Observation of a Tricyclic[4.1.0.0 2,4]heptane During a Michael Addition-Ring Closure Reaction and a Computational Study on Its Mechanism of Formation

We describe the formation of a bis-cyclopropane product, a tricyclic[4.1.0.02,4]heptane, that is formed during a Johnson-Corey-Chaykovsky reaction on a cyclopentenone. Two (of four possible) bicyclic products are selectively formed by addition of a COOEt-stabilized sulfur ylide onto the Michael acceptor. The tricyclic product is formed subsequently via a retro Michael elimination of a hindered ether followed by addition of a further cyclopropyl moiety, affecting only one of the two bicyclic products initially formed. The experimental reaction outcome was rationalized using density functional theory (DFT), investigating the different Michael-addition approaches of the sulfur ylide, the transition state (TS) energies for the formation of possible zwitterionic intermediates and subsequent reactions that give rise to cyclopropanation. Selective formation of only two of the four possible products occurs due to the epimerization of unreactive intermediates from the other two pathways, as revealed by energy barrier calculations. The formation of the tricyclic product was rationalized by evaluation of energy barriers for proton abstraction required to form the intermediate undergoing the second cyclopropanation. The selectivity-guiding factors discussed for the single and double cyclopropanation of this functionalized Michael-acceptor will be useful guidelines for the synthesis of future singly and doubly cyclopropanated compounds

Grazing incidence synchrotron X-ray diffraction of marbles consolidated with diammonium hydrogen phosphate treatments : non-destructive probing of buried minerals

Diammonium hydrogen phosphate (DAP)-based consolidating treatments react with carbonatic stones and form calcium phosphates phases, whose composition depends on the availability of free calcium ions. In this work, an innovative non-destructive approach based on grazing incidence X-ray diffraction (GIXRD) with synchrotron radiation (SR) is used to investigate DAP-treated Carrara marble specimens and to study the influence of the substrate composition on the crystallization of calcium phosphate phases. The outcomes indicate that the presence of compositional micro-heterogeneity of Carrara marble favours the formation of specific phases. Dicalcium phosphate dihydrate, a calcium phosphate with a low Ca/P molar ratio, is formed on carbonatic phases with a low Ca amount, such as dolomite grains and Mg-containing veins. Furthermore, this study highlights the potentialities of SR-GIXRD as a powerful non-destructive tool for the diagnostic of Cultural Heritage objects since it allows investigating the conservation history of stone materials and their interaction with the environment

Dynamical Dark Energy model parameters with or without massive neutrinos

We use WMAP5 and other cosmological data to constrain model parameters in quintessence cosmologies, focusing also on their shift when we allow for non-vanishing neutrino masses. The Ratra-Peebles (RP) and SUGRA potentials are used here, as examples of slowly or fastly varying state parameter w(a). Both potentials depend on an energy scale \Lambda. Here we confirm the results of previous analysis with WMAP3 data on the upper limits on \Lambda, which turn out to be rather small (down to ~10^{-9} in RP cosmologies and ~10^{-5} for SUGRA). Our constraints on \Lambda are not heavily affected by the inclusion of neutrino mass as a free parameter. On the contrary, when the neutrino mass degree of freedom is opened, significant shifts in the best-fit values of other parameters occur.Comment: 9 pages, 3 figures, submitted to JCA

Optimal low-thrust trajectories to asteroids through an algorithm based on differential dynamic programming

In this paper an optimisation algorithm based on Differential Dynamic Programming is applied to the design of rendezvous and fly-by trajectories to near Earth objects. Differential dynamic programming is a successive approximation technique that computes a feedback control law in correspondence of a fixed number of decision times. In this way the high dimensional problem characteristic of low-thrust optimisation is reduced into a series of small dimensional problems. The proposed method exploits the stage-wise approach to incorporate an adaptive refinement of the discretisation mesh within the optimisation process. A particular interpolation technique was used to preserve the feedback nature of the control law, thus improving robustness against some approximation errors introduced during the adaptation process. The algorithm implements global variations of the control law, which ensure a further increase in robustness. The results presented show how the proposed approach is capable of fully exploiting the multi-body dynamics of the problem; in fact, in one of the study cases, a fly-by of the Earth is scheduled, which was not included in the first guess solution

Ewald methods for polarizable surfaces with application to hydroxylation and hydrogen bonding on the (012) and (001) surfaces of alpha-Fe2O3

