Oxidation reactions of azines.

Condensation of 2-([2.2]paracyclophan-4-yl)propene with formaldehyde and amines gave 4-paracyclophanyl substituted -piperidols which were readily dehydrated to the corresponding tetrahydropyridines. N-Methyl substituted 4-paracyclophanyltetrahydropyridine has been oxidized to the corresponding piperidin-2-one.For communication 2, see [1]. This article is also communication 4 in the series Synthesis, structure and biological activity of [2.2]paracyclophanes (for communication 3, see [2]).Russian University of National Friendship, Moscow 117198. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 653–658, May, 1997,     

Diffusion of condensable vapors in single adsorbent particles measured via concentration-swing frequency response

A concentration-swing frequency response method is extended to examine mass transfer mechanisms and the concentration dependence of mass transfer rates for adsorption of condensable vapors in single adsorbent particles. The adsorption kinetics of water and hexane in BPL activated carbon and the adsorption of water in silica gel are determined at several different concentrations. The mechanism that best describes the adsorption of water in BPL activated carbon is nanopore diffusion. The diffusivity of water in BPL activated carbon has a clear minimum at approximately P/Po = 0.5, and the concentration dependence of the diffusion data are not described well by the Darken relationship. Both nanopore diffusion and the Glueckauf linear driving force models can be used to describe the diffusion of hexane in BPL activated carbon for the pressure range studied, and the dependence of the diffusivity on concentration can be described approximately using the Darken relationship. However, the diffusion of water in silica gel cannot be described by the nanopore diffusion model and is best characterized by the Glueckauf linear driving force model. The results illustrate the ability of concentration-swing frequency response to accurately determine adsorption rate mechanisms and quantify the complex adsorption kinetics of condensable vapors using small quantities of adsorbent.     

Optical scattering measurements and implications on thermal noise in Gravitational Wave detectors test-mass coatings

Photographs of the LIGO Gravitational Wave detector mirrors illuminated by the standing beam were analyzed with an astronomical software tool designed to identify stars within images, which extracted hundreds of thousands of point-like scatterers uniformly distributed across the mirror surface, likely distributed through the depth of the coating layers. The sheer number of the observed scatterers implies a fundamental, thermodynamic origin during deposition or processing. These scatterers are a possible source of the mirror dissipation and thermal noise foreseen by V. Braginsky and Y. Levin, which limits the sensitivity of observatories to Gravitational Waves. This study may point the way towards the production of mirrors with reduced thermal noise and an increased detection range.     

Extended Lagrange and Penalty Functions in Optimization

We consider nonlinear Lagrange and penalty functions for optimization problems with a single constraint. The convolution of the objective function and the constraint is accomplished by an increasing positively homogeneous of the first degree function. We study necessary and also sufficient conditions for the validity of the zero duality gap property for both Lagrange and penalty functions and for the exact penalization. We also study the so-called regular weak separation functions.     

A novel high-gradient permanent magnet for the profiling of planar films and coatings.

The design and construction of a low-cost, permanent magnet is described. The magnet is intended for applications which require a large static gradient, such as those for which stray field imaging or fringe field diffusometry are conventionally employed. The magnet has been designed using the scalar potential method. Particular features of the magnet include a field profile such that ||B || is constant in the horizontal plane and such that B is horizontal at the midpoint between the poles. There is a vertical, and therefore orthogonal, strong gradient, G, in ||B ||. The ratio G/ ||B || is constant within a large volume and so allows measurements at a range of gradient strengths. It is this ratio which governs the shape of the pole-pieces. The constructed magnet has a typical operating field of 0.8 T, gives a gradient of 20 Tm-1, and has a useable interpole access of 20 mm. Field plot data show values consistent with the theory. In particular ||B || has a curvature of less than +/-5 microm over a 5 x 5 mm area at the target field. The magnet is most suitable for the one-dimensional profiling of thin planar samples. As an example of the magnet's use, a profile of a sandwich structure made of several polymer layers is shown. In addition, a set of one-dimensional profiles of an alkyd coating, recorded during solvent loss and cross-linking, is presented. This example demonstrates quantitative T2 measurements at a resolution of 6.5 microm across a 70-microm-thick film.     

