n/a

n/a

The mechanism proposed by Evans to justify the selectivity obtained in Lewis acid catalyzed Diels-Alder reactions of cyclopentadiene with acyloxazolidinones has been generalized and used in the rationalization of selectivities obtained in many other systems. However, we recently proposed an alternative mechanism, on the basis of open-chain mono- and bicomplexes, that avoids the need for chelates and explains the selectivity obtained by Evans. In this manuscript we apply our proposal to the catalyzed conjugated addition of amines to acylimidazolidinones, reported by Cardillo, and we clearly show that aluminum chelates are not involved in the reaction, as they induce no selectivity, while Cardillo observed high experimental selectivities. Our data equally show that bicomplexes with carbonyl parallel orientation, proposed by Cardillo to justify the experimental selectivity with nonchelating Lewis acids, indeed induce the opposite selectivity and have also to be dismissed. On the other hand, our mechanistic proposal allows for the full rationalization of the data obtained by Cardillo with aluminum, boron, or zinc Lewis acids and supports our previous proposal on DA cycloadditions of dienes to Evans chiral auxiliary derivatives.

Given graphs G and H and a positive number b, a weighted (H,b)-decomposition of G is a partition of the edge set of G such that each part is either a single edge or forms an H-subgraph. We assign a weight of b to each H-subgraph in the decomposition and a weight of 1 to single edges. The total weight of the decomposition is the sum of the weights of all elements in the decomposition. Let f(n,H,b) be the the smallest number such that any graph G of order n admits an (H,b)-decomposition with weight at most f(n,H,b). The value of the function f(n,H,b) when b=1 was determined, for large n, by Pikhurko and Sousa [Pikhurko, O. and Sousa, T., Minimum H-Decompositions of Graphs, Journal of Combinatorial Theory, B, 97 (2007), 1041--1055.Here we determine the asymptotic value of f(n,H,b)for any fixed bipartite graph H and any value of b as n tends to infinity.

n/a

In 1968, Gohberg and Krupnik found a Fredholm criterion for singular integral operators of the form \(aP+bQ\), where \(a,b\) are piecewise continuous functions and \(P,Q\) are complementary projections associated to the Cauchy singular integral operator, acting on Lebesgue spaces over Lyapunov curves. We extend this result to the case of Nakano spaces (also known as variable Lebesgue spaces) with certain weights having finite sets of discontinuities on arbitrary Carleson curves.

This paper presents StarTM , an automatic verification tool for transactional memory Java programs executing under relaxed isolation levels. We certify which transactions in a program are safe to execute under Snapshot Isolation without triggering the write-skew anomaly, opening the way to run-time optimizations that may lead to considerable performance enhancements.
Our tool builds on a novel shape analysis technique based on Separation Logic to statically approximate the read- and write-sets of a transactional memory Java program. This technique is particularly challenging due to the presence of dynamically allocated memory.
We implement our technique and apply our tool to a set of intricate examples. We corroborate known results, certifying some of the examples for safe execution under Snapshot Isolation by proving the absence of write-skew anomalies. In other cases we identify transactions that potentially trigger the write-skew anomaly.

The increase focus of companies in clients’ satisfaction, independently of the market they operate in, results from a growing degree of consumers expectations. To fulfill such increase, companies have to arm themselves with the correct internal capabilities, achieving not only efficacy in the satisfaction of each customer, but also efficiency, by operating at the lower possible cost. One of those internal capabilities is the logistics network, which is representing, more and more, a great challenge for companies, given the complexity of the variables that compose it. In this paper, an optimization model is developed that contemplates simultaneously the design and planning of supply chains with reversed flows, through a multi-period and a multi-product network. The proposed model acts as a support tool for the decisions to be made in a real case of a Portuguese telecommunications company, in order to optimize its logistics network.

Spreadsheets are notoriously error-prone. To help avoid the introduction of errors when changing spreadsheets, models that capture the structure and interdependencies of spreadsheets at a conceptual level have been proposed. Thus, spreadsheet evolution can be made safe within the confines of a model. As in any other model/instance setting, evolution may not only require changes at the instance level but also at the model level. When model changes are required, the safety of instance evolution can not be guarded by the model alone. We have designed an appropriate representation of spreadsheet models, including the fundamental notions of formulæand references. For these models and their instances, we have designed coupled transformation rules that cover specific spreadsheet evolution steps, such as the insertion of columns in all occurrences of a repeated block of cells. Each model-level transformation rule is coupled with instance level migration rules from the source to the target model and vice versa. These coupled rules can be composed to create compound transformations at the model level inducing compound transformations at the instance level. This approach guarantees safe evolution of spreadsheets even when models change.

n/a

Superoxide reductases are enzymes involved in bacterial resistance to reactive oxygen species, catalyzing the reduction of superoxide anions to hydrogen peroxide. So far three structural classes have been identified. Class I enzymes have two iron-center containing domains. Most studies have been focused on the catalytic iron site (center II), but the role of center I is yet poorly understood. The possible roles of this iron site were approached by an integrated study using both classical and fast kinetics measurements as well as direct electrochemistry. A new heterometallic form of the protein with a zinc-substituted center I, maintaining the iron active site center II was obtained, resulting in a stable derivative useful for comparison with the native all-iron from. Second order rate constants for the electron transfer between reduced rubredoxin and the different SOR forms were determined to be 2.8x107 (M-1s-1) and 1.3x106 (M-1s-1) for SORFe(IIII)-Fe(II) and for SORFe(IIII)-Fe(III) forms respectively, and 3.2x106 (M-1s-1) for the SORZn(II)-Fe(III) form. The results obtained seem to indicate that center I transfers electrons from the putative physiologic donor, rubredoxin, to the catalytic active iron site (intramolecular process). In addition, electrochemical results show that conformational changes are associated to the redox state of center I, which may enable a faster catalytic response towards superoxide anion. The apparent rate constants calculated for the SOR-mediated electron transfer also support this observation.

n/a

n/a

n/a

n/a

A new approach is laid out to investigate two-photon atomic transitions. It is based on the application of the finite-basis solutions constructed from the Bernstein polynomial (B-polynomial) sets. We show that such an approach provides a very promising route for the relativistic second-order (and even higher-order) calculations since it allows for analytical evaluation of the involved matrices elements. In order to illustrate possible applications of the method and to verify its accuracy, detailed calculations are performed for the 2 s 1/2 ‚Üí 1 s 1/2 transition in neutral hydrogen and hydrogen-like ions, which are compared with the theoretical predictions based on the well-established B-spline basis-set approach.