We present a clear and rigorous derivation of the Ewald-like method for calculation of the electrostatic energy of the systems infinitely periodic in two-dimensions and of finite size in the third dimension (slabs) which is significantly faster than existing methods. Molecular dynamics simulations using the transferable/polarizable model by Rustad et al. were applied to study the surface relaxation of the nonhydroxylated, hydroxylated, and solvated surfaces of alpha-Fe2O3 (hematite). We find that our nonhydroxylated structures and energies are in good agreement with previous LDA calculations on alpha-alumina by Manassidis et al. [Surf. Sci. Lett. 285, L517, 1993]. Using the results of molecular dynamics simulations of solvated interfaces, we define end-member hydroxylated-hydrated states for the surfaces which are used in energy minimization calculations. We find that hydration has a small effect on the surface structure, but that hydroxylation has a significant effect. Our calculations, both for gas-phase and solution-phase adsorption, predict a greater amount of hydroxylation for the (012) surface than for the (001) surface. Our simulations also indicate the presence of four-fold coordinated iron ions on the (001) surface.Comment: 23 pages, REVTeX (LaTeX), 8 figures not included, e-mail to [email protected], paper accepted in Surface Scienc

What’s underneath? : A non-destructive depth profile of painted stratigraphies by synchrotron grazing incidence X-ray diffraction

Many works of art are complex systems consisting of a core finished by the overlapping of several painted layers. In this work, we apply an innovative method based on grazing incidence X-ray diffraction (GIXRD) with synchrotron radiation (SR) to investigate polychrome stratigraphies with a completely non-destructive approach. The SR-GIXRD measurements provided direct and unambiguous compositional and stratigraphic information of the crystalline species lying in different layers. The investigations performed on a small fragment sampled from a painted terracotta statue allowed identifying pigments, fillers, aggregates of the matrix and newly formed decay salts in micrometric-thin paint layers. Furthermore, the great potentiality of this study is the feasibility of depth profile investigations on multi-layered painted samples from Cultural Heritage objects without resorting to cross sectional analyses. Currently, the method is non-destructive but it can be potentially non-invasive in situations where small moveable artworks can be placed into the measurement chamber of the SR-XRD beamlines. The overall study paves the way to a new scenario of artwork investigations, shading light on new unexplored approaches for non-destructive studies of Cultural Heritage objects, their conservation history and their interaction with the environment

Do WMAP data favor neutrino mass and a coupling between Cold Dark Matter and Dark Energy?

Within the frame of cosmologies where Dark Energy (DE) is a self--interacting scalar field, we allow for a CDM--DE coupling and non--zero neutrino masses, simultaneously. In their 0--0 version, i.e. in the absence of coupling and neutrino mass, these cosmologies provide an excellent fit to WMAP, SNIa and deep galaxy sample spectra, at least as good as \LambdaCDM. When the new degrees of freedom are open, we find that CDM--DE coupling and significant neutrino masses (~0.1eV per \nu species) are at least as likely as the 0--0 option and, in some cases, even statistically favoured. Results are obtained by using a Monte Carlo Markov Chain approach.Comment: 18 pages, 10 figures, submitted to JCA

A systematic cross-search for radio/infrared counterparts of XMM-Newton sources

We present a catalog of cross-correlated radio, infrared and X-ray sources using a very restrictive selection criteria with an IDL-based code developed by us. The significance of the observed coincidences was evaluated through Monte Carlo simulations of synthetic sources following a well-tested protocol. We found 3320 coincident radio/X-ray sources with a high statistical significance characterized by the sum of error-weighted coordinate differences. For 997 of them, 2MASS counterparts were found. The percentage of chance coincidences is less than 1%. X-ray hardness ratios of well-known populations of objects were used to provide a crude representation of their X-ray spectrum and to make a preliminary diagnosis of the possible nature of unidentified X-ray sources. The results support the fact that the X-ray sky is largely dominated by Active Galactic Nuclei at high galactic latitudes (|b| >= 10^\circ). At low galactic latitudes (|b| <= 10^\circ) most of unidentified X-ray sources (~94%) lie at |b| <= 2^\circ. This result suggests that most of the unidentified sources found toward the Milky Way plane are galactic objects. Well-known and unidentified sources were classified in different tables with their corresponding radio/infrared and X-ray properties. These tables are intended as a useful tool for researchers interested in particular identifications.Comment: Accepted for publication in Ap&SS. 47 pages, 10 figures. On-line material: figures and table