Synthesis and structural characterisation of new Re(III) complexes using aldimines of α-amino acids as coligands

Complexes of the general formula [Re^III(L)Cl(PPh₃)₂] have been synthesised by reacting H₂L and [ReOCl₃(PPh₃)₂] in ethanol. Here H₂L represents imines of α-amino acids (glycine, l-alanine, l-valine, l-phenylalanine) derived from salicylaldehyde and naphthaldehyde. The crystal structure of one complex has been determined. The complexes are mononuclear, paramagnetic and display paramagnetic ¹H NMR in CDCl₃ solution. Their spectral and redox properties are scrutinised.     

A novel editing technique for F MRI: Molecule-specific imaging

A novel technique is proposed to facilitate the selective imaging of specific molecules from a mixture. The application of the technique presented here demonstrates the ability to selectively produce ¹⁹F MR images of either trifluoroacetic acid or the perfluorocarbon emulsion Oxypherol-ET (perfluorotributylamine), when both molecules are present simultaneously. Selective detection is based on the presence of homonuclear J-modulation in one molecule and differential spin-spin relaxation time (T₂). Perfluorotributylamine, an A₃B₂ system, is subject to homonuclear J-modulation, which produces a null signal from the antiphase components of the triplet (A₃) when an echo time is used in a spin-echo image. At this echo time the second molecule, in this example trifluoroacetic acid, a non-coupled spin system, is selectively imaged. At longer echo times, e.g., TE = 1/J there is substantial recovery of the J-modulated signal, which may be solely observed due to T₂ decay of the trifluoroacetic acid signal. The method is demonstrated both using phantoms and in vivo.     

Differential pulse polarographic determination of uranium(VI) in complex materials after adsorption of its trifluoroethylxanthate cetyltrimethylammonium ion-associated complex on naphthalene adsorbent.

Uranium(VI) is adsorbed as a uranium trifluoroethylxanthate (TFEX)-cetyltrimethylammonium (CTMA) ion-pair complex on microcrystalline naphthalene quantitatively in the pH range 4.2 - 7.0. Without cetyltrimethylammonium as the counter ion, the adsorption is hardly 70%. The metal has been desorbed with HCI and determined with a differential pulse polarograph. Uranium can alternatively be quantitatively adsorbed on TFEX-CTMA-naphthalene adsorbent packed in a column at a flow rate of 1 - 5 ml/min and determined similarly. A well-defined peak has been obtained in this medium at -0.20 V versus a saturated calomel electrode. Cyclic voltammetry, differential pulse polarography and D.C. polarography studies indicate that uranium has been reduced irreversibly under these conditions. The detection limit is 0.30 microg/ml at the minimum instrumental settings (signal-to-noise ratio of 2) (with a preconcentration factor of 10, the detection limit would be 30 ng/ml for uranium when the volume in the cell is 15 ml). However if the volume in the cell is 5 ml, it would have been 10 ng/ml with a preconcentration factor of 30. Linearity is maintained in a concentration range of 0.5 - 19.0 microg/ml (2.1 - 79.83 x 10(-9) M) with a correlation factor of 0.9994 and a relative standard deviation of +/-1.1% (in this case 7.5 microg may be concentrated from 150 ml of the aqueous sample where its concentration is as low as 50 ng/ml). Various parameters, such as the effect of the pH, volume of the aqueous phase, flow rate and the interference of a large number of metal ions and anions on the determination of uranium, have been studied in detail to optimize the conditions for its trace determination in various complex materials, like alloys, coal fly ash, biological, synthetic, and waste-water samples.     

Spin squeezing and quantum correlations

We discuss the notion of spin squeezing considering two mutually exclusive classes of spin-s states, namely, oriented and non-oriented states. Our analysis shows that the oriented states are not squeezed while non-oriented states exhibit squeezing. We also present a new scheme for construction of spin-s states using 2s spinors oriented along different axes. Taking the case of s=1, we show that the ‘non-oriented’ nature and hence squeezing arise from the intrinsic quantum correlations that exist among the spinors in the coupled state.     

Uhf to Ka band upconverter

A balanced upconverter circuit has been developed in planar transmission line configuration using NEC GaAs beam lead Schottky barrier diodes. RF power output of +1.6 dBm SSB is obtained at Ka-band when up converter is driven by +17 dBm IF and +20 dBm LO signal.     

Improved MR imaging in extremely inhomogeneous radio-frequency fields

An improvement to the method for imaging with extremely inhomogeneous radio-frequency fields is presented which uses a pseudo-noise-modulated selective (PNMS) excitation prepulse to randomize the signal from outside the selected slice. This prepulse reduces the problems that arise from imperfect subtraction involved with the one-dimensional ISIS-type slice selection procedures. The results demonstrate two to three times improvement in the signal-to-noise ratio and reduction in the image artifacts when this prepulse is used.     

Stabilization of the collagen structure by hydroxyproline residues

The molecular structure of collagen is now accepted to be based on a triple-stranded coiled-coil, in which the three strands are held together predominantly by hydrogen bonds. Recent experimental evidence has shown that the presence of hydroxyproline residues in the third position of the repeating tripeptide unit lends additional stability to the collagen structure. In this paper, we report a model structure, which is supported by these observations. In a model structure proposed earlier, there are two hydrogen bonds per tripeptide unit, one of which is a direct interchain hydrogen bond, while the second hydrogen bond can be formedvia a water molecule. It has now been shown that the same water molecule can also form a hydrogen bond with the oxygen of theγ-hydroxyl group of hydroxyproline in the third position in the sequence (Gly-R₂-R₃). This hydroxyl group can also take part in an inter-triple-helix hydrogen bond. Our studies thus show the role played by hydroxyproline residues in the structure and stability of collagen.     

Mössbauer isomer shifts and electric field grandients in Cr1−xFex Alloys

Room temperature Mössbauer spectra of Cr_1?xFe_x alloys (x=0.05–0.26) have been fitted using a pseudo-lorentzian lineshape; this leads to the widths of gaussian processes which contribute to the line broadening. The variation of isomer shift with composition can be described well by an extension to the cellular model of Miedema and co-workers. Estimations of the contributions of the s electron charge transfer and the s-d electron conversions to the isomer shift are presented.     

On the topological characterization of two-dimensional phase transitions

It is shown that for the two-dimensional planar-rotator model the variance of the number of vortices inside a large loop is proportional to the perimeter of the loop at all temperatures. A similar result holds for the variance of the charge inside a loop in the lattice Coulomb gas model. Hence a topological distinction between the high and low temperature phases of these models (area law versus perimeter law) is not possible.     

Sensitivity of Bayes decisions for the success probability for samples from a nonbinomial population

Summary A family of generalised negative binomial distributions is employed to investigate inference robustness of the Bayes estimator of the unknown parameter of the binomial distribution. A zone of sensitivity for the test of significance is constructed to forewarn the pro-Jeffreys Bayesians against indiscriminate choice of the probability in favour of the null hypothesis. A few selected tables are presented to illustrate the effect of relaxation of the ‘binomiality’ assumption.