly to prove or disprove the global safety properties on the updated system. When upgrades are found to be non-substitutable, our solution generates constructive feedback to developers showing how to improve the components. The substitutability approach has been implemented and validated in the ComFoRT reasoning framework, and we report encouraging results on an industrial benchmark. This is an extended version of a paper, Dynamic Component Substitutability Analysis, published in the Proceedings of the Formal Methods 2005 Conference, Lecture Notes in Computer Science, vol. 3582, by the same authors. This research was sponsored by the National Science Foundation under grant nos. CNS-0411152, CCF-0429120, CCR-0121547, and CCR-0098072, the Semiconductor Research Corporation under grant no. TJ-1366, the US Army Research Office under grant no. DAAD19-01-1-0485, the Office of Naval Research under grant no. N00014-01-1-0796, the ICAST project and the Predictable Assembly from Certifiable Components (PACC) initiative at the Software Engineering Institute, Carnegie Mellon University. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing the official policies, either expressed or implied, of any sponsoring institution, the US government or any other entity.