Metathesis as a versatile tool in oleochemistry

Olefin metathesis, awarded with the Nobel Prize in Chemistry 2005 for Chauvin, Grubbs and Schrock, has emerged as a powerful tool for organic as well as polymer chemistry. In oleochemistry, this reaction is well known and has been applied for many decades. Examples include the functionalization of the double bonds of different oleochemicals or the (direct) polymerization of plant oils via metathesis. More recent developments, particularly the development of better and more robust catalysts, allow for highly efficient cross‐metathesis reactions opening new possibilities for the direct introduction of chemical functionalities. Within this contribution, the development of metathesis in oleochemistry will be discussed, covering self‐metathesis as well as more recent developments in the field of cross‐metathesis that lead to desired platform chemicals.     

Responses of ligamentous fibroblasts to mechanical stimulation

Mechanical stimulation, as provided by physiotherapy or controlled motion is essentially the only factor able to improve anterior cruciate ligament (ACL) healing. We investigate the cellular effects of such stimulus. Two types of stimulations are applied on canine ACL fibroblasts: repetitive stretch of an elastomeric adhesion substrate and a laminar flow of culture media over the culture surface. Cell orientation, proliferation rate, synthesis and type of collagen as well as proteoglycans (PG) synthesis and hydrodynamic characteristics have been studied. According to our results, the fibroblasts tend to align perpendicularly to the deformation axis of their substrate, and along a laminar flow. The shear stress induced by the laminar flow does not modify significantly proliferation rate nor extracellular matrix synthesis. Substrate stretching however, increases proliferation rate, collagen synthesis, mostly type III, and PG synthesis, principally of small sizes. The characteristics of fibroblasts submitted to repeated deformation match those of fibroblasts from ligament scar tissues. Their orientation perpendicular to substratum deformation differs from the one usually encountered in the undamaged tissue: aligned on the ligament axis.     

The topographic normalization of hyperspectral data: implications for the selection of spectral end members and lithologic mapping

Compact Airborne Spectrographic Imager (CASI) hyperspectral data is used to investigate the effects of topography on the selection of spectral end members, and to assess whether the topographic correction improves the discrimination of rock units for lithologic mapping. A publicly available Digital Elevation Model (DEM), at a scale of 1:50,000, is used to model the radiance variation of the scene as a function of topography, assuming a Lambertian surface. Skylight is estimated and removed from the airborne data using a dark object correction. The CASI data is corrected on a pixel-by-pixel basis to normalize the scene to a uniform solar illumination and viewing geometry. The results show that topography has the effect of expanding end member clusters at times resulting in the overlap of clusters and that the correction process can effectively reduce the variation in detected radiance due to changes in local illumination. When topographic effects are embedded in the hyperspectral data, methods typically used for the selection of end members, such as the convex hull method, can miss end members or result in the selection of nonrepresentative pixels as end members. Thus, end members selected by some conventional methods are very likely “incomplete” or “nonrepresentative” if the topographic effect is embedded in the data. As shown in this study, the topographic correction can reveal hidden end members and achieve a better representation of end members via the statistical center of isolated clusters.     

An investigation of carbon nanotube jet grinding

Since their observation in 1976 and 1991, carbon nanotubes (CNTs) have generated much interest due to their properties and potential applications. CNTs are tubular carbon molecules with remarkable mechanical, electrical, chemical and thermal properties, which make them useful in various applications. Industries producing CNTs via the fluidized bed chemical vapor deposition technique face challenges related to the size of CNT bundles. The two main challenges are agglomeration and agglomerate size distribution control. A solution to these challenges involves the use of jet mills to grind the CNT agglomerates. The goal of this study was to determine whether the nanotubes could be ground with air jets using a commercial jet mill and apply a two-parameter model to describe the grinding process. The present study has indicated that air-jet grinding of CNTs is feasible with a typical commercial jet mill. This paper presents the effect of operational parameters on the arithmetic mean diameter of the ground product. Sonic velocity through the grinding nozzles was required to obtain reasonable grinding rates and relatively narrow particle size distributions. This occurs at high air to solids feedrate ratios. Additionally, a simple attrition model can describe the grinding process in the spiral jet mill.     

