Soot oxidation catalyzed by a Cu/K/Mo/Cl catalyst: evaluation of the chemistry and performance of the catalyst

Several non-supported oxidic compounds potentially present in a Cu/K/Mo/Cl catalyst (copper molybdates, potassium molybdates, and a mixed copper-potassium molybdate (K₂Cu₂(MoO₄)₃)) have been tested individually on their activity in the oxidation of a model soot (Printex-U, which non-catalytically oxidizes at 875 K). These oxidic compounds are active between 665 and 720 K, but only after establishment of ‘tight contact’ between the catalyst and soot in a ball mill. Without the ball mill procedure (‘loose contact’) these oxides are less active (the soot oxidation temperature is shifted to about 790 K), while a ZrO₂ supported Cu/K/Mo/Cl catalyst still shows a high activity around 670 K. Hence, the ‘loose contact’ activity of the supported Cu/K/Mo/Cl catalyst is not explained by the presence of an active oxidic compound. DRIFT and XRD analyses have shown that addition of KCl to CuMoO₄ (two compounds present within the Cu/K/Mo/Cl catalysts) followed by calcination at 950 K in air, eventually results in the formation of a mixed potassium-copper molybdate. Simultaneously several volatile copper, potassium and chlorine containing compounds (e.g. K₂CuCl₄) are formed. These copper and chlorine containing compounds possess a high ‘loose contact’ soot oxidation activity between 600 and 690 K. A catalytic cycle, involving Cu₂OCl₂, is proposed to explain the high ‘loose contact’ activity of copper chlorides and supported Cu/K/Mo/Cl catalysts. The activity of the latter catalyst will be maintained as long as Cu₂OCl₂ can be reformed by reaction of copper molybdates with KCl, which serves as a chlorine supplier.     

Localized measurement of optical attenuation coefficients of atherosclerotic plaque constituents by quantitative optical coherence tomography

Optical coherence tomography (OCT) is a novel, high-resolution diagnostic tool that is capable of imaging the arterial wall and plaques. The differentiation between different types of atherosclerotic plaque is based on qualitative differences in gray levels and structural appearance. We hypothesize that a quantitative data analysis of the OCT signal allows measurement of light attenuation by the local tissue components, which can facilitate quantitative spatial discrimination between plaque constituents. High-resolution OCT images (at 800 nm) of human atherosclerotic arterial segments obtained at autopsy were histologically validated. Using a new, simple analysis algorithm, which incorporates the confocal properties of the OCT system, the light attenuation coefficients for these constituents were determined: for diffuse intimal thickening (5.5 +/- 1.2 mm(-1)) and lipid-rich regions (3.2 +/- 1.1 mm(-1)), the attenuation differed significantly from media (9.9 +/- 1.8 mm(-1)), calcifications (11.1 +/- 4.9 mm(-1) ) and thrombi (11.2 +/- 2.3 mm(-1)) (p < 0.01). These proof of principle studies show that simple quantitative analysis of the OCT signals allows spatial determination of the intrinsic optical attenuation coefficient of atherosclerotic tissue components within regions of interest. Combining morphological imaging by OCT with the observed differences in optical attenuation coefficients of the various regions may enhance discrimination between various plaque types.     

The influence of cap rock composition on hydrocarbon seep type in the Zagros oil fields,a study using Advanced Spaceborne Thermal Emission and Reflection Radiometer mineral map

The persistent natural hydrocarbon seepage in onshore basins challenges observation and exploration technologies, which are required to document and assess these valuable indications of the presence of oil and gas in the subsurface. This paper aims at demonstrating the relationship between the compositional variation of an evaporite cap rock and the types of seeps occurring at the surface. For this purpose, the multispectral Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) data was utilized for mapping mineral variations of a petroleum system in the Zagros oil fields. Relative absorption-band depth (RBD), band rationing and the boosted regression trees (BRT) were applied to enhance and classify the mineral composition of evaporite, sandstone, and marly limestone formations. The gas seeps were associated with the areas of gypsum-bearing evaporite cap rock while oil seeps were mostly associated with calcite and clay zones within the cap rock, which was more prone to fracturing during the tectonic activities of the basin. It is suggested that the application of remote sensing in the oil and gas industry could be widened by detection of sleep-induced alteration to assess the efficiency of cap rock and to evaluate the productivity of reservoirs at a regional scale.     

