Base‐dependent selectivity of an SNAr reaction

A detailed kinetic analysis and computational study of an S_NAr reaction between 2,5,6‐trifluoronicotinonitrile, 2 , and the ambident 3‐isopropoxy‐1H‐pyrazol‐5‐amine, 3 , is presented. The selectivity with respect to the reaction at the primary amino group of 2 , to give the desired product, 2,5‐difluoro‐6‐[(3‐isopropoxy‐1H‐pyrazol‐5‐yl)amino]nicotinonitrile, 1 , is strongly dependent upon reaction conditions. Reaction is found to proceed via both uncatalysed and base catalysed routes, and selectivity towards 1 is strongly enhanced in the presence of the base diazabicyclo[2,2,2]octane (DABCO). Computational studies in tetrahydrofuran solution at the B3LYP/6‐31G* level of theory have provided valuable insight into alternative kinetically indistinguishable reaction pathways. The results suggest that for reaction at the primary amino group, proton removal by DABCO accompanying amine addition allows avoidance of a high‐energy, zwitterionic Meisenheimer intermediate. Reactions at the alternative pyrazole nitrogen atoms are less sensitive to the presence of base because of stabilisation of the Meisenheimer zwitterions by intramolecular hydrogen bonding. Copyright © 2010 John Wiley & Sons, Ltd.     

Increased and balanced light emission of transparent organic light-emitting diodes by enhanced microcavity effects

We report on improved and controlled light outcoupling of transparent organic light-emitting diodes (TOLEDs) by inserting thin silver layers between the indium tin oxide anode and the hole transporting layer. The introduction of Ag layers influences both the bottom and top emission of the TOLEDs, and it results in dramatic changes in the electroluminescence spectra and angular distribution. We find that the overall external quantum efficiency can be increased up to 18.8%, and the ratio of bottom and top emission can be almost identical.     

Influence of organic capping layers on the performance of transparent organic light-emitting diodes

We investigate a set of transparent organic LEDs (TOLEDs) with different organic capping layer (OC) thicknesses to understand the capping layer effect. We find that thickness variation of the OC strongly influences the emission properties of TOLEDs and exhibits different trends for top or bottom emission. The external quantum efficiency for the top side can be enhanced by a factor of 63%, but that of the bottom side only by 4% compared to a reference device without an OC. Additionally, we demonstrate that the introduction of the OC is an effective method to control the bottom-to-top emission ratio within a measured range from 2.87 to 6.05.     

Modeling,simulation and validation of material flow on conveyor belts

In this paper a model comparison approach based on material flow systems is investigated that is divided into a microscopic and a macroscopic model scale. On the microscopic model scale particles are simulated using a model based on Newton dynamics borrowed from the engineering literature. Phenomenological observations lead to a hyperbolic partial differential equation on the macroscopic model scale. Suitable numerical algorithms are presented and both models are compared numerically and validated against real-data test settings.     

A vanishing result for strictly p-convex domains

In view of Andreotti and Grauert (Bull Soc Math France 90:193–259, 1962) vanishing theorem for \(q\) -complete domains in \(\mathbb C ^{n}\) , we reprove a vanishing result by Sha (Invent Math 83(3):437–447, 1986), and Wu (Indiana Univ Math J 36(3):525–548, 1987), for the de Rham cohomology of strictly \(p\) -convex domains in \(\mathbb R ^n\) in the sense of Harvey and Lawson (The foundations of \(p\) -convexity and \(p\) -plurisubharmonicity in riemannian geometry. arXiv:1111.3895v1 [math.DG]). Our proof uses the \({L}^2\) -techniques developed by Hörmander (An introduction to complex analysis in several variables, 3rd edn. North-Holland Publishing Co, Amsterdam 1990), and Andreotti and Vesentini (Inst Hautes Études Sci Publ Math 25:81–130, 1965).     

Adaptive and multi-mining versions of the DM-GRASP hybrid metaheuristic

Metaheuristics represent an important class of techniques to solve, approximately, hard combinatorial optimization problems for which the use of exact methods is impractical. Some researches have been combining machine learning techniques with metaheuristics to adaptively guide and improve the search for near optimal solutions. An example of such development is the DM-GRASP, a hybrid version of the Greedy Randomized Adaptative Search Procedures (GRASP) metaheuristic which incorporates a data mining process. In this hybrid proposal, after executing half of the total number of iterations, the data mining process extracts patterns from an elite set of sub-optimal solutions for the optimization problem. These patterns present characteristics of near optimal solutions and can be used to guide the following half GRASP iterations in the search through the solution space. In this work, we explore new versions of the DM-GRASP metaheuristic to experiment, not a single activation, but multiple and adaptive executions of the data mining process during the metaheuristic execution. We also applied the data mining technique into a reactive GRASP to show that a more sophisticated and not memoryless GRASP approach can also benefit from the use of this technique. In order to evaluate these new proposals, we adopted the server replication for reliable multicast problem since the best known results for this problem were obtained by GRASP and DM-GRASP implementations. The computational experiments, comparing traditional GRASP, DM-GRASP, and the new proposals, showed that multiple and adaptive executions of the data mining process can improve the results obtained by the DM-GRASP hybrid metaheuristic—the new proposals were able to find better results in less computational time for the reliable multicast problem.     

Principal differential analysis of the Aneurisk65 data set

We explore the use of principal differential analysis as a tool for performing dimensional reduction of functional data sets. In particular, we compare the results provided by principal differential analysis and by functional principal component analysis in the dimensional reduction of three synthetic data sets, and of a real data set concerning 65 three-dimensional cerebral geometries, the AneuRisk65 data set. The analyses show that principal differential analysis can provide an alternative and effective representation of functional data, easily interpretable in terms of exponential, sinusoidal, or damped-sinusoidal functions and providing a different insight to the functional data set under investigation. Moreover, in the analysis of the AneuRisk65 data set, principal differential analysis is able to detect interesting features of the data, such as the rippling effect of the vessel surface, that functional principal component analysis is not able to detect.     

Crystallization of glasses in the germanium-tellurium-sulphur system

The glasses of the germanium-tellurium-sulphur ternary system were investigated in order to determine the formation and crystallization processes. Vitreous samples were prepared by quenching. The vitreous transition and crystallization temperatures, together with microhardnesses, were measured throughout the vitreous region. The latter was sub-divided into several zones, and the behaviour of the glasses in each of these zones was analyzed separately.