Biomedical subjects

P T Callaghan

Publications and source records attributed to P T Callaghan.

At least 19 recordsLinked to original sources

PubMed2006

Tracking pore to pore exchange using relaxation exchange spectroscopy.

We observe the movement of water over time between pores of differing sizes in Castlegate sandstone. To achieve this, we perform an NMR transverse relaxation exchange experiment for several mixing times. The resulting data are converted to 2D T2 distributions using a 2D inverse Laplace transform (ILT). We show for the first time that quantitative analysis of ILT distributions enables one to extract characteristic times for different pores sizes. This information is potentially useful for permeability determination as well as better understanding of exchange between specific pore subpopulations.

Magnetic Resonance Spectroscopy↗

PubMed2006

A mobile one-sided NMR sensor with a homogeneous magnetic field: the NMR-MOLE.

A new portable NMR sensor with a novel one-sided access magnet design, termed NMR-MOLE (MObile Lateral Explorer), has been characterised in terms of sensitivity and depth penetration. The magnet has been designed to be portable and create a volume with a relatively homogeneous magnetic field, 15,000 ppm over a region from 4 to 16 mm away from the probe, with maximum sensitivity at a depth of 10 mm. The proton NMR frequency is 3.3 MHz. We have demonstrated that with this approach a highly sensitive, portable, unilateral NMR sensor can be built. Such a design is especially suited for the characterisation of liquids in situations where unilateral or portable access is required.

Complex Mixtures↗

PubMed2006

Measurement of diffusion in the presence of shear flow.

We demonstrate here a method whereby molecular diffusion coefficients may be measured in the presence of the deformational flow field of a rheo-NMR cell. The method, which uses a repetitive CPMG train of rf pulses interspersed with magnetic field gradient pulses, allows the anisotropic diffusion spectrum to be directly probed. We focus on the cylindrical Couette cell, for which the radial, tangential, and axial directions correspond to the hydrodynamic velocity gradient, velocity, and vorticity directions. While ideal Couette flow does not perturb the vorticity direction, it does perturb diffusion measurements for the velocity gradient direction, and to a lesser extent, the velocity direction. We show that with closely spaced gradient pulses operating in a flow-compensating mode, there exists a diffusion limit below which one cannot measure, that scales as T(2)gamma(4), where gamma is the shear rate and T the gradient pulse repetition period. For a typical rheo-NMR cell, and for the more challenging velocity gradient direction, diffusion rates above 10(-12) m(2) s(-1) can be accurately measured (to 1% error) at shear rates up to 3s(-1). We demonstrate the use of the method in measuring the diffusion spectrum of a lyotropic lamellar phase under shear.

Journal Article↗

PubMed2006

Undulations and fluctuations in a lamellar phase lyotropic liquid crystal and their suppression by weak shear flow.

Using multi-echo pulsed gradient nuclear magnetic resonance (NMR) we measure the anisotropic diffusion of water molecules in the lamellar phase of lyotropic system composed of cetylpyridinium chloride/hexanol diluted in brine. The technique reveals the Fourier spectrum of the molecular velocity autocorrelation function, and its repetitive compensating nature permits effective measurement in the presence of shear flow. We show that under zero shear the phase is highly oriented and that both the amplitude and fluctuation correlation time of lamellar undulations can be measured. The suppression of undulations by weak shear is apparent. We further measure transverse lamellae permeability arising from defects.

Journal Article↗

PubMed2005

NMR velocimetry studies of the steady-shear rheology of a concentrated hard-sphere colloidal system.

NMR velocimetry has been used to observe the steady-shear rheological behaviour of a concentrated suspension of hard-sphere like 370 nm diameter PMMA core-shell latex particles at the volume fraction phi = 0.46, the liquid core of the spheres rendering possible NMR observation of the particles themselves. Rheological measurements in a cone-and-plate geometry indicate that when aged (i.e. left at rest for two weeks), the material exhibits yield stress behaviour at very low shear rates. For shear rates greater than 1 s(-1) a transition to liquid-like behaviour was observed, leading to a rejuvenated fluid state which exhibits shear-thinning behaviour over a wide range of shear rates. A similar yield stress behaviour was reflected in NMR velocimetry measurements in a Couette geometry, where the solid-to liquid transition could be clearly observed. Under steady-state flow, the fluid state inside the radius at which yield stress was observed, exhibited shear-thinning behaviour with a power law exponent n slowly approaching unity with increasing shear rate. This behaviour has some similarities with a model of Derec et al. in which aging and rejuvenation effects compete. Substantial wall slip was observed both at the inner and at the outer wall, an effect which disappeared as the shear rate was increased. No radial particle migration from the high-shear region at the inner wall was observed.

