Generation and intramolecular reactivity of acyl radicals from alkynylthiol esters under reducing tin-free conditions

[reaction: see text] The radical chain reaction of benzenethiol with alkynylthiol esters provides a new, valuable protocol for the tin-free generation of acyl radicals that arise from intramolecular substitution at sulfur by the initial sulfanylvinyl radicals.     

Are the Elements Elementary? Nineteenth-Century Chemical and Spectroscopical Answers

We analyze the role and influence of a tradition of research linked to the concept of primary matter in nineteenth-century studies on the nature of the elements.The suggestion of William Prout (1785-1850) in 1816 that the atomic weights of pure chemical elements are whole numbers and multiples of the atomic weight of hydrogen, taken as unity, was met with serious confutations,which in turn prompted several attempts to save Prouts hypothesis.We discuss these attempts in detail and the objections raised against them, for instance by Dmitry Ivanovich Mendeleev (1834-1907). We pay particular attention to the use of spectroscopy as a method for proving the existence of elementary forms of matter inside atoms. Leaders in this field of research were two English scientists, the astrophysicist Norman Lockyer (1836-1920) and the chemist William Crookes (1832- 1919). Both of their approaches involved the idea of primary matter. However, while Crookess approach proved to be incorrect, Lockyers ideas survived for several years and supported the discovery of the electron by J.J.Thomson (1856-1940).     

Local branching

The availability of effective exact or heuristic solution methods for general Mixed-Integer Programs (MIPs) is of paramount importance for practical applications. In the present paper we investigate the use of a generic MIP solver as a black-box ``tactical' tool to explore effectively suitable solution subspaces defined and controlled at a ``strategic' level by a simple external branching framework. The procedure is in the spirit of well-known local search metaheuristics, but the neighborhoods are obtained through the introduction in the MIP model of completely general linear inequalities called local branching cuts. The new solution strategy is exact in nature, though it is designed to improve the heuristic behavior of the MIP solver at hand. It alternates high-level strategic branchings to define the solution neighborhoods, and low-level tactical branchings to explore them. The result is a completely general scheme aimed at favoring early updatings of the incumbent solution, hence producing high-quality solutions at early stages of the computation. The method is analyzed computationally on a large class of very difficult MIP problems by using the state-of-the-art commercial software ILOG-Cplex 7.0 as the black-box tactical MIP solver. For these instances, most of which cannot be solved to proven optimality in a reasonable time, the new method exhibits consistently an improved heuristic performance: in 23 out of 29 cases, the MIP solver produced significantly better incumbent solutions when driven by the local branching paradigm. Mathematics Subject Classification (2000):90C06, 90C10, 90C11, 90C27, 90C59     

Constraining extended theories of gravity using Solar System tests

Solar System tests give nowadays constraints on the estimated value of the cosmological constant, which can be accurately derived from different experiments regarding gravitational redshift, light deflection, gravitational time-delay and geodesic precession. Assuming that each reasonable theory of gravitation should satisfy Solar System tests, we use these limits on the estimated value of the cosmological constant to constrain extended theories of Gravity, which are nowadays studied as possible theories for cosmological models and provide viable solutions to the cosmological constant problem and the explanation of the present acceleration of the Universe. We obtain that the estimated values, from Solar System tests, for the parameters appearing in the extended theories of Gravity are orders of magnitude bigger than the values obtained in the framework of cosmologically relevant theories.     

A corresponding states principle-based equation for the surface tension of Alkenes

This study presents a new formula for the surface tension prediction of alkenes. As a first step, an analysis of the available data of the experimental surface tension data for alkenes was performed. The experimental data were collected, after a careful literature survey, for the following pure fluids: propene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, and 1-pentadecene. Then, the experimental data were regressed with the most reliable semi-empirical correlating methods based on the corresponding state theory existing in the literature. As a final step, an analysis of the available data of the experimental surface tension data for alkenes was performed starting from the two recently proposed equations for the prediction of the surface tension of refrigerants based on the corresponding states principle. To minimize the deviation between the predicted data and the experimental data and to find the optimal equation coefficients for experimental data regression, a (μ + λ)-evolution strategy was adopted. The analysis showed that the equation that gave the best results for the prediction of the surface tension of alkenes was the one with a very limited number of parameters. The finally proposed equation is very simple and gives a noticeable improvement with respect to the existing equations. It is based on the corresponding state principle, containing the acentric factor, the critical temperature, and pressure.     

