On the Smith normal form of a skew‐symmetric d‐optimal design of order

We show that the Smith normal form of a skew‐symmetric D ‐optimal design of order is determined by its order. Furthermore, we show that the Smith normal form of such a design can be written explicitly in terms of the order , thereby proving a recent conjecture of Armario. We apply our result to show that certain D ‐optimal designs of order are not equivalent to any skew‐symmetric D ‐optimal design. We also provide a correction to a result in the literature on the Smith normal form of D ‐optimal designs.     

19F-detected dual-optimized inverted 1JCC 1,n-ADEQUATE

Modification of the recently reported ¹⁹F-detected 1,1-ADEQUATE experiment that incorporates dual-optimization to selectively invert a wide range of ¹J_CC correlations in a 1,n-ADEQUATE experiment is reported. Parameters for the dual-optimization segment of the pulse sequence were modified to accommodate the increased size of ¹J_CC homonuclear coupling constants of poly- and perfluorinated molecules relative to protonated molecules to allow broadband inversion of the ¹J_CC correlations. The observation and utility of isotope shifts are reported for the first time for 1,1- and 1,n-ADEQUATE correlations.     

Cover Picture: Turning Spiroketals Inside Out: A Rearrangement Triggered by an Enol Ether Epoxidation (ChemistryOpen 5/2015)

Invited for this month''s cover picture is the group of Professor Mark Peczuh at the University of Connecticut. The cover picture compares the rearrangement of a small molecule to the process of turning a stuffed animal inside out. The recycled, inside-out stuffed animals are both artistic and philosophically provocative. They capture the essence of the rearrangement reaction because the compounds themselves turn inside out over the course of the reaction, extending the diversity of products that can arise from simple starting materials. Small molecules often have functional groups with latent reactivity; under the appropriate conditions, those groups can react with other compounds (e.g., reagents) and also with other groups in the same molecule in an intramolecular reaction. The research team found that the epoxidation of some highly functionalized spiroketal compounds promoted rearrangements of their structures that turned them inside out. Some of the features of the products led them to use X-ray crystallography or a combination of computer-assisted structure elucidation, computation, and a new version of the 1,1-ADEQUATE NMR experiment to determine their structures. For more details, see the Communication on p. 577 ff.     

Configurational Lability at Tetrahedral Phosphorus: syn/anti-Isomerization of a P-Stereogenic Phosphiranium Cation by Intramolecular Epimerization at Phosphorus

Tetrahedral main-group compounds are normally configurationally stable, but P-epimerization of the chiral phosphiranium cations syn- or anti-[Mes*P(Me)CH₂CHPh][OTf] (Mes*=2,4,6-(t-Bu)₃C₆H₂) occurred under mild conditions at 60 °C in CD₂Cl₂, resulting in isomerization to give a syn-enriched equilibrium mixture. Ion exchange with excess [NBu₄][Δ-TRISPHAT] (Δ-TRISPHAT=Δ-P(o-C₆Cl₄O₂)₃) followed by chromatography on silica removed [NBu₄][OTf] and gave mixtures of syn- and anti-[Mes*P(Me)CH₂CHPh][Δ-TRISPHAT]?x[NBu₄][Δ-TRISPHAT]. NMR spectroscopy showed that isomerization proceeded with epimerization at P and retention at C. DFT calculations are consistent with a mechanism involving P-C cleavage to yield a hyperconjugation-stabilized carbocation, pyramidal inversion promoted by σ-interaction of the P lone pair with the neighboring β-carbocation, and ring closure with inversion of configuration at P.     

Reversible Modulation of Surface Plasmons in Gold Nanoparticles Enabled by Surface Redox Chemistry

Switchable surface redox chemistry is demonstrated in gold@iron/iron oxide core–shell nanoparticles with ambient oxidation and plasmon‐mediated reduction to modulate the oxidation state of shell layers. The iron shell can be oxidized to iron oxide through ambient oxidation, leading to an enhancement and red‐shift of the gold surface plasmon resonance (SPR). This enhanced gold SPR can drive reduction of the iron oxide shell under broadband illumination to reversibly blue‐shift and significantly dampen gold SPR absorption. The observed phenomena provide a unique mechanism for controlling the plasmonic properties and surface chemistry of small metal nanoparticles.     

On the stability of a deep beam subjected to nonconservative and dissipative forces

Summary For the case of a simply supported deep beam subjected to a transverse follower load applied at its center, the dependence of the critical flutter load upon the effects of internal and external damping and warping rigidity is considered. A Kelvin-Voigt solid is assumed, the external damping is assumed to be proportional to the velocity of the beam at a point, and, due to the nature of the nonconservative applied load, the flexural and torsional deformations of the beam are coupled. The resulting boundary value problem is nonself-adjoint in character, and the stability problem is solved in an approximate manner by means of an adjoint variational principle. Several graphs are presented to demonstrate the effect of the various damping and rigidity parameters on the value of the critical flutter load. The numerical results obtained here reveal that in the absence of external damping, the value of the critical flutter load becomes arbitrarily small as the internal damping parameter associated with flexure tends to zero.

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Sommario Per una trave alta, incernierata agli estremi e sollecitata da un carico rotante con la sezione cui sia applicato e distribuito simmetricamente rispetto alla mezzeria della trave, si considera la dipendenza del carico critico di flutter dagli effetti di smorzamento interno ed esterno e della rigidezza biflessionale. Si assnmono (i) un solido di tipo Kelvin-Voigt e (ii) uno smorzamento esterno che sia proporzionale alla velocità. Dovuta al genere del carico non conservativo, la deformazione consiste di spostamenti di flessione e torsione. Poichè il problema ai limiti che descrive il moto del sistema possiede coefficienti variabili e non è antoaggiunto, si risolve il problema di constatare il valore del carico critico per un procedimento approssimativo mediante un principio variazionale. Si mostrano grafici che rivelano gli effetti dei diversi parametri di smorzamento e rigidezza sul valore del carico critico. I risultati numerici ottenuti qui mostrano che nell'assenza di smorzamento esterno il valore del carico critico diviene arbitrariamente minnto qualora il parametro di smorzamento interim associate con flessione lenda a zero.

     

An optimisation method for separating and rebuilding one-dimensional dispersive waves from multi-point measurements. Application to elastic or viscoelastic bars

When using a classical SHPB (split Hopkinson pressure bar) set-up, the useful measuring time is limited by the length of the bars, so that the maximum strain which can be measured in material testing applications is also limited. In this paper, a new method with no time limits is presented for measuring the force and displacement at any station on a bar from strain or velocity measurements performed at various places on the bar. The method takes the wave dispersion into account, as must inevitably be done when making long time measurements. It can be applied to one-dimensional and single-mode waves of all kinds propagating through a medium (flexural waves in beams, acoustic waves in wave guides, etc.). With bars of usual sizes, the measuring time can be up to 50 times longer than the time available with classical methods. An analysis of the sensitivity of the results to the accuracy of the experimental data and to the quality of the wave propagation modelling was also carried out. Experimental results are given which show the efficiency of the method.