Rapid three-dimensional functional magnetic resonance imaging of the initial negative BOLD response

Functional MRI is most commonly used to study the local changes in blood flow that accompanies neuronal activity. In this work we introduce a new approach towards acquiring and analyzing fMRI data that instead provides the potential to study the initial oxygen consumption in the brain that accompanies activation. As the oxygen consumption is closer in timing to the underlying neuronal activity than the subsequent blood flow, this approach promises to provide more precise information about the location and timing of activity. Our approach is based on using a new single shot 3D echo-volumar imaging sequence which samples a small central region of 3D k-space every 100ms, thereby giving a low spatial resolution snapshot of the brain with extremely high temporal resolution. Explicit and simple rules for implementing the trajectory are provided, together with a straightforward reconstruction algorithm. Using our approach allows us to effectively study the behavior of the brain in the time immediately following activation through the initial negative BOLD response, and we discuss new techniques for detecting the presence of the negative response across the brain. The feasibility and efficiency of the approach is confirmed using data from a visual-motor task and an auditory-motor-visual task. The results of these experiments provide a proof of concept of our methodology, and indicate that rapid imaging of the initial negative BOLD response can serve an important role in studying cognition tasks involving rapid mental processing in more than one region.     

Fully fluorinated imidodiphosphinate shells for visible- and NIR-emitting lanthanides: hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties

In this paper we demonstrate that the effect of aromatic C--F substitution in ligands does not always abide by conventional wisdom for ligand design to enhance sensitisation for visible lanthanide emission, in contrast with NIR emission for which the same effect coupled with shell formation leads to unprecedented long luminescence lifetimes. We have chosen an imidodiphosphinate ligand, N-{P,P-di(pentafluorophinoyl)}-P,P-dipentafluorophenylphosphinimidic acid (HF20tpip), to form ideal fluorinated shells about all visible- and NIR-emitting lanthanides. The shell, formed by three ligands, comprises twelve fully fluorinated aryl sensitiser groups, yet no-high energy X--H vibrations that quench lanthanide emission. The synthesis, full characterisation including X-ray and NMR analysis as well as the photophysical properties of the emissive complexes [Ln(F20tpip)3], in which Ln=Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Y, Gd, are reported. The photophysical results contrast previous studies, in which fluorination of alkyl chains tends to lead to more emissive lanthanide complexes for both visible and NIR emission. Analysis of the fluorescence properties of the HF20tpip and [Gd(F20tpip)3] reveals that there is a low-lying state at around 715 nm that is responsible for partially quenching of the signal of the visible emitting lanthanides and we attribute it to a pi-sigma* state. However, all visible emitting lanthanides have long lifetimes and unexpectedly the [Dy(F20tpip)3] complex shows a lifetime of 0.3 ms, indicating that the elimination of high-energy vibrations from the ligand framework is particularly favourable for Dy. The NIR emitting lanthanides show strong emission signals in powder and solution with unprecedented lifetimes. The luminescence lifetimes of [Nd(F20tpip)3], [Er(F20tpip)3] and [Yb(F20tpip)3] in deuteurated acetonitrile are 44, 741 and 1111 micros. The highest value observed for the [Yb(F20tpip)3] complex is more than half the value of the Yb ion radiative lifetime.     

Synthesis of saramycetic acid

The first reported synthesis of saramycetic acid, a degradation product of the complex thiopeptide antibiotic cyclothiazomycin, is achieved in nine steps and 11% overall yield from diethoxyacetonitrile by a strategy, which incorporates two Hantzsch thiazole syntheses using thioamides prepared from the corresponding nitriles without the use of gaseous H₂S. The synthetic material was transformed to methyl saramycetate, which had spectroscopic properties in excellent agreement with the literature data.