Vibrational spectra and crystal structure of the di‐amino acid peptide cyclo(L‐Met‐L‐Met): comparison of experimental data and DFT calculations

Experimental Raman and FT‐IR spectra of solid‐state non‐deuterated and N‐deuterated samples of cyclo(L ‐Met‐L ‐Met) are reported and discussed. The Raman and FT‐IR results show characteristic amide I vibrations (Raman: 1649 cm⁻¹, infrared: 1675 cm⁻¹) for molecules exhibiting a cis amide conformation. A Raman band, assigned to the cis amide II vibrational mode, is observed at ∼1493 cm⁻¹ but no IR band is observed in this region. Cyclo(L ‐Met‐L ‐Met) crystallises in the triclinic space group P1 with one molecule per unit cell. The overall shape of the diketopiperazine (DKP) ring displays a (slightly distorted) boat conformation. The crystal packing employs two strong hydrogen bonds, which traverse the entire crystal via translational repeats. B3‐LYP/cc‐pVDZ calculations of the structure of the molecule predict a boat conformation for the DKP ring, in agreement with the experimentally determined X‐ray structure. Copyright © 2009 John Wiley & Sons, Ltd.     

Comovements in government bond markets: A minimum spanning tree analysis

The concept of a minimum spanning tree (MST) is used to study patterns of comovements for a set of twenty government bond market indices for developed North American, European, and Asian countries. We show how the MST and its related hierarchical tree evolve over time and describe the dynamic development of market linkages. Over the sample period, 1993-2008, linkages between markets have decreased somewhat. However, a subset of European Union (EU) bond markets does show increasing levels of comovements. The evolution of distinct groups within the Eurozone is also examined. The implications of our findings for portfolio diversification benefits are outlined.     

MRICOM–MRI COntrast Modelling using 2D T1–T2 correlation spectra and relaxation signatures

Image contrast is calculated by inputting experimental 2D T₁–T₂ relaxation spectra into the ODIN software interface. The method involves characterising a magnetic resonance imaging pulse sequence with a “relaxation signature” which describes the sensitivity of the sequence to relaxation and is independent of sample parameters. Maximising (or minimising) the overlap between the experimental 2D T₁–T₂ relaxation spectra and the relaxation signature can then be used to maximise image contrast. The concept is illustrated using relaxation signatures for the echo planar imaging and Turbo spin-echo imaging sequences, together with in-vitro 2D T₁–T₂ spectra for liver and cartilage.     

The flipped longitudinal polarization sequence

By flipping the longitudinal magnetization with a chain of 180° pulses it is possible to effectively restore the effects of relaxation so that the same longitudinal magnetization is periodically recovered. The pulse sequence for achieving this, called Flipped LOngitudinal Polarization (FLOP), can be incorporated into any pulse sequence whenever it is desired to stop the attenuation in longitudinal magnetization caused by relaxation. We illustrate its use for fast, single-shot measurements of the longitudinal relaxation time and for three-dimensional T₁ mapping.     

Fast volumetric spatial-spectral MR imaging of hyperpolarized C-labeled compounds using multiple echo 3D bSSFP

Purpose

The goal of this work was to develop a fast 3D chemical shift imaging technique for the noninvasive measurement of hyperpolarized ¹³C-labeled substrates and metabolic products at low concentration.

Materials and Methods

Multiple echo 3D balanced steady state magnetic resonance imaging (ME-3DbSSFP) was performed in vitro on a syringe containing hyperpolarized [1,3,3-2H3; 1-¹³C]2-hydroxyethylpropionate (HEP) adjacent to a ¹³C-enriched acetate phantom, and in vivo on a rat before and after intravenous injection of hyperpolarized HEP at 1.5 T. Chemical shift images of the hyperpolarized HEP were derived from the multiple echo data by Fourier transformation along the echoes on a voxel by voxel basis for each slice of the 3D data set.

Results

ME-3DbSSFP imaging was able to provide chemical shift images of hyperpolarized HEP in vitro, and in a rat with isotropic 7-mm spatial resolution, 93 Hz spectral resolution and 16-s temporal resolution for a period greater than 45 s.

Conclusion

Multiple echo 3D bSSFP imaging can provide chemical shift images of hyperpolarized ¹³C-labeled compounds in vivo with relatively high spatial resolution and moderate spectral resolution. The increased signal-to-noise ratio of this 3D technique will enable the detection of hyperpolarized ¹³C-labeled metabolites at lower concentrations as compared to a 2D technique.     

Coupling p-multigrid to geometric multigrid for discontinuous Galerkin formulations of the convection–diffusion equation

An improved p-multigrid algorithm for discontinuous Galerkin (DG) discretizations of convection–diffusion problems is presented. The general p  -multigrid algorithm for DG discretizations involves a restriction from the p=1$p=1$ to p=0$p=0$ discontinuous polynomial solution spaces. This restriction is problematic and has limited the efficiency of the p  -multigrid method. For purely diffusive problems, Helenbrook and Atkins have demonstrated rapid convergence using a method that restricts from a discontinuous to continuous polynomial solution space at p=1$p=1$. It is shown that this method is not directly applicable to the convection–diffusion (CD) equation because it results in a central-difference discretization for the convective term. To remedy this, ideas from the streamwise upwind Petrov–Galerkin (SUPG) formulation are used to devise a transition from the discontinuous to continuous space at p=1$p=1$ that yields an upwind discretization. The results show that the new method converges rapidly for all Peclet numbers.     

Disorder-induced freezing of dynamical spin fluctuations in underdoped cuprate superconductors

We study the dynamical spin susceptibility of a correlated d-wave superconductor (dSC) in the presence of nonmagnetic disorder, using an unrestricted Hartree-Fock approach. This model provides a concrete realization of the notion that disorder slows down spin fluctuations, which eventually "freeze out." The evolution of disorder-induced spectral weight transfer agrees qualitatively with experimental observations on underdoped cuprate superconductors. For sufficiently large disorder concentrations, static spin density wave (SDW) order is created when droplets of magnetism nucleated by impurities overlap. We also study the disordered stripe state coexisting with a dSC and compare its magnetic fluctuation spectrum to that of the disorder-generated SDW phase.