Rigid ferrocenophane and its metal complexes with transition and alkaline-earth metal ions

The rigid [6]ferrocenophane, L-1, was synthesised by condensation of 1,1'-ferrocene dicarbaldehyde with trans-1,2-diaminocyclohexane in high dilution at r.t. followed by reduction. When other experimental conditions were employed, the [6,6,6]ferrocenephane (L-2) was also obtained. Both compounds were characterised by single crystal X-ray crystallography. The protonation of L-1 and its metal complexation were evaluated by the effect on the electron-transfer process of the ferrocene (fc) unit of L-1 using cyclic voltammetry (CV) and square wave voltammetry (SWV) in anhydrous CH3CN solution and in 0.1 M (Bu4NPF6)-Bu-n as the supporting electrolyte. The electrochemical process of L-1 between 300 and 900 mV is complicated by amine oxidation. On the other hand, an anodic shift from the fc/fc(+) wave of L-1 of 249, 225, 81 and 61 mV was observed by formation of Zn2+, Ni2+, Pd2+ and Cu2+ complexes, respectively. Whereas Mg2+ and Ca2+ only have with L-1 weak interactions and they promote the acid-base equilibrium of L-1. This reveals that L-1 is an interesting molecular redox sensor for detection of Zn2+ and Ni2+, although the kinetics of the Zn2+ complex formation is much faster than that of the Ni2+ one. The X-ray crystal structure of [(PdLCl2)-Cl-1] was determined and showed a square-planar environment with Pd(II) and Fe(II) centres separated by 3.781(1) angstrom. The experimental anodic shifts were elucidated by DFT calculations on the [(MLCl2)-Cl-1] series and they are related to the nature of the HOMO of these complexes and a four-electron, two-orbital interaction.

Peptidomimetic design of unusual turns by incorporating flexible and rigid omega-amino acids simultaneously

The tripeptides Boc-Gly-Aib-m-ABA-OMe (I), Boc-beta Ala-Aib-m-ABA-OMe (II) and Boc-gamma Abu-Aib-rn-ABA-OMe (III) (Aib: alpha-aminoisobutyric acid, beta Ala: beta-alanine, gamma Abu: gamma-aminobutyric acid, m-ABA: meta-aminobenzoic acid) with homologated amino acids at the N-terminus, the rigid gamma-amino acid m-ABA at the C-terminus and the helicogenic Aib at the central position have been chosen to create unusual turns. Single crystal X-ray diffraction studies, solvent dependent NMR titrations and 2D NMR analysis reveal that peptides II and III adopt unusual turns of 11- and 12-membered rings stabilized by modified 4 -> 1 type intramolecular hydrogen bonds. Solution phase studies indicate that peptide I exists in the beta-turn conformation stabilized by 10-membered intramolecular hydrogen bonding.

Rigid body trajectories in different 6D spaces

The objective of this paper is to show that the group SE(3) with an imposed Lie-Poisson structure can be used to determine the trajectory in a spatial frame of a rigid body in Euclidean space. Identical results for the trajectory are obtained in spherical and hyperbolic space by scaling the linear displacements appropriately since the influence of the moments of inertia on the trajectories tends to zero as the scaling factor increases. The semidirect product of the linear and rotational motions gives the trajectory from a body frame perspective. It is shown that this cannot be used to determine the trajectory in the spatial frame. The body frame trajectory is thus independent of the velocity coupling. In addition, it is shown that the analysis can be greatly simplified by aligning the axes of the spatial frame with the axis of symmetry which is unchanging for a natural system with no forces and rotation about an axis of symmetry.

Acoustic scattering by an inhomogeneous layer on a rigid plate

The problem of scattering of time-harmonic acoustic waves by an inhomogeneous fluid layer on a rigid plate in R2 is considered. The density is assumed to be unity in the media: within the layer the sound speed is assumed to be an arbitrary bounded measurable function. The problem is modelled by the reduced wave equation with variable wavenumber in the layer and a Neumann condition on the plate. To formulate the problem and prove uniqueness of solution a radiation condition appropriate for scattering by infinite rough surfaces is introduced, a generalization of the Rayleigh expansion condition for diffraction gratings. With the help of the radiation condition the problem is reformulated as a system of two second kind integral equations over the layer and the plate. Under additional assumptions on the wavenumber in the layer, uniqueness of solution is proved and the nonexistence of guided wave solutions of the homogeneous problem established. General results on the solvability of systems of integral equations on unbounded domains are used to establish existence and continuous dependence in a weighted norm of the solution on the given data.

