Synthesis and Structure of Chromium(II) Complexes Supported by Both a β-Diketiminate and an Amidinate Ligand

Abstract  

The complexes (bis(2,6-diisopropylphenyl)pentane-2,4-ketiminato)(μ₂-diisopropylacetamidinato) chromium(II) (1) and (bis(2,6-diisopropylphenyl)pentane-2,4-ketiminato)(μ₂-dicyclohexylacetamidinato) chromium(II) (2) have been synthesized and structurally characterized. Complex 1 crystallizes in space group Pbcn with crystal cell parameters a = 10.7183(13) ?, b = 16.4093(19) ?, c = 20.687(2) ?, V = 3,638.3(7) ?³ and Z = 4. Complex 2 crystallizes in triclinic space group P-1 with crystal cell parameters a = 10.750(3) ?, b = 12.174(3) ?, c = 16.308(4) ?, α = 75.903(4)°, β = 82.137(4)°, γ = 85.511(4), V = 2,048.4(8) ?³ and Z = 2. The complexes adopt a spiro distorted square planar geometry and have similar structural parameters.     

Adamantyl‐endcapped polyynes

Polyynes spanning from a diyne to a dodecayne with adamantyl endgroups have been synthesized using the Fritsch–Buttenberg–Wiechell rearrangement as a key step to construct the acetylenic framework. Molecular properties as a function of polyyne length have been analyzed by UV–Vis spectroscopy, cyclic voltammetry, differential scanning calorimetry, and X‐ray crystallography. Copyright © 2011 John Wiley & Sons, Ltd.     

A Thermodynamic Study of 1-Propanol–Glycerol–H2O at 25°C: Effect of Glycerol on Molecular Organization of H2O

The excess chemical potential, partial molar enthalpy, and volume of 1-propanol were determined in ternary mixtures of 1-propanol–glycerol–H₂O at 25°C. The mole fraction dependence of all these thermodynamic functions was used to elucidate the effect of glycerol on the molecular organization of H₂O. The glycerol molecules do not exert a hydrophobic effect on H₂O. Rather, the hydroxyl groups of glycerol, perhaps by forming clusters via its alkyl backbone with hydroxyl groups pointing outward, interact with H₂O so as to reduce the characteristics of liquid H₂O. The global hydrogen bond probability and, hence, the percolation nature of the hydrogen bond network is reduced. In addition, the degree of fluctuation inherent in liquid H₂O is reduced by glycerol perhaps by participating in the hydrogen bond network via OH groups. At infinite dilution, the pair interaction coefficients in enthalpy were evaluated and these data suggest a possibility that the interaction is mediated through H₂O.     

Polydomain model predictions of liquid crystalline polymer orientation in mixed shear/extensional channel flows

 The Larson-Doi (LD) polydomain model is used to simulate orientation development along the centerline of slit-expansion and slit-contraction flows of liquid crystalline polymers (LCPs). Orientation is computed using the LD structural evolution equations, subject to an imposed velocity field that accounts for the spatial variation of both shear and extension rates characteristic of this class of flows. Computed axial distributions of orientation averaged through the sample thickness are qualitatively similar to birefringence and X-ray scattering measurements of molecular orientation in similar flows of lyotropic and thermotropic LCPs. In slit-expansion flows, the simulations predict a 90^∘ flip in orientation direction near the midplane due to transverse stretching in the expansion region. Far away from the midplane where shear gradients dominate, orientation remains primarily along the flow direction. Within the LD model, tumbling and flow aligning materials respond in a qualitatively similar manner to mixed shear and extension, although tumbling materials are systematically more susceptible to the effects of extension. Received: 22 October 1999/Accepted: 13 January 2000     

Effect of Bauhinia monandra Kurz Leaf Preparations on Embryonic Stages and Adult Snails of Biomphalaria glabrata (Say, 1818), Schistosoma mansoni Cercariae and Toxicity in Artemia salina

Biomphalaria glabrata snails constitute the main vector of schistosomiasis in Brazil, and Bauhinia monandra Kurz, the leaves of which contain BmoLL lectin with biocidal action, is a plant widely found on continents in which the disease is endemic. This work describes the composition of B. monandra preparations and the effect on embryos and adult snails, their reproduction parameters and hemocytes. We also describe the results of a comet assay after B. glabrata exposure to sublethal concentrations of the preparations. Additionally, the effects of the preparations on S. mansoni cercariae and environmental monitoring with Artemia salina are described. In the chemical evaluation, cinnamic, flavonoid and saponin derivatives were detected in the two preparations assessed, namely the saline extract and the fraction. Both preparations were toxic to embryos in the blastula, gastrula, trochophore, veliger and hippo stages (LC₅₀ of 0.042 and 0.0478; 0.0417 and 0.0419; 0.0897 and 0.1582; 0.3734 and 0.0974; 0.397 and 0.0970 mg/mL, respectively) and to adult snails (LC₅₀ of 6.6 and 0.87 mg/mL, respectively), which were reproductively affected with decreased egg deposition. In blood cell analysis, characteristic cells for apoptosis, micronucleus and binucleation were detected, while for comet analysis, different degrees of nuclear damage were detected. The fraction was able to cause total mortality of the cercariae and did not present environmental toxicity. Therefore, B. monandra preparations are promising in combating schistosomiasis since they can control both the intermediate host and eliminate the infectious agent, besides being safe to the environment.     

