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Biomedical subjects

P T Callaghan

Publications and source records attributed to P T Callaghan.

At least 19 recordsLinked to original sources
PubMed2003

Diffusion-relaxation correlation in simple pore structures.

The effects of independent encoding for relaxation and for diffusion using separate time and gradient dimensions are calculated for spins diffusing in plane parallel and spherical pores with relaxing walls. Two-dimensional inverse Laplace transformation is used to obtain computed (D,T(2)) maps for both geometries, in the regime in which the dimensionless diffusion coefficient is less than unity and the dimensionless relaxation parameter of order unity or greater. It is shown that there exist two distinct branches on the (D,T(2)) maps, one with diffusion and relaxation strongly correlated and one in which the diffusion coefficients vary widely independently of relaxation.

Biological Transport↗
PubMed2002

NMR visualization of displacement correlations for flow in porous media.

The temporal correlations of velocities for both water and a water-glycerol mixture flowing through a random packings of monodisperse spherical particles have been investigated using two-dimensional nuclear magnetic resonance methods. By combining various flow rates, fluid viscosities, and bead sizes, a wide range of flow parameters has been covered, the dimensionless Peclet number ranging from 100 to 100 000. The velocity exchange spectroscopy (VEXSY) technique has been employed to measure the correlation between velocities during two intervals separated from each other by a mixing time tau(m). This time is made both large and small compared with the time constant tau(c), required for a fluid element possessing the average flow velocity to cover a distance equal to the characteristic size in the system, the bead diameter. The two-dimensional conditional probability of displacement resulting from the VEXSY method reveals the existence of different "subensembles" of molecules, including a slow moving pool whose displacement is dominated by Brownian motion, an intermediate ensemble whose velocities change little over the mixing time, and a fast flowing ensemble which loses correlation due to mechanical dispersion. We find that that the approach to asymptotic dispersion, as tau(c)/tau(m) increases, depends strongly on the Peclet number, the deviation of the velocity autocorrelation function from a monoexponential Ornstein-Uhlenbeck process becoming more pronounced with increasing Peclet number.

Journal Article↗
PubMed2001

Biaxial deformation of a polymer under shear: NMR test of the Doi-Edwards model with convected constraint release.

2H NMR quadrupole interaction spectroscopy has been used to measure the deformation of a 670 kD poly(dimethylsiloxane) melt under shear in a Couette cell. The signals were acquired from a per deuterated benzene probe molecule which provides a motionally averaged sampling of the entire segmental ensemble. We have measured the dependence on shear rate of the S(XX) (velocity), S(YY) (velocity gradient), S(ZZ) (vorticity), and S(XY) (shear) elements of the segmental alignment tensor, as well as the angular dependence of the deuterium quadrupole splitting at fixed shear rate. We show that the data agree quite well with the Doi-Edwards theory but significantly better when convected constraint release effects are included. These fits return a value for the tube disengagement time of 100 ms.

Journal Article↗
PubMed2001

Shear banding and the isotropic-to-nematic transition in wormlike micelles.

Using deuterium NMR spectroscopy in a Couette cell, we observe shear-induced nematic ordering in the concentrated wormlike-micelle system CTAB/D(2)O, and our results are qualitatively consistent with birefringence studies, and in exact quantitative agreement with the degree of order measured in neutron-diffraction measurements. The width of the nematic region depends on shear rate, as well as on the temperature proximity to the equilibrium isotropic-nematic transition. Comparison of the nematic order profiles with velocity profiles obtained under identical conditions shows quite clearly that the nematic state is not identifiable with a highly sheared, low viscosity layer, and we conclude that the process of shearing induces a nematic state of high viscosity, possibly associated with mesoscale ordering. We present a simple model in which transition from the high shear branch to the viscous nematic branch is counterbalanced by subsequent relaxation of nematic order.

Biophysics↗
PubMed2001

One-shot velocimetry using echo planar imaging microscopy.

A rapid version of PEPI (pi-echo planar imaging) velocimetry has been implemented, enabling a velocity image, at microscopic resolution, to be acquired in less than 1 s. The velocity map was reconstructed using the phase information from the ratio of two PEPI images, one obtained with a velocity-encoding filter applied prior to the imaging sequence and the other image without. The acquisition time for each image was about 80 ms and the two complete image acquisitions were acquired in one shot in 500 ms. This rapid velocimetry sequence gave a good representation of laminar pipe flow. It has also been used to examine extensional flow in a biaxial extension in which the transient extension takes about 3 s.

Journal Article↗
PubMed2001

Selective storage of magnetization in strongly relaxing spin systems.

We have investigated the use of a "split-sinc" RF pulse to selectively store magnetization from a selected region of a sample, for later recall in imaging or spectroscopy experiments. The pulse sequence is based on an original suggestion by Post et al. (West German Patent No. P3209263.6, 13 March 1982), later implemented by Aue et al. (J. Magn. Reson. 56, 350 (1984)). We have carried out detailed numerical calculations using the Bloch equations and show that this particular sequence is robust in the face of strong transverse relaxation, and we demonstrate its application to imaging of polymer samples in shearing and extensional flow cells.

Journal Article↗
PubMed2001

Two-dimensional NMR of velocity exchange: VEXSY and SERPENT.

Two different multidimensional pulsed field gradient sequences are compared which have the purpose of correlating spin displacements in different time intervals with each other. The simplest possible sequence, three-pulse SERPENT, measures displacements in two interleaved time intervals, while in VEXSY, consisting of two independent pairs of gradient pulses separated by a mixing time, displacements during the two encoding intervals are compared to each other. The formalism for both sequences is discussed in q space and in displacement space and common features as well as differences between the two types of experiments are highlighted, employing the particular case of the concurrent VEXSY scheme which allows treatment according to both formalisms.

Magnetic Resonance Spectroscopy↗
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↗