Metal Organic Framework Crystals in Mixed‐Matrix Membranes: Impact of the Filler Morphology on the Gas Separation Performance

Mixed‐matrix membranes comprising NH₂‐MIL‐53(Al) and Matrimid or 6FDA‐DAM have been investigated. The metal organic framework (MOF) loading has been varied between 5 and 20 wt%, while NH₂‐MIL‐53(Al) with three different morphologies, nanoparticles, nanorods, and microneedles has been dispersed in Matrimid. The synthesized membranes have been tested in the separation of CO₂ from CH₄ in an equimolar mixture. At 3 bar and 298 K for 8 wt% MOF loading, incorporation of NH₂‐MIL‐53(Al) nanoparticles leads to the largest improvement compared to nanorods and microneedles. The incorporation of the best performing filler, i.e., NH₂‐MIL‐53(Al) nanoparticles, into the highly permeable 6FDA‐DAM has a larger effect, and the CO₂ permeability increases up to 85% with slightly lower selectivities for 20 wt% MOF loading. Specifically, these membranes have a permeability of 660 Barrer with a CO₂/CH₄ separation factor of 28, leading to a performance very close to the Robeson limit of 2008. Furthermore, a new non‐destructive technique based on Raman spectroscopy mapping is introduced to assess the homogeneity of the filler dispersion in the polymer matrix. The MOF contribution can be calculated by modeling the spectra. The determined homogeneity of the MOF filler distribution in the polymer is confirmed by focused ion beam scanning electron microscopy analysis.     

A Genus-Wide Bioactivity Analysis of Daboia (Viperinae: Viperidae) Viper Venoms Reveals Widespread Variation in Haemotoxic Properties

The snake genus Daboia (Viperidae: Viperinae; Oppel, 1811) contains five species: D. deserti, D. mauritanica, and D. palaestinae, found in Afro-Arabia, and the Russell’s vipers D. russelii and D. siamensis, found in Asia. Russell’s vipers are responsible for a major proportion of the medically important snakebites that occur in the regions they inhabit, and their venoms are notorious for their coagulopathic effects. While widely documented, the extent of venom variation within the Russell’s vipers is poorly characterised, as is the venom activity of other species within the genus. In this study we investigated variation in the haemotoxic activity of Daboia using twelve venoms from all five species, including multiple variants of D. russelii, D. siamensis, and D. palaestinae. We tested the venoms on human plasma using thromboelastography, dose-response coagulometry analyses, and calibrated automated thrombography, and on human fibrinogen by thromboelastography and fibrinogen gels. We assessed activation of blood factors X and prothrombin by the venoms using fluorometry. Variation in venom activity was evident in all experiments. The Asian species D. russelii and D. siamensis and the African species D. mauritanica possessed procoagulant venom, while D. deserti and D. palaestinae were net-anticoagulant. Of the Russell’s vipers, the venom of D. siamensis from Myanmar was most toxic and D. russelli of Sri Lanka the least. Activation of both factor X and prothrombin was evident by all venoms, though at differential levels. Fibrinogenolytic activity varied extensively throughout the genus and followed no phylogenetic trends. This venom variability underpins one of the many challenges facing treatment of Daboia snakebite envenoming. Comprehensive analyses of available antivenoms in neutralising these variable venom activities are therefore of utmost importance.     

Strong overtones and combination bands in ultraviolet resonance Raman spectroscopy

Ultraviolet resonance Raman spectroscopy is carried out using a continuous wave frequency-doubled argon ion laser operated at 229, 244, and 257 nm in order to characterize the overtones and combination bands for several classes of organic compounds in liquid solutions. Contrary to what is generally anticipated, for molecules such as pyrene and anthracene, strong overtones and combination bands can show up; it is demonstrated that their intensity depends critically on the applied laser wavelength. If the excitation wavelength corresponds with a purely electronic transition--this applies to a good approximation for 244-nm excitation in the case of pyrene and for 257-nm excitation in the case of anthracene--mostly fundamental vibrations (up to 1700 cm(-1)) are observed. Overtones and combination bands are detected but are rather weak. However, if the laser overlaps with the vibronic region--as holds for 229- and 257-nm excitation for pyrene and 244-nm excitation for anthracene--very strong bands are found in the region 1700-3400 cm(-1). As illustrated for pyrene at 257 nm, all these bands can be assigned to first overtones or binary combinations of fundamental vibrations. Their intensity distribution can roughly be simulated by multiplying the relative intensities of the fundamental bands. Significant bands can also be found in the region 3400-5000 cm(-1), corresponding with second overtones and ternary combinations. It is shown that these findings are not restricted to planar and rigid molecules with high symmetry. Substituted pyrenes exhibit similar effects, and relatively strong overtones are also observed for adenosine monophosphate and for abietic acid. The reasons for these observations are discussed, as well as the potential applicability for analytical purposes.     

