Cobalt-Molybdenum Sulfide Catalysts Prepared by In Situ Activation of Bimetallic (Co-Mo) Alkylthiomolybdates

Unsupported cobalt-molybdenum sulfide catalysts were prepared from bimetallic CoMo alkyl precursors by in situ activation during the hydrodesulfurization (HDS) of dibenzothiophene (DBT). The bimetallic CoMo precursors were prepared by reaction of tetraalkylammonium thiomolybdate salts, (R₄N)₂MoS₄ (where R = H, methyl, butyl, pentyl or hexyl), with CoCl₂ in water at a Co/Mo molar ratio of 0.3. These catalysts exhibit a Swiss-cheese-like morphology, high surface areas (from 52 up to 320 m²/g), high content of carbon (C/Mo = 2.2-3.3) and type IV adsorption-desorption isotherms of nitrogen. The in situ activation of these tetraalkylammonium thiobimetalate precursors leads to a mesoporous structure with pore size ranging from 2 to 4.5 nm. X-ray diffraction showed that the structure of unsupported cobalt-molybdenum sulfide catalysts corresponds to a poorly crystalline structure characteristic of 2H-MoS₂ with low-stacked layers. The nature of the alkyl group strongly affects both the surface area and the HDS activity. The catalytic activity is strongly enhanced when using carbon-containing precursors; the CoMo catalysts prepared by in situ activation of Co/[N(C₄H₉)₄]₂MoS₄ presents the highest HDS activity. The highest surface area of the catalysts was observed for the CoMo catalyst formed from Co/[N(C₆H₁₃)₄N]₂MoS₄.     

The role of lanthana loading on the catalytic properties of Pd/Al2O3-La2O3 in the NO reduction with H2

The role of La₂O₃ loading in Pd/Al₂O₃-La₂O₃ prepared by sol–gel on the catalytic properties in the NO reduction with H₂ was studied. The catalysts were characterized by N₂ physisorption, temperature-programmed reduction, differential thermal analysis, temperature-programmed oxidation and temperature-programmed desorption of NO.

The physicochemical properties of Pd catalysts as well as the catalytic activity and selectivity are modified by La₂O₃ inclusion. The selectivity depends on the NO/H₂ molar ratio (GHSV = 72,000 h⁻¹) and the extent of interaction between Pd and La₂O₃. At NO/H₂ = 0.5, the catalysts show high N₂ selectivity (60–75%) at temperatures lower than 250 °C. For NO/H₂ = 1, the N₂ selectivity is almost 100% mainly for high temperatures, and even in the presence of 10% H₂O vapor. The high N₂ selectivity indicates a high capability of the catalysts to dissociate NO upon adsorption. This property is attributed to the creation of new adsorption sites through the formation of a surface PdO_x phase interacting with La₂O₃. The formation of this phase is favored by the spreading of PdO promoted by La₂O₃. DTA shows that the phase transformation takes place at temperatures of 280–350 °C, while TPO indicates that this phase transformation is related to the oxidation process of PdO: in the case of Pd/Al₂O₃ the O₂ uptake is consistent with the oxidation of PdO to PdO₂, and when La₂O₃ is present the O₂ uptake exceeds that amount (1.5 times). La₂O₃ in Pd catalysts promotes also the oxidation of Pd and dissociative adsorption of NO mainly at low temperatures (<250 °C) favoring the formation of N₂.     

Malicious uses of blockchains by malware: from the analysis to Smart-Zephyrus

The permanent availability and relative obscurity of blockchains is the perfect ground for using them for malicious purposes. However, the use of blockchains by malwares has not been characterized yet. This paper analyses the current state of the art in this area. One of the lessons learned is that covert communications for malware have received little attention. To foster further defence-oriented research, a novel mechanism (dubbed Smart-Zephyrus) is built leveraging smart contracts written in Solidity. Our results show that it is possible to hide 4 Kb of secret in 41 s. While being expensive (around USD 1.82 per bit), the provided stealthiness might be worth the price for attackers.

