The intramolecular asymmetric Pauson-Khand cyclization as a novel and general stereoselective route to benzindene prostacyclins: synthesis of UT-15 (treprostinil)

A general and novel solution to the synthesis of biologically important stable analogues of prostacyclin PGI(2), namely benzindene prostacyclins, has been achieved via the stereoselective intramolecular Pauson-Khand cyclization (PKC). This work illustrates for the first time the synthetic utility and reliability of the asymmetric PKC route for synthesis and subsequent manufacture of a complex drug substance on a multikilogram scale. The synthetic route surmounts issues of individual step stereoselectivity and scalability. The key step in the synthesis involves efficient stereoselection effected in the PKC of a benzoenyne under the agency of the benzylic OTBDMS group, which serves as a temporary stereodirecting group that is conveniently removed via benzylic hydrogenolysis concomitantly with the catalytic hydrogenation of the enone PKC product. Thus the benzylic chiral center dictates the subsequent stereochemistry of the stereogenic centers at three carbon atoms (C(3a), C(9a), and C(1)).     

Analysis of Wind Fluctuations Using the Orthogonal Wavelet Transform

This paper presents a study of velocity fluctuations occurring in the stably stratified atmospheric boundary layer over an Antarctic ice shelf. The approach is based on wavelet analysis which has advantages over conventional Fourier analysis. Two case studies are presented, comprising: pure turbulent flow and a large amplitude solitary wave.     

Nonlocal elasticity in shape memory alloys modeled using peridynamics for solving dynamic problems

Nonlinear Dynamics - The work is primarily devoted to the peridynamic model elaborated for a solid body made of shape memory alloys (SMAs). The superelasticity effect is taken into consideration as...     

Density functional approach to the adsorption of spherical molecules on a surface modified with attached short chains

A density functional and Monte Carlo simulation study of end-grafted polymers immersed by simple fluids is presented. The polymer molecules are modeled as freely jointed tangent hard spheres with the end segments linked to the surface. The authors analyze an influence of the chain length, the grafting density, and a nature of solvent on the brush structure. Adsorption of hard-sphere mixtures on the modified surface is also discussed. The theory precisely approximates simulation data.     

Detection of changes in cracked aluminium plate determinism by recurrence analysis

The paper investigates changes in determinism of undamaged and cracked aluminium plates with respect to excitation frequencies. Harmonic excitation of frequencies corresponding to structural resonances has been used to vibrate the plates. Vibration responses have been analysed using recurrence plots and recurrence quantification analysis. The smallest sufficient embedding dimension has been estimated using the false nearest neighbour??s algorithm. Mutual information analysis has been applied to determine the relevant time delays. The results demonstrate that performed analysis indicates changes in dynamic behaviour of the plates with respect to various excitation frequencies and crack modes.     

Adsorption of ions on surfaces modified with brushes of polyampholytes

We apply density functional theory to study adsorption of ions, treated in the framework of the restricted primitive model (RPM), on surfaces modified by tethered polyampholytes. The residual electrostatic contribution to the free energy functional is approximated by using the approach proposed by Wang et al. [J. Phys.: Condens. Matter 23, 175002 (2011)] for simple nonuniform RPMs systems. Our research concentrates on the problems how the distribution of the charges within chains of polyampholytes changes the selectivity of adsorption of ions species, the structure of the surface layer, and its electric properties.     

Impact detection in an aircraft composite panel—A neural-network approach

This paper presents the latest results from a programme of work aiming to design impact detectors for structures. The results are from an aircraft component which is substantially more complex than the structures previously investigated by the authors. The paper also illustrates three different approaches to the impact location problem, namely, regression, classification and a combination of both.