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P T Callaghan

Publications and source records attributed to P T Callaghan.

At least 37 records · Page 2Linked to original sources
PubMed1999

Multiple echoes, multiple quantum coherence, and the dipolar field: demonstrating the significance of higher order terms in the equilibrium density matrix.

It is well known that dipolar field effects lead to multiple spin echoes in a simple two-RF pulse experiment (the MSE experiment). We show here that coherence transfer echoes (which identify the existence of multiple quantum coherences in liquid NMR) and multiple spin echoes have a common origin. Using density matrix theory we have calculated the phase and timing of multiple spin echoes from all quadrature phase combinations of RF pulses. We show for the MSE experiment that there is a one-to-one correspondence between the time domain echo order and the multiple quantum coherence order. The experimental confirmation of these phase predictions shows that multiple spin echoes provide independent evidence for the breakdown of the high temperature approximation as proposed by Warren et al. (Science 262, 2005 (1993)).

Artifacts↗
PubMed1999

11B magnetic resonance imaging and MAS spectroscopy of trimethylborate-treated radiata pine wood.

Boron-11 nuclear magnetic resonance imaging and spectroscopy have been used to characterise the nature and distribution of boron compounds after preservative treatment of radiata pine wood with trimethylborate (TMB). One day after treatment, 11B magnetic resonance imaging microscopy showed significant differences in the morphological distribution of boron species, with there apparently being no treatment penetration of the latewood. 11B MAS NMR spectroscopy of freshly preservative-treated radiata pine wood, which had been separated into latewood and earlywood, showed the only boron species present in the latewood to be boric acid while in the earlywood both TMB and boric acid were initially present. Due to quadrupolar broadening and a short T2 value, the boric acid signal relaxed too quickly to be observable and this caused the apparent lack of 11B in the image when only boric acid was present. TMB undergoes hydrolysis to form boric acid and in radiata pine latewood, this hydrolysis reaction is rapid.

Borates↗
PubMed1999

Taylor dispersion and molecular displacements in Poiseuille flow.

We have used pulsed gradient spin echo (PGSE) NMR to measure longitudinal displacements of octane molecules undergoing Poiseuille flow in a 150 microm diameter pipe, accessing time scales which approach the Taylor dispersion limit. We monitor the change in displacement distribution which occurs as molecules undergoing Brownian motion sample an increasing proportion of the ensemble of streamlines, observing the effects of wall collisions and the gradual transition of the propagator from Poiseuille to Taylor-Aris behavior. The further use of a double PGSE sequence allows the direct measurement of the stochastic part of the motion alone.

Journal Article↗
PubMed1996

NMR imaging, NMR diffraction and applications of pulsed gradient spin echoes in porous media.

Diffraction ideas were first introduced to NMR by Mansfield and Grannell. Here we compare "Mansfield (k-space) diffraction" with the "diffusive (q-space) diffraction," noting their similarities and differences. The diffusive-diffraction concept is extremely helpful in elucidating the Pulsed Gradient Spin Echo NMR experiment for fluid molecules in porous media and has been applied successfully to the model isolated pore (the "single slit" case) and the orientationally disordered interconnected pore glass (the "powder grating" case). This picture is based on the idea that the PGSE experiment has a scattering analogy in which a wavevector (q) is conjugate to the displacement of the spins over the time, D, between the gradient pulses. Recently, the theory has been extended to allow for both wall relaxation effects and finite gradient pulse width effects.

Fourier Analysis↗
PubMed1995

A method to distinguish between chemical shift and susceptibility effects in NMR microscopy and its application to insect larvae.

We propose a simple method of distinguishing Zeeman broadening arising from susceptibility inhomogeneity and chemical shift variation, applicable to NMR microscopy. The method is based on the use of a specially built probe-head in which orthogonal sample alignment is possible using the same radiofrequency (RF) coil. This allows the investigation of alignment effects in image distortion and relies on the fact that the isotropic chemical shift is invariant under reorientation, whereas the susceptibility-related local field will depend strongly on relative orientation of bounding surfaces with the external polarizing field. We apply this approach to the study of a simple phantom, and an insect larva (Spodoptera litura Fabricius), demonstrating in the latter case that susceptibility variations are sufficiently small to allow chemical shift imaging on a scale greater than 1 ppm.

Animals↗
PubMed1994

Use of static and dynamic NMR microscopy to investigate the origins of contrast in images of biological tissues.

NMR imaging experiments have been carried out on a fruit (Actinidia deliciosa) and plant stem (Stachys sylvatica) using a wide range of image contrasts. These included T1, T2, T2*, diffusion, flow and chemical shift selection. In the case of fruit imaging we calculated relaxation time and diffusion maps and established that the imaged parameters varied significantly with fruit ripening. These changes we attribute to changes in water dynamics resulting from elevated sugar concentrations. For the plant stem, water flow has been observed in the xylem vessels with a maximum velocity of 70 microns s-1. The role of image artifacts is considered and, in the case of transverse relaxation, we have demonstrated that it is necessary to use a precursor Carr-Purcell-Meiboom-Gill pulse train if additional diffusive attenuation is to be avoided.

