Dehydrocyclization of Alkanes Over Zeolite-Supported Metal Catalysts: Monofunctional or Bifunctional Route

The direct catalytic conversion of alkanes into aromatics has found potentially important industrial applications. Initially only alkanes with 6 and more carbon atoms in the chain were concerned. Supported platinum catalysts were found active for the aromatization of alkanes; the drawbacks of these catalysts were their deactivation with time on stream and the existence of simultaneous parallel reactions. Much discussion has been published on the aromatization of C₆₊ alkanes. A bifunctional mechanism which involves both the metal and the acid sites of the support and a monofunctional mechanism involving only the metallic sites operate over, respectively, Pt supported on acidic support and Pt supported on nonacidic support. In the present review the mechanisms proposed for the aromatization of alkanes are described. Over monofunctional Pt catalysts two possible mechanisms prevail: 1,6 ring closure on the Pt surface involving primary and secondary C-H bond rupture, followed by dehydrogenation of the cycloalkanes into aromatics (1,5 ring closure to a lesser extent also contributes to aromatic production); or dehydrogenation of the alkanes into olefins, dienes, and trienes followed by thermal ring closure. Zeolites were found most suitable as support for preparing catalysts more active and more selective in the alkane aromatization. In addition catalysts based on noble metals supported on zeolite appeared more resistant against deactivation by coke. In this review the aromatization of hexane, heptane, and octane over Pt-zeolite catalysts is discussed in detail. Comparisons between different zeolite structures and different dehydrogenation sites are given. In particular a critical analysis of the results and interpretation concerning Pt-KL catalysts strongly suggests that the exceptional high selectivity towards aromatization of n-hexane exhibited by Pt-KL could not be explained by only the nest or constraint effect exerted by the channel dimension and morphology, not by only the terminal cracking properties, not by only the partial electron transfer from the zeolite support to the Pt particles, and not by only the Pt particle size. Zeolite structure also affects the aromatic product distribution, in particular when the alkane contains more than 7 carbon atoms. It is shown how Pt on medium-pore zeolites such as In-ZSM-5, silicalites will favor the aromatization of C₈ alkane isomers into ethylbenzene-styrene with respect to other C₈ aromatics. Aromatization of light alkanes, C₂-C₅, requires the increase of the hydrocarbon chain length up to 6 carbon atoms and higher, followed by cyclization reaction. Recently new processes to convert C₂-C₅ alkanes into aromatics have been disclosed, M2-forming from Mobil, Cyclar from BP-UOP, and Aroforming from IFP-Saluted. In general these processes use bifunctional catalysts possessing a dehydrogenating and an acid function. The catalysts consist of a metal ion or metal oxide supported on a microporous acid solid. In this review we analyze the results concerning mainly platinum supported on pentasil-type zeolite. It is shown that althoug Pt has better dehydrogenating properties as compared with gallium and zinc, the efficiency of catalysts based on Pt-ZSM-5 for light alkane aromatization is less because undersirable reactions such as hydrogenolysis and ethene (olefins) hydrogenation occur on the platinum surface, resulting in the production of unreactive alkanes, CH₂, C₂H₆. These drawbacks could be partially suppressed by alloying Pt and by increasing the reaction temperature.     

Observability of linear systems with commensurate delays and unknown inputs

This paper investigates the observability analysis for linear time systems whose outputs are affected by unknown inputs. Three different definitions of observability are proposed. By introducing the Smith form and comparing the invariant factors, a sufficient condition is deduced for each proposed observability definition. Three examples are given for the purpose of highlighting the effectiveness of the proposed approach.     

Fractal Characteristics of Fracture Surfaces

Quantitative fractography is often used to study material failure mechanisms. During calculation of surface or profile roughness parameters, the magnification used in obtaining fractographic data is found to influence the value of the parameters. Fractal geometry has been developed into a tool capable of defining surface and profile topography without sensitivity to magnification, and several studies have related fractal dimension ( D _F) to other physical or mechanical properties. In this study, we obtained the fractal dimension of profiled fracture surfaces of one glass and three proprietary dental porcelains. The fracture toughness ( K _1c) of these materials was also measured using the indentation-strength method. Results show the surfaces to be fractal. No quantitative relationship between fractal dimension and toughness was found. Differences in K _1c were demonstrated between some materials. It is postulated that the size range within which fractal dimension can be defined as constant is dependent on the toughening mechanism, and that the relationship between K _Ic and D _F cannot be identical for all materials.     

