Diffusion measurements to understand dynamics and structuring in solutions involving a homologous series of ionic liquids

The self-diffusion coefficients of each of the components in mixtures containing pyridine and each of the homologous series 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imides in acetonitrile were determined using NMR diffusometry (i. e., Pulsed Gradient Spin Echo). The nature of solvation was found to change significantly with the proportion of salt in the mixtures. Increased diffusion coefficients (when corrected for viscosity) for the molecular components were observed with increasing proportion of ionic liquid and with increasing alkyl chain length on the cation. Comparison of the molecular solvents suggests increased interactions in solution of the pyridine with other components of the mixture, consistent with the proposed interactions shown previously to drive changes in reaction kinetics. Discontinuities were seen in the diffusion data for each species in solution across different ionic liquids between the hexyl and octyl derivatives, suggesting a change in the structuring in solution as the alkyl chain on the cation changes and demonstrating the importance of such when considering homologous series

Ultra-high field MRI for evaluation of rectal cancer stroma ex vivo : correlation with histopathology

Purpose or Objective: Current clinical MRI techniques in rectal cancer are unable to differentiate Stage T1 from T2 (invasion of muscularis propria) tumours, and the differentiation of tumour from desmoplastic reaction or fibrous tissue remains a challenge1. Diffusion tensor imaging (DTI) MRI has potential to assess collagen structure and organisation (anisotropy). To our knowledge, there have been no MRI studies assessing DTI MRI for rectal cancer ex vivo. The purpose of this study was to examine DTI MRI derived biomarkers of rectal cancer stromal heterogeneity at high field strength ex vivo

Better, faster, more versatile NMR diffusion measurements

The range of applications and versatility of NMR diffusion measurements [1,2] increase with the speed, accuracy, and the practical lower concentration limits that can be used. For example, faster measurements expand the horizons of diffusion measurements to study reaction kinetics [3,4], as well as simply increasing throughput. Our group has been investigating various approaches for improving the performance of NMR diffusion measurements. Here we present some of our recent advances

NMR diffusometry

Over the last several decades NMR diffusion measurements have evolved into an ever more powerful suite of tools for non-invasively studying translational dynamics. Most modern spectrometers are now capable of performing standard NMR diffusion measurements. The information content available ranges from estimates of translational diffusion in free solution from which solution structure and molecular size can be studied, to information on characteristic distances when the motion occurs within restricted systems. When coupled with electric field pulses it is possible to measure electrophoretic mobility. Thus, it is now possible to separate the resonances from a sample containing a mixture of species on the basis of size or charge. Experimental and theoretical advances in NMR diffusometry have increased the accuracy, information content and range of applicable systems including clinical applications. This chapter touches upon all of these issues

Direct hydrodynamic radius measurement on dissolved organic matter in natural waters using diffusion NMR

Dissolved organic matter from natural waters is a complex mixture of various chemical components, which play vital roles in many environmental processes such as the global carbon cycle and the fate of many key anthropogenic pollutants. Despite its environmental significance, dissolved organic matter in natural form has never been studied using nuclear magnetic resonance based hydrodynamic radius measurements due to its extremely low concentration (e.g., a few mg/L) in natural waters. In this study, NMR-based hydrodynamic radius measurements were performed directly on unconcentrated pond, river, and sea waters. The key chemical components of the dissolved organic matters from different sources were identified as carbohydrates, carboxyl-rich alicyclic molecules, and aliphatic molecules. By using the Stokes-Einstein-Sutherland equation, the average hydrodynamic radii of the three key components were calculated

1H NMR diffusion studies of water self-diffusion in supercooled aqueous sodium chloride solutions

The physical properties of aqueous sodium chloride solutions have been studied theoretically, but so far no experimental diffusion data have been obtained under supercooled conditions. Here the results of 1H NMR translational diffusion measurements of water in sodium chloride solutions in the temperature range 230 to 300 K and sodium chloride concentrations up to 4.2 mol/kg are presented. It was found that the diffusion data were well-described by the Vogel–Tamman–Fulcher relationship with concentration-dependent parameters D0, B, and T0. The results indicate that under supercooled conditions the influence of sodium chloride on water diffusion is much smaller than predicted by molecular dynamics simulations