RESPONSE TO NELDER AND LEE

Sufficient dimension-reduction methods provide effective ways to visualize discriminant analysis problems. For example, Cook and Yin showed that the dimension-reduction method of sliced average variance estimation (SAVE) identifies variates that are equivalent to a quadratic discriminant analysis (QDA) solution. This article makes this connection explicit to motivate the use of SAVE variates in exploratory graphics for discriminant analysis. Classification can then be based on the SAVE variates using a suitable distance measure. If the chosen measure is Mahalanobis distance, then classification is identical to QDA using the original variables. Just as canonical variates provide a useful way to visualize linear discriminant analysis (LDA), so do SAVE variates help visualize QDA. This would appear to be particularly useful given the lack of graphical tools for QDA in current software. Furthermore, whereas LDA and QDA can be sensitive to nonnormality, SAVE is more robust.     

The pressure drop experiment to determine slug lengths in multiphase monoliths

The length of the liquid slugs, that separate the elongated bubbles in Taylor flow, is an important parameter for mass transfer, flow stability and pressure drop in capillary microchannels. In this work, pressure drop measurements are used to determine the length of slug in Taylor flow in downflow monoliths. The method is sensitive if the slugs are relatively short, less than 10 times the channel diameter. The pressure drop measurements are a cheap and fast alternative to tomographic or electric methods. Experiments using different distributors indicate that the slug length varies significantly with changes in the hydrodynamics in the feed section of the monoliths. Slug length correlations that are based on parameters inside the channels can therefore not safely be used for a different setup. As a result, the slug length should be measured in each experimental setup, which makes a inexpensive and robust method to do so very welcome.     

Modelling of reactive stripping in monolith reactors

In this work, (reactive) stripping carried out in film flow monolith reactors developed for counter-current operation is investigated. Usually mass transfer in reactive separation has to be determined experimentally due to the complex flow patterns. However, monoliths have a simple geometry; only laminar flow is present throughout the column. This allows the calculation of the thickness of the liquid layer directly using Navier–Stokes equations. With this thickness known, the mass transfer can be calculated based on the convection in axial direction, diffusion in radial direction and vapour–liquid equilibrium. A model has been developed and implemented in Fortran^® based on the concept of a direct solution of convective diffusion equations, using the Thomas algorithm for solving the counter-current operation mode. Experimental data from literature have been used to validate the model for a binary and a multi-component system. The stripping of oxygen from saturated water by nitrogen was modelled assuming Fickian diffusion and vapour–liquid transfer based on the Henry constants. In a second step, multi-component diffusion and complex mass transfer at the interface were taken into account to describe the stripping of water by nitrogen from a mixture of hexyl-octanoate and cumene (solvent) under reactive stripping conditions.     

CO2 gasification of carbon catalysed by alkali metals: Reactivity and mechanism

A systematic study of the catalytic activity of alkali metal carbonates on the CO₂ gasification of activated carbon revealed the following order: Li < Na < K < Rb < Cs. Outgassing in an inert gas results in a pronounced activity decrease for Cs, whereas the other alkali metals show a slight increase. The activated carbon itself is unaffected. Apparent activation energies for the CO₂ gasification are also changed by outgassing and decrease from Li to Cs. Upon outgassing of the samples, CO₂ and CO are released in five distinguishable temperature regions, arising from decomposition of surface complexes and carbonate-like species, gasification phenomena and reduction of oxidic species. Outgassing patterns of all alkali metals are quite similar. During alkali-metal-catalysed gasification in CO₂ two types of oxidic species are present: surface bonded -OM species of high stability and oxidic species having less interaction with the carbon surface.