Mechanisms of hydrocarbon conversion reactions on heterogeneous catalysts: analogies with organometallic chemistry

Catalysis is central to most industrial processes for chemical manufacturing. As catalytic processes have become more complex and more demanding, selectivity has become the central issue in their design. Selectivity is defined by the relative rates of competing reaction pathways available to crucial intermediates, and can be controlled by subtle changes in the nature of the catalyst, the reactants, and/or the reaction conditions. In order to be able to do this in a systematic manner, a good understanding of the catalytic reaction mechanisms is needed. Here a connection is drawn between the key elementary steps comprising hydrocarbon conversion reactions on surfaces and those known to occur on discrete organometallic complexes. This way, the hydrogenation, dehydrogenation, hydrogenolysis, chain growth, and isomerization reactions typical in heterogeneous catalysis are redefined in terms of hydride elimination, oxidative addition, reductive elimination, migratory insertion, and 1, 2-shift elementary steps, among others. It is suggested that the knowledge already available from organometallic chemistry can be used to further advance the understanding of the surface science involved in heterogeneous catalysis. Thanks to the commonality of the chemistry involved, a better synergy could also be established between homogeneous and heterogeneous catalytic development. These ideas are discussed in this article in a critical and personal way.*Invited contribution to the special volume entitled The Interface between Heterogeneous and Homogeneous Catalysis, stemming from contributions at the recent International Symposium on Relations between Heterogeneous and Homogeneous Catalysis, and dedicated to the memory of Robert L. Burwell.     

Vessel Inspection: A Micro-Aerial Vehicle-based Approach

Vessel maintenance entails periodic visual inspections of the internal and external parts of the hull in order to detect the typical defective situations affecting metallic structures, such as coating breakdown, corrosion, cracks, etc. The main goal of project MINOAS is the automation of the inspection process, currently undertaken by human surveyors, by means of a fleet of robotic agents. This paper overviews an approach to the inspection problem based on an autonomous Micro Aerial Vehicle (MAV) which, as part of this fleet, is in charge of regularly supplying images that can teleport the surveyor from a base station to the areas of the hull to be inspected. The control software approach adopted for the MAV is fully described, with a special emphasis on the self-localization capabilities of the vehicle. Experimental results showing the suitability of the platform to the application are as well reported and discussed.     

Change detection by probabilistic segmentation from monocular view

We present a method for foreground/background video segmentation (change detection) in real-time that can be used, in applications such as background subtraction or analysis of surveillance cameras. Our approach implements a probabilistic segmentation based on the Quadratic Markov Measure Field models. This framework regularizes the likelihood of each pixel belonging to each one of the classes (background or foreground). We propose a new likelihood that takes into account two cases: the first one is when the background is static and the foreground might be static or moving (Static Background Subtraction), the second one is when the background is unstable and the foreground is moving (Unstable Background Subtraction). Moreover, our likelihood is robust to illumination changes, cast shadows and camouflage situations. We implement a parallel version of our algorithm in CUDA using a NVIDIA Graphics Processing Unit in order to fulfill real-time execution requirements.     

Agricultural use of three organic residues: effect on orange production and on properties of a soil of the ‘Comarca Costa de Huelva’ (SW Spain)

Disposal of urban, agricultural and industrial organic residues impliesan increasing problem because of all the economic and environmentalrepercussions involved. One of the most adequate ways of managing this problemis the agricultural use of these wastes as organic amendments. Three organicresidues (AC, olive mill waste water sludge compost; MWC, municipal solid wastecompost; and PS, paper mill sludge) were used in a 3-year field experimentinvolving orange production. The effect of their application on crop productionand on soil quality was investigated. Soil samples (0–20 cm depth)collected 11 months after the last soil amendment were analysed for: pH and EC,Kjeldahl-N, available-P, available-K, total organic carbon, humic substances,dehydrogenase, phosphatase, -glucosidase, urease andbenzoyl-argininamidehydrolysing protease (BAA-protease) activities. Generally, the application of the MWC and PSincreased orange yield when compared to control. Moreover, total organic carbonand humic substances significantly increased in soils treated with all theorganic amendments. Organic fertilisation increased the Kjeldahl-N andavailable-P contents of the soil. The application of the organic residues also causedsignificant increases in dehydrogenase, -glucosidase, urease andBAA-protease activities of the soil. Significant positive correlations (p <0.01) between these enzymatic activities and total organic carbon were foundforall treatments. Significant positive correlation between dehydrogenase, urease,-glucosidase, and BAA-protease and orange yield was also found. However,a clear inhibition of phosphatase activity was observed in soils treated withPS. The results indicate that the repeated application to the soil of moderateamounts of organic amendments has positive effects on the chemical andbiochemical properties of the soil, as well as on the orange yield.     