Padé approximants for the acoustical properties of rigid frame porous media with pore size distributions

Expressions for the viscosity correction function, and hence bulk complex impedance, density, compressibility, and propagation constant, are obtained for a rigid frame porous medium whose pores are prismatic with fixed cross-sectional shape, but of variable pore size distribution. The lowand high-frequency behavior of the viscosity correction function is derived for the particular case of a log-normal pore size distribution, in terms of coefficients which can, in general, be computed numerically, and are given here explicitly for the particular cases of pores of equilateral triangular, circular, and slitlike cross-section. Simple approximate formulae, based on two-point Pade´ approximants for the viscosity correction function are obtained, which avoid a requirement for numerical integration or evaluation of special functions, and their accuracy is illustrated and investigated for the three pore shapes already mentioned

Padé approximants for the acoustical characteristics of rigid frame porous media

In this paper it is shown that a number of theoretical models of the acoustical properties of rigid frame porous media, especially those involving ratios of Bessel functions of complex argument, can be accurately approximated and greatly simplified by the use of Padé approximation techniques. In the case of the model of Attenborough [J. Acoust. Soc. Am. 81, 93–102 (1987)] rational approximations are produced for the characteristic impedance, propagation constant, dynamic compressibility, and dynamic density, as a function of frequency and the material parameters. The model proposed by Stinson and Champoux

Active control of rod vibrations using magnetic fluids

The use of magnetic fluids in controlling rod vibrations is investigated. A prototype of ferrofluid vibration damper is designed and experimentally set up based on the principle of anti-resonance. The efficiency of this damping system is verified in experiments and well explained with classical equations of motion. The improvement of the present system towards active control of rod vibration is also discussed.

Connexin36, an Essential Element in the Rod Pathway, Is Highly Expressed in the Essentially Rodless Retina of Gallus gallus

Electrical coupling provided by connexins (Cx) in gap junctions (GJ) plays important roles in both the developing and the mature retina. In mammalian nocturnal species, Cx36 is an essential component in the rod pathway, the retinal circuit specialized for night, scotopic vision. Here, we report the expression of Cx36 in a species (Gallus gallus) that phylogenetic development endows with an essentially rodless retina. Cx36 gene is very highly expressed in comparison with other Cxs previously described in the adult retina, such as Cx43, Cx45, and Cx50. Moreover, real-time PCR, Western blot, and immunofluorescence all revealed that Cx36 expression massively increased over time during development. We thoroughly examined Cx36 in the inner and outer plexiform layers, where this protein was particularly abundant. Cx36 was observed mainly in the off sublamina of the inner plexiform layer rather than in the on sublamina previously described in the mammalian retina. In addition, Cx36 colocalized with specific cell markers, revealing the expression of this protein in distinct amacrine cells. To investigate further the involvement of Cx36 in visual processing, we examined its functional regulation in retinas from dark-adapted animals. Light deprivation markedly up-regulates Cx36 gene expression in the retina, resulting in an increased accumulation of the protein within and between cone synaptic terminals. In summary, the developmental regulation of Cx36 expression results in particular circuitry-related roles in the chick retina. Moreover, this study demonstrated that Cx36 onto- and phylogenesis in the vertebrate retina simultaneously exhibit similarities and particularities. J. Comp. Neurol. 512:651-663, 2009. (C) 2008 Wiley-Liss, Inc.

Rod bipolar cells in the retina of the capuchin monkey (Cebus apella): Characterization and distribution

Rod bipolar cells in Cebus apella monkey retina were identified by an antibody against the alpha isoform of protein kinase C (PKC alpha). which has been shown to selectively identify rod bipolars in two other primates and various mammals. Vertical sections were used to confirm the identity of these cells by their characteristic morphology of dendrites and axons. Their topographic distribution was assessed in horizontal sections; counts taken along the dorsal, ventral, nasal, and temporal quadrants. The density of rod bipolar cells increased from 500 to 2900 cells/mm(2) at 1 mm from the fovea to reach a peak of 10,000-12,000 cellss/mm(2) at 4 mm, approximately 5 deg of eccentricity, and then gradually decreased toward retinal periphery to values of 5000 cells/mm(2) or less. Rod to rod bipolar density ratio remained between 10 and 20 across most of the retinal extension. The number of rod bipolar cells per retina was 6,360,000 +/- 387,433 (mean +/- S.D., n = 6). The anti-PKC alpha antibody has shown to be a good marker of rod bipolar cells of Cebus, and the cell distribution is similar to that described for other primates. In spite of the difference in the central retina, the density variation of rod bipolar cells in the Cebus and Macaca as well as the convergence from rod to rod bipolar cells are Generally similar, suggesting that both retinae stabilize similar sensitivity (as measured by rod density) and convergence.

Behaviour of Surface Defects in Wire Rod Rolling

Defects are often present in rolled products, such as wire rod. The markets demand for wire rod without any defects has increased. In the final wire rod products, defects originating from the steel making, casting, pre-rolling of billets and during the wire rod rolling can appear. In this work, artificial V-shaped longitudinal surface cracks has been analysed experimentally and by means of FEM. The results indicate that the experiments and FEM calculations show the same tendency except in two cases, where instability due to a fairly “round” false round bars disturbed the experiment. FE studies in combination with practical experiments are necessary in order to understand the behaviour of the material flows in the groove and to explain whether the crack will open up as a V-shape or if it will be closed as an I-shape.

Short-Term Effects of the Use of Non-Rigid Tools for Postural Control by Adults with Intellectual Disabilities

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The rigid-flexible nonlinear robotic manipulator: Modeling and control

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)