Fruit↗
PubMed1994

Practical aspects of shielded gradient-coil design for localised in vivo NMR spectroscopy and small-scale imaging.

For a number of NMR applications the availability of screened gradients is crucial to minimize the effect of eddy currents on the NMR signal. In this paper we review two types of shielded gradient design: the target field and minimum inductance methods. The two designs are compared and construction details are presented. A novel coil design constructed with a double-sided primary and a single layered screen is outlined. Experimental results for both target field and minimum inductance coils are presented and compared.

Magnetic Resonance Spectroscopy↗
PubMed1992

"One-shot" velocity microscopy: NMR imaging of motion using a single phase-encoding step.

The use of the pulsed gradient spin-echo sequence in NMR microscopy enables the measurement of molecular translational motion and simultaneous construction of velocity and self-diffusion images, a technique that has been termed dynamic NMR microscopy. In this method the PGSE contrast gradient is stepped in a fourth dimension (q space) and so is inherently inefficient. Provided that one is prepared to sacrifice some of the additional information provided by the multiple PGSE gradient approach, it is possible to construct a velocity image alone by means of a single PGSE phase-encoding step. We illustrate applications of this method in which a signal from the stationary spins is nulled by the use of both gradient phase cycling and a final "z-storage" rf pulse. The limits to velocity resolution are around 10 microns s-1 in free water but can be considerably smaller for molecules with a low self-diffusion coefficient. We demonstrate this method in a study of water capillary flow at 12 microns transverse pixel resolution, extending the velocity range by employing a four-quadrant analysis method. This method is also used to measure vascular transport in a living plant and find a flow rate of around 45 microns s-1.

Diffusion↗
PubMed1992

Purpose-designed probes and their applications for dynamic NMR microscopy in an electromagnet.

The electromagnet provides a favorable environment for certain applications of NMR microscopy. These include plant imaging experiments and measurements of slow molecular diffusion, where high magnetic field gradients for the pulsed gradient spin echo (PGSE) technique are required. In this paper, two probes designed specifically for these two applications are described. In the first case, the open space within the probe has been maximized in order to incorporate environmental support systems for the plant, while in the second the smallest possible PGSE gradient coil former has been used to maximize the gradient strength. Examples are given of Dynamic NMR Microscopy experiments on a castor bean stem and on poly(ethylene oxide)/water solutions under shear thinning conditions.

Magnetic Resonance Spectroscopy↗
PubMed1991

Some biophysical applications of motional contrast in n.m.r. microscopy.

The principal advantage of the n.m.r. imaging method lies in the specific contrasts which are available. In this work we describe the use of velocity and diffusion contrast methods in biophysical applications and at microscopic spatial resolution. In the first example, involving water-protein interactions, the relationship between water self-diffusion and water concentration, as measured using pulsed gradient spin echo n.m.r., is shown. It is demonstrated that this relationship can be used to provide a water concentration image. The result is compared with the conventional proton density and transverse relaxation maps. The next example concerns the use of dynamic n.m.r. microscopy to obtain water diffusion and velocity maps for wheat grain in vivo. Finally we suggest how the method may be used in the study of polymer-water interactions in an unusual adjunct to conventional polymer self-diffusion studies.

Animals↗
PubMed1988

In vitro tracheal mechanics by nuclear magnetic resonance imaging.

Images of rabbit tracheal cross sections were obtained at a series of transmural pressures ranging from 22 to -95 cmH2O by use of a nuclear magnetic resonance imaging microscope. The excised, washed tracheas were immersed in a solution of phosphate-buffered saline made up in deuterium oxide (D2O, pH 7.3). The images are maps of proton density in the image slice (2.5 mm thick). All but one series of images showed a collapse process in which the trachealis muscle invaginated asymmetrically, i.e., the muscle appeared to favor one side of the cartilage ring system more than the other. The connecting tissue between the cartilage rings appeared to be more compliant than the rings themselves, thus suggesting that the tracheal lumen became corrugated at negative pressures. In the plane of a cartilage ring, the lumen appeared to remain patent at pressures as low as -95 cmH2O. However, between rings, where the tracheal wall was more compliant, the lumen appeared to be totally occluded at -53 cmH2O. Lumen areas in both the plane of the cartilage rings and in a plane between rings were measured from each series of printed images for six tracheas. These measurements, when normalized, averaged, and plotted against transmural pressure gave asymptotic logarithmic compliances (n1 in the model of Lambert et al., J. Appl. Physiol. 52: 44-56, 1982) of 1.2 +/- 0.4 and 20 +/- 7 for the interring and ring regions, respectively. These values are greater than the critical value of 0.5 (J. Appl. Physiol. 62: 2426-2435, 1987) and are thus consistent with wave speed flow limitation being possible anywhere in the trachea during forced expiration.

