Organozinc Pivalate Reagents: Segregation,Solubility, Stabilization,and Structural Insights

The pivalates RZnOPiv⋅Mg(OPiv)X⋅n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D₈]THF solution these reagents exist as separated Me(p‐C₆H₄)ZnCl and Mg(OPiv)₂ species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)₂ enhances the air stability of aryl zinc species by sequestering H₂O contaminants. Coupling reactions of Me(p‐C₆H₄)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)₂. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)₂Li₂(Cl)₂(OPiv)₂Zn].     

Large deflection of a non-linear,elastic, asymmetric Ludwick cantilever beam subjected to horizontal force,vertical force and bending torque at the free end

The investigated cantilever beam is characterized by a constant rectangular cross-section and is subjected to a concentrated constant vertical load, to a concentrated constant horizontal load and to a concentrated constant bending torque at the free end. The same beam is made by an elastic non-linear asymmetric Ludwick type material with different behavior in tension and compression. Namely the constitutive law of the proposed material is characterized by two different elastic moduli and two different strain exponential coefficients. The aim of this study is to describe the deformation of the beam neutral surface and particularly the horizontal and vertical displacements of the free end cross-section. The analysis of large deflection is based on the Euler–Bernoulli bending beam theory, for which cross-sections, after the deformation, remain plain and perpendicular to the neutral surface; furthermore their shape and area do not change. On the stress viewpoint, the shear stress effect and the axial force effect are considered negligible in comparison with the bending effect. The mechanical model deduced from the identified hypotheses includes two kind of non-linearity: the first due to the material and the latter due to large deformations. The mathematical problem associated with the mechanical model, i.e. to compute the bending deformations, consists in solving a non-linear algebraic system and a non-liner second order ordinary differential equation. Thus a numerical algorithm is developed and some examples of specific results are shown in this paper.     

Optimisation of sensor positions in random linear arrays based on statistical relations between geometry and performance

Due to the widespread use of acoustic arrays, optimisation techniques for array design, focused on improving array performance, have been widely published. This paper exploits the statistical relation between different measures of sidelobe levels and the spacing of elements in random linear arrays made up of a small number of sensors. This paper defines the methodology to obtain maximum probability functions, associating array geometry and performance. These maximum probability functions allow a pre-selection of those array geometries that are more likely to be associated to specified sidelobe level values. This pre-selection results in a significantly reduced computational burden.     

Electrolytes for quasi solid‐state dye‐sensitized solar cells based on block copolymers

The first use of PS_n‐b‐PEO_m‐b‐PS_n block copolymers (PS = polystyrene, PEO = poly(ethylene oxide)) as solid hosts for iodine/iodide electrolytes in dye‐sensitized solar cells (DSSCs) is described. Using the benchmark photosensitizer N719, DSSC based on the quasi solid‐state electrolytes afforded efficiencies up to 6.7%, to be compared with an efficiency of 7.3% obtained in similar conditions with a conventional iodine/iodide liquid electrolyte. By varying the PS:PEO relative volume ratio in the block copolymers different properties and morphologies were obtained. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 719–727     

Photochemistry in Real Space: Batho- and Hypsochromism in the Water Dimer

The development of chemical intuition in photochemistry faces several difficulties that result from the inadequacy of the one-particle picture, the Born–Oppenheimer approximation, and other basic ideas used to build models. It is shown herein how real-space approaches can be efficiently used to gain valuable insights in photochemistry through a simple example of red and blue shift effects: the double hypso- and bathochromic shifts in the low-lying valence excited states of (H₂O)₂. It is demonstrated that 1) the use of these techniques allows the perturbative language used in the theory of intermolecular interactions, even in the strongly interacting short-range regime, to be maintained; 2) one and only one molecule is photoexcited in each of the addressed excited states and 3) the electrostatic interaction between the in-the-cluster molecular dipoles provides a fairly intuitive rationalisation of the observed batho- and hypsochromism. The methods exploited and illustrated herein are able to maintain the individuality and properties of the interacting entities in a molecular aggregate, and thereby they allow chemical intuition in general states, at any geometry and using a broad variety of electronic structure methods to be kept and built.     

Automorphisms of Hilbert schemes of points on a generic projective K3 surface

We study automorphisms of the Hilbert scheme of n points on a generic projective K3 surface S, for any . We show that is either trivial or generated by a non‐symplectic involution and we determine numerical and divisorial conditions which allow us to distinguish between the two cases. As an application of these results we prove that, for any , there exist infinitely many admissible degrees for the polarization of the K3 surface S such that admits a non‐natural involution. This provides a generalization of the results of [7] for .