Field-induced anisotropy in concentrated systems of rigid particles and macromolecules

This paper presents experimental results on the use of spectroscopic optical polarimetry to study structure in dense systems of rigid particles and rigid polymer liquid crystals. These measurements probe microstructural anisotropy induced by the application of electric fields in the case of dense suspensions of rigid spheres, or flow fields in the case of polymer liquid crystals. It is demonstrated that conservative linear dichroism can measure moments of the particle pair distribution function in dense suspensions. In liquid crystals, the dichroism is a result of field-induced anisotropy in the defect structure of the material.     

Empirically correct electrodynamics

The electrodynamics that predicts all known relevant observations is based upon the force F=(qq ′R/R³) [1 − 2v·v′/c² + 3(v·R) (v′·R)/c²R² + (a — a′)·R/c²] on charge q at r with the absolute velocity v and acceleration a due to charge q′ at r′ with absolute velocity v′ and acceleration a′, where R=r − r′. This force yields Ampere’s original empirical law for the force between current elements, which predicts the many effects due to Ampere tension between colinear current elements. It yields Faraday induction as well as Müller’s localized unipolar induction. The force on an accelerating charge due to a stationary charge yields Lenz’s law for the induced back emf; and, when applied to gravitation, qq′ being replaced by — Gmm′, it yields the inertial force ma, confirming Mach’s priniciple. For charge velocities approaching the velocity of light c it predicts the results of the Kaufmann-Bucherer experiments and the Bertozzi experiment, assuming neomechanics, or mass change with velocity. It is readily written as a field theory. Introducing time retardation, it yields waves and radiation. It predicts the observed zero self-torque on the Pappas-Vaughan Z-shaped antenna. Energy is conserved. The Weber electrodynamic theory is shown to fail.     

Mapping the Excited‐State Potential Energy Surface of a Photomolecular Motor

A detailed understanding of the operation and efficiency of unidirectional photomolecular rotary motors is essential for their effective exploitation in molecular nanomachines. Unidirectional motion relies on light‐driven conversion from a stable ( 1 a ) to a metastable ( 1 b ) conformation, which then relaxes through a thermally driven helix inversion in the ground state. The excited‐state surface has thus far only been experimentally characterised for 1 a . Here we probe the metastable, 1 b , excited state, utilising ultrafast transient absorption and femtosecond stimulated Raman spectroscopy. These reveal that the “dark” excited‐state intermediate between 1 a and 1 b has a different lifetime and structure depending on the initial ground‐state conformation excited. This suggests that the reaction coordinate connecting 1 a to 1 b differs to that for the reverse photochemical process. The result is contrasted with earlier calculations.     

Pseudo-spectral methods and linear instabilities in reaction-diffusion fronts

We explore the application of a pseudo-spectral Fourier method to a set of reaction-diffusion equations and compare it with a second-order finite difference method. The prototype cubic autocatalytic reaction-diffusion model as discussed by Gray and Scott [Chem. Eng. Sci. 42, 307 (1987)] with a nonequilibrium constraint is adopted. In a spatial resolution study we find that the phase speeds of one-dimensional finite amplitude waves converge more rapidly for the spectral method than for the finite difference method. Furthermore, in two dimensions the symmetry preserving properties of the spectral method are shown to be superior to those of the finite difference method. In studies of plane/axisymmetric nonlinear waves a symmetry breaking linear instability is shown to occur and is one possible route for the formation of patterns from infinitesimal perturbations to finite amplitude waves in this set of reaction-diffusion equations. (c) 1996 American Institute of Physics.     

Waiakeamide, a Cyclic Hexapeptide from the Sponge Ircinia dendroides(1)

From the sponge, Ircinia dendroides, collected in Indonesia we isolated a new cyclic hexapeptide, waiakeamide (1). Its structure, consisting of three proline residues, two methionine sulfoxides, and one thiazolylphenylalanine, was elucidated by spectral analysis and chemical degradation. Isolation and structural elucidation of waiakeamide is described.