Animals↗
PubMed1979

Diffusion of water in the endosperm tissue of wheat grains as studied by pulsed field gradient nuclear magnetic resonance.

Pulsed field gradient nuclear magnetic resonance has been used to measure water self-diffusion coefficients in the endosperm tissue of wheat grains as a function of the tissue water content. A model that confines the water molecules to a randomly oriented array of capillaries with both transverse dimension less than 100 nm has been used to fit the data and give a unique diffusion coefficient at each water content. The diffusion rates vary from 1.8 x 10(-10) m2s-1 at the lowest to 1.2 x 10(-9) m2s-1 at the highest moisture content. This variation can be explained in terms of an increase in water film thickness from approximately 0.5 to approximately 2.5 nm over the moisture range investigated (200-360 mg g-1).

Diffusion↗
PubMedDate not supplied

Time-dependent velocities in porous media dispersive flow.

Pulsed Gradient Spin Echo (PGSE) NMR methods may be used to measure the asymptotic dispersion coefficient as well as the velocity autocorrelation function (VACF) in porous media flow. The VACF can be measured in the frequency domain using repetitive gradient pulse trains, and in the time domain using double PGSE encoding. The one dimensional double PGSE method, and the two dimensional velocity exchange experiment (VEXSY) are briefly outlined and their application to flow in monodisperse 0.5 mm diameter beads packs described, both axial and transverse VACFs being examined. The measured correlation times are shown to agree well with calculated values. The asymptotic dispersion coefficients agree with literature values in the case of transverse flow while in axial flow it is shown that asymptotic conditions are not achieved, even for observation times longer than the correlation time for flow around a bead.

Magnetic Resonance Imaging↗
PubMedDate not supplied

Low-frequency velocity correlation spectrum of fluid in a porous media by modulated gradient spin echo.

In addition to the fast correlation for local stochastic motion, the molecular velocity correlation function in a fluid enclosed within the pore boundaries features a slow long time-tail decay. Here we present its study by the NMR modulated gradient spin-echo method (MGSE) [1] on a system of water trapped in the space between the closely packed polystyrene beads. With MGSE pulse sequence, a repetitive train of RF pulses with interspersed gradient pulses periodically modulates the spin phase. It gives the spin echo attenuation proportional to a value of the molecular velocity correlation spectrum at the modulation frequency. Covering the frequency range between Hz and MHz, it is a complement to the quasi-elastic neutron scattering, and so a suitable technique for the investigation of low frequency molecular dynamics in fluids. In our experiment, it enables to extract the low frequency correlation spectrum of water molecules confined in porous media. The function exhibits a negative long time-tail characteristic (a low frequency decay of the spectrum), which can be interpreted as a molecular back scattering on boundaries. The results can be well fitted with the spectrum calculated from the solution of the Langevin equation for restricted diffusion (which exhibits an exponential decay) [2] as well as with the spectrum obtained when simulating the hydrodynamics of molecular motion constrained by capillary walls (which gives an algebraic decay) [3]. Despite much work on theories and simulation, which predict slow negative long time tail of molecular velocity correlation dynamics in confined fluids, the obtained velocity correlation spectrum is the first experimental evidence to confirm these effects. The obtained dependence of spin echo attenuation on time, gradient strength and modulation frequency is also the first experimental verification of the recently developed approach to the spin echo in porous media, that uses the spin phase average with the cumulant expansion to get the attenuation as a discord of spin spatial coherence [4].

Magnetic Resonance Spectroscopy↗
PubMedDate not supplied

Use of the second dimension in PGSE NMR studies of porous media.

2-dimensional methods based on PGSE NMR may be used to correlate or separate molecular dynamical properties, or to elucidate fluctuations. These may utilize either the gradient (q-vector) domain, in which molecular displacements are measured, or the time domain, in which relaxation is measured, and may be analyzed by combinations of inverse Fourier or Laplace transforms. Existing methodologies are reviewed and new experiments proposed. In particular the use of diffusion-diffusion exchange and correlation analysis is demonstrated using the case of water diffusion in a lamellar phase liquid crystal.

Anisotropy↗
PubMedDate not supplied

Spatial dependence of dispersion.

The use of Pulsed Gradient Spin Echo (PGSE) NMR to investigate flow in porous media is well established. Using two pairs of position-encoding pulses in the PGSE experiment gives the possibility of examining velocity fluctuations, by comparing displacements, during the two encoding intervals. This method may be used to measure the asymptotic dispersion coefficient as well as the Velocity Auto-Correlation Function (VACF) in porous media flow. Some examples of two-dimensional maps of density and velocity distributions are accompanied by the first attempt to perform localized measurements of flow dispersion in porous media.

Magnetic Resonance Spectroscopy↗