Enantiospecific synthesis fromd-fructose of (2S,5R)- and (2R,5R)-2-methyl-1,6-dioxaspiro[4.5]decane [the odor bouquet minor components ofParavespula vulgaris (L.)]

The synthesis of (2S,5R)-(1) and (2R,5R)-2-methyl-1,6-dioxaspiro [4.5]decane (2) from (2RS,5R,8R,9R,10S)-8,9,10-trihydroxy-2-methyl-1, 6-dioxaspiro[4.5]decane (8), obtained in five steps fromd-fructose using Wittig's methodology, reduction, and spiroketalation, has been accomplished by a Corey dideoxygenation at C-8,9, followed by a Barton deoxygenation at C-10, of the appropriately protected derivatives.Enantiospecific synthesis of spirocetals. Part V. For Part IV, see Izquierdo et al. (1992).     

Lightweight dynamic symmetry breaking

Symmetries in constraint problems present an opportunity for reducing search. This paper presents Lightweight Dynamic Symmetry Breaking, an automatic symmetry breaking method that is efficient enough to be used as a default, since it never yields a major slowdown while often giving major performance improvements. This is achieved by automatically exploiting certain kinds of symmetry that are common, can be compactly represented, easily and efficiently processed, automatically detected, and lead to large reductions in search. Moreover, the method is easy to implement and integrate in any constraint system. Experimental results show the method is competitive with the best symmetry breaking methods without risking poor performance.     

Computational Aspects of Uncertainty Profiles and Angel-Daemon Games

We analyze the complexity of equilibria problems for a class of strategic zero-sum games, called angel-daemon games. Those games were introduced to asses the performance of the execution of a web orchestration on a moderate faulty or under stress environment. Angel-daemon games are a natural example of zero-sum games whose representation is naturally succinct. We show that the problems of deciding the existence of a pure Nash equilibrium or of a dominant strategy for a given player are ${\Sigma}^{p}_{2}$ -complete. Furthermore, computing the value of an angel-daemon game is EXP-complete. Thus, our results match the already known classification of the corresponding problems for the generic families of succinctly represented games with exponential number of actions.     

Reciprocal Tree-Like Fractal Structures

Sometimes the complex structures of nature inspire human constructions. Gothic construction has shown that forces can cross space along intricate paths that may even be arbitrary if correctly dimensioned. In some way, ribbed structures are like trees where the branches conduct forces instead of sap; they operate as branches and trunks descending by fractal ways. Here we discuss reciprocal tree-like fractal structures and the difficulty in their design and erection and solutions for constructive details, as well as the possible analytical questions and automatic generation by means of proper software. The results are shown in the design of the Natural Interpretation Centre in Melilla where we have proposed two connected trees like shown at figures included below.     

Effect of patchwise slip on fluid flow

In this paper, we show that large connected slip patches (hydrophobic patches) are a necessity to induce macroscopic slip effects of water flow in microchannels. For this purpose, the 2D fluid flow between a planar stationary surface with alternating stick and slip patches and a parallel planar surface moving with a constant relative velocity has been studied by computer simulations based on Navier–Stokes equations. A slip patch is defined as the slipping length in a 2D system or a slip area of the surface in a 3D system. The simulations reveal that the ratio (size of each slip patch)/(distance between the two parallel interfaces) has profound effect on the viscous stress on the moving surface when this ratio is around and above one. However, when the ratio is much below one, the effect of the slip patches are minor, even if the area fraction of slip patches are higher than 50 %. Obviously, the stick patches adjacent to the slip patches act as effective barriers, preventing the fluid velocity to increase near the surface with alternating stick and slip patches. The obtained results are scalable and applicable on all length scales, with an exception for narrow channels in the subnano regime, i.e. <1 nm where specific effects as the atomistic composition and the nanostructure of the wall as well as the interactions between the wall and the water molecules have an effect.     

A method for predicting the probability of business network profitability

In the design phase of business collaboration, it is desirable to be able to predict the profitability of the business-to-be. Therefore, techniques to assess qualities such as costs, revenues, risks, and profitability have been previously proposed. However, they do not allow the modeler to properly manage uncertainty with respect to the design of the considered business collaboration. In many real collaboration projects today, uncertainty regarding the business’ present or future characteristics is so significant that ignoring it becomes problematic. In this paper, we propose an approach based on the predictive, probabilistic architecture modeling framework (P²AMF), capable of advanced and probabilistically sound reasoning about profitability risks. The P²AMF-based approach for profitability risk prediction is also based on the e³-value modeling language and on the object constraint language. The paper introduces the prediction and modeling approach, and a supporting software tool. The use of the approach is illustrated by means of a case study originated from the Stockholm Royal Seaport smart city project.     

