Engineering reactions in crystalline solids: predicting photochemical decarbonylation from calculated thermochemical parameters

A detailed thermochemical analysis of the alpha-cleavage and decarbonylation reactions of acetone and several ketodiesters was carried out with the B3LYP/6-31G* density functional method. The heats of formation of several ground-state ketones and radicals were calculated at 298 K to determine bond dissociation energies (BDE) and radical stabilization energies (RSE) as a function of substituents. Results show that the radical-stabilizing abilities of the ketone substituents play a very important role on the thermodynamics of the alpha-cleavage and decarbonylation steps. An excellent correlation between calculated values and previous experimental observations suggests that photochemical alpha-cleavage and decarbonylation in crystals should be predictable from knowledge of excitation energies and the RSE of the substituent.     

Complete 1H and 13C NMR assignments of aurasperone A and fonsecinone A, two bis-naphthopyrones produced by Aspergillus aculeatus

Complete assignments of 1H and 13C NMR chemical shifts of the polyketides aurasperone A and fonsecinone A were made by means of nuclear Overhauser enhancement and heteronuclear NMR correlation experiments. These compounds were isolated for the first time from Aspergillus aculeatus, an endophytic fungus obtained from leaves of Melia azedarach(Meliaceae).     

On the domain of attraction of an operator between supremum and sum

Summary Between the operations which produce partial maxima and partial sums of a sequenceY ₁,Y ₂, ..., lies the inductive operation:X _n =X _n-1(X _n-1+Y _n ),n1, for 0<<1. If theY _n are independent random variables with common distributionF, we show that the limiting behavior of normed sequences formed from {X _n ,n1}, is, for 0<<1, parallel to the extreme value case =0. ForFD() we give a full proof of the convergence, whereas forFD()D(), we only succeeded in proving tightness of the involved sequence. The processX _n is interesting for some applied probability models.     

Cohen and multiple Cohen strongly summing multilinear operators

Considering the successful theory of multiple summing multilinear operators as a prototype, we introduce the classes of multiple Cohen strongly p-summing multilinear operators and polynomials. The adequacy of these classes under the viewpoint of the theory of multilinear and polynomial ideals and holomorphy types is discussed in detail.     

Phenomenology tools on cloud infrastructures using OpenStack

We present a new environment for computations in particle physics phenomenology employing recent developments in cloud computing. On this environment users can create and manage “virtual” machines on which the phenomenology codes/tools can be deployed easily in an automated way. We analyze the performance of this environment based on “virtual” machines versus the utilization of physical hardware. In this way we provide a qualitative result for the influence of the host operating system on the performance of a representative set of applications for phenomenology calculations.     

Determination of Sulfaguanidine in Food and Veterinary Pharmaceuticals by Flow Injection Analysis with Spectrophotometric Detection

This work proposes a flow injection analysis system for sulfaguanidine determination in pharmaceutical and food samples. The method was based on the reaction of sulfaguanidine with nitronium ion to produce a colored complex whose absorbance was measured at 545?nm. The flow injection analysis system’s significant parameters were checked by a fractional factorial design 2^7–2 and optimization by a Doehlert matrix. The flow injection analysis system shows optimum values at 0.28, 2.00, and 0.11% (w/v) for N-naphtil ethylenediamine, ammonium sulfamate, and sodium nitrite concentrations, respectively. The possible interferents present in pharmaceutical and food samples were assessed by a multivariate technique and depicted on probability charts, indicating no significant interferences at the 95% level of confidence interval. The method showed detection and quantification limits of 0.012 and 0.039?mg?L^?1, an analytical frequency of 30 readings h^?1 and precision always lower than 5.0% expressed as the relative standard deviation. The obtained results were in accordance with those obtained by high-performance liquid chromatography.     

Strategies for spectrum slicing based on restarted Lanczos methods

In the context of symmetric-definite generalized eigenvalue problems, it is often required to compute all eigenvalues contained in a prescribed interval. For large-scale problems, the method of choice is the so-called spectrum slicing technique: a shift-and-invert Lanczos method combined with a dynamic shift selection that sweeps the interval in a smart way. This kind of strategies were proposed initially in the context of unrestarted Lanczos methods, back in the 1990’s. We propose variations that try to incorporate recent developments in the field of Krylov methods, including thick restarting in the Lanczos solver and a rational Krylov update when moving from one shift to the next. We discuss a parallel implementation in the SLEPc library and provide performance results.