Spin dynamics in conducting polymers studied by μSR

We report studies of spin dynamics in the conducting polymers polyaniline and polypyrrole using both μ⁺SR and μ^-SR techniques. These measurements reveal characteristic field dependences and cutoff frequencies for the muon spin relaxation which can be related to the spin diffusion process. Clear evidence is seen for increased spin localisation at low temperatures where a crossover occurs from two or three dimensional spin diffusion to a one dimensional diffusion regime. This revised version was published online in August 2006 with corrections to the Cover Date.     

A convenient method for 3-pyrroline synthesis

[reaction: see text]. The synthesis of a range of 3-pyrrolines has been achieved from primary amine starting materials using a two-step alkylation/alkylidene carbene CH-insertion reaction sequence. We have shown that insertion into a range of CH-bond types is possible, and the formation of nitrogen-bearing quaternary stereocenters is a relatively facile process. The insertion reaction occurs with >95% retention of stereochemistry, but the presence of protecting groups on nitrogen is generally deleterious to the cyclization process.     

Synthesis of hyperbranched poly(aryl amine)s via a carbene insertion approach

A novel diazirine functionalised aniline derivative, 3-(3-aminophenyl)-3-methyldiazirine 1, was prepared and employed as an AB(2)-type monomer in the synthesis of hyperbranched polymers; thus providing the first instance in which polyamines have been prepared via carbene insertion polymerisation. Photolysis of the monomer 1 in bulk and in solution resulted in the formation of hyperbranched poly(aryl amine)s with degrees of polymerisation (DP) varying from 9 to 26 as determined by gel permeation chromatography (GPC). In solution, an increase in the initial monomer concentration was generally found to result in a decrease in the molecular weight characteristics of the resulting poly(aryl amine)s. Subsequent thermal treatment of the poly(aryl amine)s caused a further increase in the DP values up to a maximum of 31. Nuclear magnetic resonance (NMR) spectroscopic analysis revealed that the increase in molecular weight upon thermal treatment resulted from hydroamination of styrenic species formed in the initial photopolymerisation or activation of diazirine moieties.     

Amphiphilicity determines nanostructure in protic ionic liquids

The bulk structure of the two oldest ionic liquids (ILs), ethylammonium nitrate (EAN) and ethanolammonium nitrate (EtAN), is elucidated using neutron diffraction. The spectra were modelled using empirical potential structure refinement (EPSR). The results demonstrate that EAN exhibits a long-range structure of solvophobic origin, similar to a bicontinuous microemulsion or disordered L(3)-sponge phase, but with a domain size of only 1 nm. The alcohol (-OH) moiety in EtAN interferes with solvophobic association between cation alkyl chains resulting in small clusters of ions, rather than an extended network.     

Finite amplitude waves superimposed on pseudoplanar motions for Mooney-Rivlin viscoelastic solids

This paper deals exclusively with finite amplitude motions in viscoelastic materials for which the stress is the sum of a part corresponding to the classical Mooney-Rivlin incompressible isotropic elastic solid and of a dissipative part corresponding to the classical viscous incompressible fluid. Of particular interest is a finite pseudoplanar elliptical motion which is an exact solution of the equations of motion. Superposed on this motion is a finite shearing motion. An explicit exact solution is presented. It is seen that the basic pseudoplanar motion is stable with respect to the finite superposed shearing motion. Particular exact solutions are obtained for the classical neo-Hookean solid and also for the classical Navier-Stokes equations. Finally, it is noted that parallel results may be obtained for a basic pseudoplanar hyperbolic motion.     

A study of two-dimensional dispersion in unconsolidated porous media

An experimental and numerical investigation into the magnitude of longitudinal and transverse dispersion in a two-dimensional flow field over a particle Peclet number range of 50–8500 is reported. Numerical modelling using a Galerkin finite element method is used to test various models, notably those of Fried and combarnous and Koch and Brady. Dispersion at low Peclet numbers (< 200) is found to be described adequately by either model, which at large Peclet, the degree of dispersion is significantly underestimated. An improved dispersion model for Peclet numbers greater than 200 is proposed. The transverse dispersion term and the choice of inlet boundary condition are found to have a negligible effect on the shape of the breakthrough curve.Nomenclature A (z) Polynomial in the z plane - B (z) Polynomial in the z plane - C Concentration - C _f Feed concentration - C _o Concentration at the entrance - D Dispersion tensor - D _f Molecular diffusion coefficient - D ₁ Longitudinal dispersion coefficient - D _p Particle diameter - D _t Transverse dispersion coefficient - k Permeability/viscosity - k Dimensionless permiability in the Koch and Brady model - P Pressure - Pe _k Modified Peclet number, Pe _p k - Pe _p Particle Peclet number vD _p /D _f - v Velocity - z Axial coordinate or complex variable Greek letters Solution domain - Boundary - Porosity     

Separation of rat pituitary secretory granules by continuous flow electrophoresis

The separation of growth hormone-containing cytoplasmic secretory granules from the rat pituitary gland by continuous flow electrophoresis is described. The results are consistent with the hypothesis that granule subpopulations can be separated due to differences in surface charge; these, in turn, may be related to the oligomeric state of the hormone.