Enantiospecific synthesis of (R)-1,7-dioxaspiro [5.5]undecane [major component of olive fruit fly (Dacus Oleae) sex pheromone] from d-Fructose

The synthesis of the title compound13 has been carried out through the preparation of its precursor, (3R,4R,5S,6R)-3,4,5-trihydroxy-1,7-dioxaspiro[5.5]undecane (6), obtained fromd-fructose using Wittig's methodology, reduction, and spiroketalation. Compound6 was transformed into13 by a Barton deoxygenation at C-5 followed by a Corey dideoxygenation at C-3,4 of the appropriately protected derivatives.Enantiospecific synthesis of spiroacetals. Part II. For Part I, see Izquierdo and Plaza (1990).     

A voltammetric study concerning the structural stability of Li-overstoichiometric Mg-doped LiCoO2 powders

The effect of Mg-doping and Li overstoichiometry on the structural stability of LiCoO₂ powders has been investigated with emphasis to voltammetric properties. Microparticle cyclic voltammetry (CV) conducted in caustic NaOH to best simulate a non-aqueous electrolyte shows a marked improvement of the structure stability of doped LiCoO₂. In contrast to the unsubstituted LiCoO₂ sample which shows voltammetric peaks associated to the well-known two-phase domain and monoclinic distortion reactions, in Li_1.08Mg_0.06CoO₂, LiMg_0.06CoO₂ and Li_1.08CoO₂ samples these peaks are strongly suppressed providing direct evidence for the existence of a stable solid solution with negligible phase transitions in the reversible intercalation region (3.8-4.2 V vs. Li) as well as in the overcharged region. The effect is higher with Mg-doping, irrespective of the Li overstoichiometry. However, the concomitant presence of Mg and Li excess in the structure is important for obtaining small particle sizes. Since Mg-doping induces a quasi metallic behavior in the samples, whereas the Li excess may provide an higher initial capacity, it is suggested that the Li_1.08Mg_0.06CoO₂ composition may be of interest as positive cathode for advanced Li-ion batteries.     

Effect of different acids with Δ9,12-dienoic structures on Δ9 desaturation activity in rat liver microsomes

The effect of oral administration, for 24 or 48 hr, of different octadeca fatty acids containing a 9,12-dienoic structure on the fatty acid composition and Δ9 desaturation activity of liver microsomes of rat fed a fat-free diet was studied. The ethyl esters of linoelaidic and γ-linolenic acids, the methyl ester of linoleic acid and free columbinic acid were administered to rats maintained on a fat-free diet. The supplementation of the fat-free diet with linoelaidate produced no relevant changes in the fatty acid composition pattern of liver microsomes and did not modify the percentage of conversion of palmitic to palmitoleic acid. The addition of linoleate or γ-linolenate to the fat-free diet returned liver microsome Δ9 desaturation activity toward the control and partially restored the liver microsome fatty acid spectrum found in the fat-free diet. Columbinic acid (5-trans-9-cis,12-cis-18∶3), which cannot be transformed into arachidonic acid, also decreased the Δ9 desaturation activity enhanced by the fat-free diet and evoked changes in the microsomal fatty acid composition similar to those produced by the ω6 fatty acids. These results suggest that the modulation of Δ9 desaturase activity evoked by dietary administration of unsaturated acids of ω6 series would depend on thecis double bond configuration of these acids.     

Lipid composition of the membrane released after an in vitro acrosome reaction of epididymal boar sperm

Prior to fertilization, mammalian sperm must undergo the acrosome reaction, which involves modifications of the plasma and outer acrosomal membranes followed by vesiculation and release of the membranes. The membrane fraction that was released from caudal boar sperm undergoing an in vitro acrosome-like reaction was isolated and characterized with respect to density, marker enzymes and lipid composition. This membrane had a lower phospholipid/protein ratio (mg/mg) than the sperm plasma membrane, whereas both membranes had similar molar sterol/phospholipid ratios. The major phospholipid was sphingomyelin, followed by phosphatidylethanolamine and phosphatidylcholine, whereas in the plasma membrane the order was reversed; the two major phosphoglycerides contained alkylacyl and alkenylacyl species in addition to the diacyl species. The released membrane also contained lower amounts of cholesterol sulfate and unsaturated fatty acids than the plasma membranes. These results, in combination with our studies on the changes of the sperm membranes during maturation and acrosome reaction, will allow a better understanding of the mechanism of the sperm acrosome reaction.