Modeling of waveguide UV-induced Bragg gratings with arbitrary apodization function: Tools for designing high-performance related devices

We present a semi-analytical modeling suitable for the investigation of the spectral characteristics of UV-waveguide Bragg gratings (UV-WBGs) having arbitrary apodization function and extending both in the film layer and in the overlayer. The modeling is based on a proper combination of coupled mode theory and transfer matrix formalism and provides a powerful tool for designing and simulation of complex UV-grating based structures. The results of a detailed investigation of UV-WBGs in doped silica based channel optical waveguides are presented and critical issues for upgrading the performances of related device are discussed. Validation of the modeling is provided by means of an extensive comparison between theoretical and experimental results relevant to UV-WBGs realized in phosphorous (P)- and boron (B)-doped silica based waveguides.     

Multielement (H,C, N,O, S) stable isotope characteristics of lamb meat from different Italian regions

The study focuses on the ²H/H, ¹³C/¹²C, ¹⁵N/¹⁴N, ¹⁸O/¹⁶O and ³⁴S/³²S values of defatted dry matter (DFDM) and on the ²H/H, ¹³C/¹²C and ¹⁸O/¹⁶O values of the fat fraction of meat samples from various lamb types reared in seven Italian regions, following different feeding regimes (forage, concentrate, milk). The ¹³C/¹²C (r = 0.922), ²H/H (r = 0.577) and ¹⁸O/¹⁶O (r = 0.449) values of fat and DFDM are significantly correlated, the fat values being significantly lower for C and H and higher for O than for DFDM values and the differences between the two fractions not being constant for different lamb types. The feeding regime significantly affected the ¹³C/¹²C, ¹⁵N/¹⁴N, ¹⁸O/¹⁶O and ²H/H of fat. The DFDM ²H/H, and ¹⁸O/¹⁶O values, excluding an outlier, are significantly correlated with the corresponding values in meteoric waters, thus allowing us to trace the variability of geoclimatic factors. ¹⁵N/¹⁴N is influenced by pedoclimatic conditions, whereas ³⁴S/³²S is influenced by the sea spray effect and the surface geology of the provenance area. By applying stepwise linear discriminant analysis only the ²H/H of fat was found not to be significant and 97.7% of the samples were correctly assigned to the lamb type and more than 90% cross‐validated. With the feeding regime, 97.7% of the samples were both correctly assigned and cross‐validated using a predictive model including ¹³C/¹²C, ¹⁵N/¹⁴N, ¹⁸O/¹⁶O, ³⁴S/³²S of DFDM and ¹⁸O/¹⁶O of fat. Copyright © 2009 John Wiley & Sons, Ltd.     

Operator splitting for the numerical solution of free surface flow at low capillary numbers

Free surface flows are pervasive in engineering and biomedical applications. In many interesting cases—particularly when small length scales are involved—surface forces (capillarity) dominate the flow dynamics. In these cases, computing the flow together with the shape of the surfaces, requires specialized solution techniques. This article investigates the capabilities of an operator splitting/finite elements method at handling accurately incompressible viscous flow with free surfaces at low capillary numbers. The test case of flow in the downstream section of a slot coater is used for three reasons: (1) it is an established benchmark; (2) it represents an idealized, yet industrially relevant flow; (3) high-fidelity results obtained with monolithic algorithms are available in literature. The flow and free surface shape attained with the new operator splitting scheme agree very satisfactorily with the results obtained with monolithic solvers. Because of its inherent computational simplicity, the new operator splitting scheme is attractive for large-scale simulations, three-dimensional flows, and flows of complex fluids.     

From Kerr to Heisenberg

In this paper, we consider the space-time of a charged mass endowed with an angular momentum. The geometry is described by the exact Kerr–Newman solution of the Einstein equations. The peculiar symmetry, though exact, is usually described in terms of the gravito-magnetic field originated by the angular momentum of the source. A typical product of this geometry is represented by the generalized Sagnac effect. We write down the explicit form for the right/left asymmetry of the times of flight of two counter-rotating light beams along a circular trajectory. Letting the circle shrink to the origin the asymmetry stays finite. Furthermore it becomes independent both from the charge of the source (then its electromagnetic field) and from Newton’s constant: it is then associated only to the symmetry produced by the gravitomagnetic field. When introducing, for the source, the spin of a Fermion, the lowest limit of the Heisenberg uncertainty formula for energy and time appears.