Synthesis of deuterated cyclopropene fatty esters structurally related to palmitic and myristic acids

To develop a synthesis of tritiated cyclopropene fatty acids (CPFA), compounds that should prove useful for affinity labeling of desaturases in insect pheromone biosynthetic studies, a series of novel, selectively deuterated CPFA analogues was prepared and characterized. In methyl [16-²H]12,13-methylene-12-hexadecenoate, the incorporation of deuterium was achieved by treatment of the corresponding ω-chloro derivative with sodium borodeuteride in dimethylsulfoxide at 70°C for 24 h (67% yield) following conventional procedures. Alkylation of the tetrahydropyranyl derivative of 13-tridecynol in the presence of lithium diisopropylamide in tetrahydrofuran at −20°C with 1-chloro-3-iodopropane in hexamethylphosphoramide, followed by Jones oxidation of the crude product, yielded 16-chloro-12-hexadecynoic acid (54%), which was esterified to the corresponding methyl ester by treatment with potassium carbonate and methyl iodide in dimethylformamide. Treatment of this acetylenic ester with ethyldiazoacetate in the presence of activated copper-bronze as catalyst followed by hydrolysis in KOH solution at room temperature yielded 16-chloro-12,13-(carboxymethylene)-12-hexadecenoic acid. This diacid was treated with excess oxalyl chloride to give the corresponding diacyl chloride, which was decarbonylated in a diethyl ether solution with zinc chloride, and the cyclopropenium ions thus formed were added at −40°C to a methanolic sodium hydroxide solution of sodium borohydride to give methyl 16-chloro-12,13-methylene-12-hexadecenoate. Analogous procedures were followed to prepare methyl [17-²H]10,11-methylene-10-hexadecenoate, methyl [17-²H]11,12-methylene-11-hexadecenoate and methyl [17-²H]12,13-methylene-12-hexadecenoate from the corresponding diacids using sodium borodeuteride in the reduction of the cyclopropenium ions. Alternatively, methyl [2,2,3,3-²H₄]hexadecynoate, prepared by reaction of methyl 2,11-hexadecadiynoate with magnesium in deuterated methanol at room temperature, was submitted to the above cyclopropenylation and reductive decarbonylation sequence to give methyl [2,2,3,3,17-²H₅]-11,12-methylene-11-hexadecenoate. In summary, complementary methods for the selective incorporation of one to five deuterium atoms into cyclopropene fatty acids, at different sites, in moderate to high yields have been developed. The methods should easily be applicable to the preparation of the corresponding tritiated analogues.     

Composition and structure of triacylglycerols in brown adipose tissue of rats fed fish oil

This study examines the incorporation of highly unsaturated n−3 fatty acids (HUFA) into triacylglycerols (TAG) of brown adipose tissue (BAT), and their effect on the positional distribution of saturated (SFA) and of unsaturated (UFA) 16- or 18-carbon fatty acids. To this end, rats were fed a fish oil diet for up to four weeks. The stereospecific analysis of TAG was based on generation ofsn-1,2- andsn-2,3-acylglycerols by Grignard degradation, followed by synthesis of phosphatidic acid and specific hydrolysis with phospholipase A₂. From the end of the first week of fish oil feeding, a steady-state in the fatty acid composition of TAG in BAT was reached. HUFA concentration increased 30-fold, mainly at the expense of n−9 UFA and of SFA. The amount of SFA decreased selectively at position 3, where these fatty acids were progressively replaced by n−3 HUFA. By contrast, the amount of UFA decreased at all positions, and their positional distribution was not affected. About 60% of HUFA was incorporated at position 3. Nearly twice as much 22∶6n−3 was incorporated into TAG than had been previously observed in white adipose tissue (WAT) [Leray, C., Raclot, T., and Groscolas, R. (1993)Lipids 28, 279–284]. At the steady-state, the distribution of HUFA was characterized by high proportions of 22∶6n−3 and 20∶5n−3 in position 3. Moreover, in each position of TAG, a steady level was reached rapidly (within 1 wk). It is concluded that, during fish-oil feeding, fatty acids in TAG of BAT show characteristic time-course changes that lead to a characteristic composition and a tissue-specific positional distribution. This suggests that adipose tissue has its own specificity in controlling the build-up of TAG stores, which is likely to be regulated by the specificity of acylating enzymes as well as molecular rearrangements.     

Modelling the effects of human papillomavirus in cervical cells

Worldwide, cervical cancer is the second most common cancer in women, after breast cancer. The prevalence of this malignant disease is estimated at 1.4 million cases worldwide, causing about 290,000 deaths and 500,000 new cases per year, of which 80% correspond to women living in developing countries. In this work we propose a family of ordered models for basal cells of the cervix corresponding to different stages ranging from normal cells to the formation of precancerous lesions. We analyse the first member of the family analytically and for the second member we developed a non-standard numerical method in order to extract some biological information.