Conformational characterisation of valinomycin complexation with barium salts:A nuclear magnetic resonance spectroscopic study

Conformations of valinomycin and its complexes with Perchlorate and thiocyanate salts of barium, in a medium polar solvent acetonitrile, were studied using nuclear magnetic resonance spectroscopic techniques. Valinomycin was shown to have a bracelet conformation in acetonitrile. With the doubly charged barium ion, the molecule, at lower concentrations, predominantly formed a 1:1 complex. At higher concentrations, however, apart from the 1:1, peptide as well as ion sandwich complexes were formed in addition to a :final complex:. Unlike the standard 1:1 potassium complex, where the ion was centrally located in a bracelet conformation, the a 1:1 barium complex contained the barium ion at the periphery. The a :final complex: appeared to be an open conformation with no internal hydrogen bonds and has two bound barium ions. This complex was probably made of average of many closely related conformations that were exchanging very fast (on nuclear magnetic resonance time scale) among them. The conformation of the a:final complex a: resembled the conformation obtained in the solid state. Unlike the Perchlorate anion, the thiocyanate anion seemed to have a definite role in stabilising the various complexes. While the conformation of the 1:1 complex indicated a mechanism of ion capture at the membrane interface, the sandwich complexes might explain the transport process by a relay mechanism.

Resistance Minimum in Dilute Magnetic Alloys in the Absence of Impurity Moments

A possible mechanism for the resistance minimum in dilute alloys in which the localized impurity states are non-magnetic is suggested. The fact is considered that what is essential to the Kondo-like behaviour is the interaction of the conduction electron spin s with the internal dynamical degrees of freedom of the impurity centre. The necessary internal dynamical degrees of freedom are provided by the dynamical Jahn-Teller effect associated with the degenerate 3d-orbitals of the transition-metal impurities interacting with the surrounding (octahedral) complex of the nearest-neighbour atoms. The fictitious spin I characterizing certain low-lying vibronic states of the system is shown to couple with the conduction electron spin s via s-d mixing and spin-orbit coupling, giving rise to a singular temperature-dependent exchange-like interaction. The resistivity so calculated is in fair agreement with the experimental results of Cape and Hake for Ti containing 0.2 at% of Fe.

Mechanics of transition in an axisymmetric laminar boundary layer on a circular cylinder

Measurements of the growth of artificially generated turbulent spots and intermittency distribution in the transition region on a circular cylinder in axial flow show that the instability Reynolds number of 11,000 has a marked effect on the properties. In particular, it is found that the spot production in the initial region when a single turbulent spot has not yet wrapped around the cylinder and the propagation is essentially two-dimensional, is significantly altered. But the transition in the downstream or latter region, where most of the turbulent spots propagate onedimensionally (like the turbulent plugs in a pipe), is not affected. When the radius Reynolds number is more than 11,000, the intermittency law in the initial region is essentially the same as in twodimensional flow on a flat plate and in the latter region it is the one-dimensional flow in a pipe, the demarcation between the two regions being quite sharp.

Lithium nuclear-magnetic-resonance in lithium acetate dihydrate, Li(CH3COO).2H2O

Li n.m.r, in single crystals of lithium acetate dihydrate is used to determine the quadrupole coupling parameters: (e2qQ/h) and r/. The orientations of the principal z, y and x components of the electric field gradient tensor are determined to be along the crystallographic b, a and c axes respectively. The parameters experimentally determined are (e2qQ/h)= 154"6 kHz; and i/= 0.9. This study indicates a tetrahedral configuration around the Li ion, confirming the recent X-ray and p.m.r, results.

Optical and magnetic resonance studies of the interaction of metallo tetraphenylporphyrins with nitrobenzofuroxan

Metallo tetraphenylporphyrins form I : I molecular complexes with 4,6-dinitrobenzofuroxan. The molecular association is described in terms of T-n. interaction with porphyrins functioning as donors. The association constants and thermodynamic parameters have been evaluated using optical absorption and 'H nmr spectral methods. Based on the binding constants, the donor ability of various metalloporphyrins can be arranged in the following order: Pd(I1) > Co(I1) > Cu(I1) > Ni(I1) - VO(1V) - 2H > Zn(l1). Electron paramagnetic resonance studies of the complexes reveal that the IT-complexation results in changes in the electronic structure of the central metal ions which are reflected in the changes in the M-N 5 bonding. The dipolar contribution to the acceptor proton chemical shifts in the CoTPP complex has been partitioned from ring current contributions using the shifts observed in the ZnTPP complex. The shifts, along with the line broadening ratios observed for the CoTPP complex, are used to arrive at the possible solution structures of the complexes.