     

Metabolic role of glutamine and its importance in nutritional therapy

The advances in the field of nutritional support have made certain nutrients very relevant, which, although they have been known for a long time, at present represent an important chapter in nutrition, entering into what is known as "nutritional pharmacology". Among these nutrients is glutamine, an amino acid classified as non-essential, but which in certain circumstances may become to be considered as an "essential nutrient". In the present review, a review is made of its metabolic role, synthesis and degradation, metabolic routes and functions under normal conditions as well as under critical conditions. It is known that glutamine stimulates the synthesis and inhibits the degradation of proteins, it is an important vehicle for the transport of nitrogen and carbon within the tissues, it stimulates the synthesis of hepatic glycogen, it is an energy source for cell division, for the growth of different cells of rapid replication, such as enterocytes, colonocytes, and fibroblasts, as well as for other cells of the immune system, such as lymphocytes and macrophages. Thus its role in the maintenance of structure, in metabolism and function of the intestinal mucosa, and in dysfunctions of the immune system. In parenteral nutrition, at present there are no preparations which include it, given the stability problems which it presents, although attempts have been made to resolve this, using different possibilities, such as di-peptides. However, in enteral nutrition, the diets tend to include it, although in a small proportion. Nevertheless, having recognized its beneficial role in a certain type of patients, at present there are diets which contain glutamine in higher doses, with the object of attempting to cover the increased demands of glutamine which shall arise in these situations. The inclusion of glutamine in nutritional therapy is supported by multiple studies which reflect the beneficial effect of this nutrient, both in enteral nutrition as in parenteral nutrition.     

The spring paradigm in tracking control of simple mechanical systems

An intrinsic formulation of geometric proportional–derivative tracking control for fully actuated mechanical systems is developed. The region of stability is determined directly from the size of the system’s injectivity radius and, for a restricted set of control problems, the system’s locus of cut points about a desired reference point. Exponential stability is obtained under certain boundedness conditions. For controlled motion along a geodesic, the proffered scheme yields a particularly simple and elegant manifestation of the underlying use of the mass–spring–damper paradigm in the control design methodology.     

Computerized design of advanced straight and skew bevel gears produced by precision forging

The computerized design of advanced straight and skew bevel gears produced by precision forging is proposed. Modifications of the tooth surfaces of one of the members of the gear set are proposed in order to localize the bearing contact and predesign a favorable function of transmission errors. The proposed modifications of the tooth surfaces will be computed by using a modified imaginary crown-gear and applied in manufacturing through the use of the proper die geometry. The geometry of the die is obtained for each member of the gear set from their theoretical geometry obtained considering its generation by the corresponding imaginary crown-gear. Two types of surface modification, whole and partial crowning, are investigated in order to get the more effective way of surface modification of skew and straight bevel gears. A favorable function of transmission errors is predesigned to allow low levels of noise and vibration of the gear drive. Numerical examples of design of both skew and straight bevel gear drives are included to illustrate the advantages of the proposed geometry.     

Learning Dextrous Manipulation Skills for Multifingered Robot Hands Using the Evolution Strategy

We present a method for autonomous learning of dextrous manipulation skills with multifingered robot hands. We use heuristics derived from observations made on human hands to reduce the degrees of freedom of the task and make learning tractable. Our approach consists of learning and storing a few basic manipulation primitives for a few prototypical objects and then using an associative memory to obtain the required parameters for new objects and/or manipulations. The parameter space of the robot is searched using a modified version of the evolution strategy, which is robust to the noise normally present in real-world complex robotic tasks. Given the difficulty of modeling and simulating accurately the interactions of multiple fingers and an object, and to ensure that the learned skills are applicable in the real world, our system does not rely on simulation; all the experimentation is performed by a physical robot, in this case the 16-degree-of-freedom Utah/MIT hand. Experimental results show that accurate dextrous manipulation skills can be learned by the robot in a short period of time. We also show the application of the learned primitives to perform an assembly task and how the primitives generalize to objects that are different from those used during the learning phase.