Electrophilic chlorination of methane over superacidic sulfated zirconia

Catalytic chlorination of methane was studied over SO ₄ ^2– /ZrO₂, Pt/SO ₄ ^2– /ZrO₂, and Fe/Mn/SO ₄ ^2– /ZrO₂ solid superacid catalysts. The reactions were carried out in a continuous flow reactor under atmospheric pressure, at temperatures below 240°C, with a gaseous hourly space velocity of 1000 ml/g h and a methane to chlorine ratio of 4 to 1. At 200°C with 30% chlorine converted the selectivity in methyl chloride exceeds 90%. At more elevated temperatures, the selectivity decreases but stays above 80% in methyl chloride at 225°C using the sulfated zirconia catalysts. The selectivity can be enhanced by adding platinum to sulfated zirconia catalysts. An iron and manganese-doped catalyst exhibited excellent selectivities at somewhat lower conversions. Methyl chloride is obtained at 235°C in selectivities greater than 85%. No chloroform or carbon tetrachloride is formed. The electrophilic insertion involves electron-deficient metal-coordinated chlorine into the methane C-H bond.Catalysis by solid superacids, 29. For part 28 see ref. [14].     

Representations by Contact and Intersection of Segments

A necessary and sufficient condition is given for a connected bipartite graph to be the incidence graph of a contact family of segments and points. We deduce that any four-connected three-colorable plane graph is the contact graph of a family of segments and that any four-colored planar graph without an induced C₄ using four colors is the intersection graph of a family of straight line segments.     

Cracking and the Indentation Size Effect for Knoop Hardness of Glasses

The Knoop hardnesses of five glasses decreased with increasing load in accordance with the classic indentation size effect (ISE). At moderate loads, cracking dramatically altered the indentation sizes and the ISE trends in three of the five glasses. Cracked indentations were as much as 10 μm longer than uncracked indentations made under identical conditions. Diagonal length readings must be corrected for optical resolution limitations if low power lenses are used.     

Internal deterioration of concrete by the oxidation of pyrrhotitic aggregates

This paper presents research results on the causes of a severe concrete deterioration, which occurred in many building foundations approximately 2 years after construction. Concrete samples were investigated with X-ray diffraction (XRD) analysis, a scanning electron microscope (SEM) and a petrographic examination performed with a stereomicroscope. It was found that the early cracking of concrete stemmed from the oxidation of the pyrrhotite found in the anorthosite aggregates used to produce the concrete. The oxidation process led to the precipitation of iron hydroxides having a higher volume than the original pyrrhotite does. The presence of micas (biotite) close to the pyrrhotite seemed to promote and accelerate the oxidation process.     

Characterisation by TPR, XRD and NOx Storage Capacity Measurements of the Ageing by Thermal Treatment and SO2 Poisoning of a Pt/Ba/Al NOx-Trap Model Catalyst

The deactivation of a Pt/Ba/Al₂O₃ NO _x -trap model catalyst submitted to SO₂ treatment and/or thermal ageing at 800 °C was studied by H₂ temperature programmed reduction (TPR), X-ray diffraction (XRD) and NO _x storage capacity measurements.The X-ray diffractogram of the fresh sample exhibits peaks characteristic for barium carbonate. Thermal ageing leads to the decomposition of barium carbonate and to the formation of BaAl₂O₄. The TPR profile of the sulphated sample shows the presence of (i) surface aluminium sulphates, (ii) surface barium sulphates, (iii) bulk barium sulphates. The exposure to SO₂ after ageing leads to a small decrease of the surface barium-based sulphates, expected mainly as aluminate barium sulphates. This evolution can be attributed to a sintering of the storage material. TPR experiments also show that thermal treatment at 800 °C after the exposure to SO₂ involves the decomposition of aluminium surface sulphates to give mainly bulk barium sulphates, also pointed out by XRD. Thus, the thermal treatment at 800 °C leads to a stabilization of the sulphates.These results are in accordance with the NO _x storage capacity measurements. On non-sulphated catalysts, the treatment at 800 °C induces to a decrease of the NO _x storage capacity, showing that barium aluminate presents a lower NO _x storage capacity than barium carbonate. Sulphation strongly decreases the NO _x storage capacity of catalysts, whatever the initial thermal treatment, showing that barium sulphates inhibit the NO₂ adsorption. Moreover, the platinum activity for the NO to NO₂ oxidation is lowered by thermal treatments.