Townsend's First Ionization Coefficients and Sparking Potentials in Crossed Electric and Magnetic Fields

Townsend's first ionization coefficients have been measured in corssed electric and magnetic fields for values of B/p ranging from 0.013 TESLA. TORR-1 to 0.064 TESLA.TORR-1 and for 103 x 102¿ E/p 331 x 102 V.M-1. TORR-1 in oxygen and for 122 x 102¿ E/pÂ488 x 102 V.M-1.TORR-1 for dry air. The values of effective collision frequencies determined from the equivalent pressure (pe) concept generally increase with E/p at constant B/p and decrease with increasing B/p at constant E/p. Effective collision frequencies determined from measured sparking potentials at high values of E/p increase with decreasing E/pe. The drift velocity and mean energy of electrons in oxygen in crossed electric and magnetic fields have been derived.

High-pressure magnetic susceptibility of the intermediate valence system EuPd2Si2

The pressure dependence (0-7 kbar) of the magnetic susceptibility is reported for the intermediate valence system EuPd2Si2 in the temperature interval 77-300K. It is found that the thermally induced valence transition becomes more gradual on application of pressure The characteristic fluctuation temperature Tf, also seems to be pressure dependent.

Axisymmetric stress distribution in a transversely isotropic thick plate with a circular hole

An exact solution for the stresses in a transversely isotropic infinite thick plate having a circular hole and subjected to axisymmetric uniformly distributed load on the plane surfaces has been given. The solution is in the form of Fourier-Bessel series and integrals. Numerical results for the stresses are given using the elastic constants for magnesium, and are compared with the isotropic case.

A versatile and flexible digital pulse programmer for pulsed nuclear magnetic resonance

A versatile and flexible digital pulse programmer for two-pulse, three-pulse, saturation burst and Carr-Purcell sequences is described. Independently variable controls for pulse widths (0.2 mu s to 100 mu s), delay between pulses (0.2 mu s to 100 s) and for number of pulses (1 to 99) for the saturation burst and for the Carr-Purcell sequence, are brought to the front panel. The programmer can be used for one-shot experiments as well as for repetitive experiments.

Preparation, IR and nuclear magnetic resonance studies on the rare-earth perchlorate complexes of 3-methylpyridine-1-oxide

THE COMPLEXES of pyridine-l-oxide and 2- and 4-substituted pyridine-l-oxides have been investigated previously[l]. The complexes of 3-substituted pyfidine-l-oxides, however, have received little attention. The rare-earth complexes of pyridine-Ioxide[l, 2], 4-methylpyridine- l-oxide [1] and 2,6- dimethylpyfidine-l-oxide[3,4] have been reported earlier. The present paper deals with the isolation and characterisation of 3-methylpyridine-l-oxide (3-Picoline-N-oxide, 3-PicNO) complexes with rare-earth perchlorates.

Stress analysis of a thick plate having a circular hole under axisymmetric radial load

In this paper a solution for the determination of stresses and displacements in a thick plate having a cylindrical hole subjected to localised hydrostatic loading has been given. Detail numerical results have been presented and compared with the results of an infinite hole subjected to localised hydrostatic load and a semiinfinite hole subjected to localised end load. It has been shown that for certain ratio of thickness of the pate to the radius of the hole and loading, the results could be obtained by using the solution of infinite or semiinfinite hole subjected to the same hydrostatic loading.

Nonsimilar incompressible laminar boundary layers with magnetic field.

The solution of the steady laminar incompressible nonsimilar magneto-hydrodynamic boundary layer flow and heat transfer problem with viscous dissipation for electrically conducting fluids over two-dimensional and axisymmetric bodies with pressure gradient and magnetic field has been presented. The partial differential equations governing the flow have been solved numerically using an implicit finite-difference scheme. The computations have been carried out for flow over a cylinder and a sphere. The results indicate that the magnetic field tends to delay or prevent separation. The heat transfer strongly depends on the viscous dissipation parameter. When the dissipation parameter is positive (i.e. when the temperature of the wall is greater than the freestream temperature) and exceeds a certain value, the hot wall ceases to be cooled by the stream of cooler air because the ‘heat cushion’ provided by the frictional heat prevents cooling whereas the effect of the magnetic field is to remove the ‘heat cushion’ so that the wall continues to be cooled. The results are found to be in good agreement with those of the local similarity and local nonsimilarity methods except near the point of separation, but they are in excellent agreement with those of the difference-differential technique even near the point of separation.

Note on the Helmholtz instability in stratified flows with magnetic fields

The nature of the neutral curves for the stability of a Helmholtz velocity profile in a stratified, Boussinesq fluid in the presence of a uniform magnetic field for the cases (1) an infinite fluid (2) a semi-infinite fluid with a rigid boundary is discussed.

Effect of membrane action on the plastic collapse load of circular orthotropic slabs with fixed edges

In the case of reinforced concrete slabs fixed at the boundaries, considerable enhancement in the load carrying capacity takes place due to compressive membrane action. In this paper a method is presented to analyse the effects of membrane action in fixed orthotropic circular slabs, carrying uniformly distributed loads. Depending on the radial moment capacity being greater or less than the circumferential moment capacity, two cases of orthotropy have been considered. Numerical results are worked out for certain assumed physical parameters and for different coefficients of orthotropy. Variations of load and bending moments with the central deflection are presented.