MAG-PGSTE : a new STE-based PGSE NMR sequence for the determination of diffusion in magnetically inhomogeneous samples

A new stimulated echo based pulsed gradient spin-echo sequence, MAG-PGSTE, has been developed for the determination of self-diffusion in magnetically inhomogeneous samples. The sequence was tested on two glass bead samples (i.e., 212-300 and <106 μm glass bead packs). The MAG-PGSTE sequence was compared to the MAGSTE (or MPFG) (P.Z. Sun, J.G. Seland, D. Cory, Background gradient suppression in pulsed gradient stimulated echo measurements, J. Magn. Reson. 161 (2003) 168-173; P.Z. Sun, S.A. Smith, J. Zhou, Analysis of the magic asymmetric gradient stimulated echo sequence with shaped gradients, J. Magn. Reson. 171 (2004) 324-329; P.Z. Sun, Improved diffusion measurement in heterogeneous systems using the magic asymmetric gradient stimulated echo (MAGSTE) technique, J. Magn. Reson. 187 (2007) 177-183; P. Galvosas, F. Stallmach, J. Karger, Background gradient suppression in stimulated echo NMR diffusion studies using magic pulsed field gradient ratios, J. Magn. Reson. 166 (2004) 164-173, P. Galvosas, PFG NMR-Diffusionsuntersuchungen mit ultra-hohen gepulsten magnetischen Feldgradienten an mikroporosen Materialien, Ph.D. Thesis, Universitat Leipzig, 2003, P.Z. Sun, Nuclear Magnetic Resonance Microscopy and Diffusion, Ph.D. Thesis, Massachusetts Institute of Technology, 2003) sequence and Cotts 13-interval [R.M. Cotts, M.J.R. Hoch, T. Sun, J.T. Marker, Pulsed field gradient stimulated echo methods for improved NMR diffusion measurements in heterogeneous systems, J. Magn. Reson. 83 (1989) 252-266] sequence using both glass bead samples. The MAG-PGSTE and MAGSTE (or MPFG) sequences outperformed the Cotts 13-interval sequence in the measurement of diffusion coefficients; more interestingly, for the sample with higher background gradients (i.e., the <106 μm glass bead sample), the MAG-PGSTE sequence provided higher signal-to-noise ratios and thus better diffusion measurements than the MAGSTE and Cotts 13-interval sequences. In addition, the MAG-PGSTE sequence provided good characterization of the surface-to-volume ratio for the glass bead samples

Simultaneous convection compensation and solvent suppression in biomolecular NMR diffusion experiments

Thermal convection and high intensity solvent resonances can significantly hamper diffusion estimates in pulsed gradient spin-echo nuclear magnetic resonance diffusion experiments on biomolecule samples. To overcome these two problems, a new double functional NMR diffusion sequence, double echo PGSTE-WATERGATE, is presented. The new sequence provides excellent convection compensation and solvent suppression (with a suppression factor in excess of at least 105 in a single scan) in biomolecular NMR diffusion experiments. Due to its stimulated echo nature, the new sequence is much less susceptible to spin–spin relaxation than Hahn spin-echo based sequences. Furthermore, the new sequence is not susceptible to spin diffusion due to the application of bipolar pulsed gradients. The new sequence is also much easier to set up compared to previously developed stimulated echo based convection compensation and solvent suppression sequence. The utility of the new sequence is demonstrated on an aqueous lysozyme sample

Common problems and artifacts encountered in solution-state NMR experiments

NMR experiments contain many parameters that need to be set properly to produce spectra free from errors and artifacts. Modern NMR spectrometers nowadays incorporate standard experimental templates with ideal parameters that suit many common samples. These address many of the problems associated with most parameters but because of the variety of samples and various experiments that can be performed, the obtained spectra can be less than ideal displaying unwanted artifacts and inaccurate spectral properties. In this paper, some of the most common problems and artifacts in NMR experiments are presented and solutions discussed