Journal Article↗

PubMed2005

Diffusion correlation NMR spectroscopic study of anisotropic diffusion of water in plant tissues.

The anisotropic diffusion of water in chive (Allium schoenoprasum) tissues has been investigated using two-dimensional nuclear magnetic resonance methods: diffusion-diffusion correlation spectroscopy and diffusion-relaxation correlation spectroscopy. Corresponding one-dimensional T2 and diffusion measurements confirm independently the results of the two-dimensional investigations. In particular the diffusion-diffusion correlation spectroscopy method proves to be very powerful in resolving the different components of the diffusion tensor at different sites in the sample.

Algorithms↗

PubMed2005

Diffusion exchange NMR spectroscopic study of dextran exchange through polyelectrolyte multilayer capsules.

Diffusion exchange of dextran with molecular weights 4.4 and 77 kDa through polyelectrolyte multilayer (PEM) hollow capsules consisting of four bilayers of polystyrene sulfonate/polydiallyldimethylammonium chloride has been investigated using two-dimensional nuclear-magnetic-resonance methods: diffusion-diffusion exchange spectroscopy (DEXSY) and diffusion-relaxation correlation spectroscopy (DRCOSY). Results obtained in DRCOSY experiments show that the diffusion process of dextran 77 kDa exhibits an observation time dependence suggesting a diffusion behavior restricted by confinement. We find evidence for both single capsule and capsule aggregate states, with a partitioning of the 77-kDa dextran between the free and capsule states much larger than that suggested by volume fraction alone. Results from DEXSY experiments show that dextran 77 kDa is in diffusive exchange through the capsules with an exchange time of around 1 s. In contrast, the capsules have no detectable influence on the diffusion process of the dextran 4.4 kDa. This quantitative information may be used in designing PEM capsules as drug carriers.

Journal Article↗

PubMed2005

Time-dependence of nuclear magnetic resonance quadrupole interactions for polymers under shear.

We consider the problem of performing NMR spectroscopy under conditions of flow, a central issue in Rheo-NMR. By way of example, the effects of rotational motion on the deuterium NMR spectrum are considered for Couette cell experiments involving deformation of polymers under shearing conditions. The polymer was modelled as a power law fluid and for each streamline, the spin Hamiltonian evolved to allow for flow reorientation. The gap-integral spectra are compared with the 'ideal' spectra for a polymer under shear, but without reorientation. It is found that flow does affect the shape of the deuterium spectra, as well as slightly perturbing the splittings.

Deuterium↗

PubMed2004

Shear banding fluctuations and nematic order in wormlike micelles.

Using rapid NMR velocimetry we demonstrate the existence of shear band fluctuations in the Couette flow of the wormlike micelle system, 10% w/v cetylpyridinium chloride and sodium salicylate (molar ratio 2:1) in 0.5 M 2H2O NaCl brine. We show that the fluctuations may be either quasirandom or periodic, the fluctuation spectrum being similar to that observed in the stress. Despite the equilibrium fluid being far from an isotropic-nematic transition, deuterium NMR shows that the onset of shear banding is associated with a nematic micellar state whose order parameter depends on shear rate.

Animals↗

PubMed2004

Diffusion-diffusion correlation and exchange as a signature for local order and dynamics.

We demonstrate the use of new two-dimensional nuclear magnetic resonance experiments in the examination of local diffusional anisotropy under conditions of global isotropy. The methods, known as diffusion-diffusion correlation spectroscopy and diffusion exchange spectroscopy, employ successive pairs of magnetic field gradient pulses, with signal analysis using two-dimensional inverse Laplace transformation. Diffusional anisotropy is measured for water molecules in a polydomain lamellar phase lyotropic liquid crystal, 40 wt % nonionic surfactant C10E3 (C10H21O(CH2CH2O)6H) in H2O.

Journal Article↗

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↗

PubMed2003

Imaging the velocity profiles in tubeless siphon flow by NMR microscopy.

We report on the use of NMR micro-imaging to observe flow within a tubeless siphon. The flow is maintained in a visco-elastic liquid of high extensional viscosity, namely 0.5% w/v 8 million Dalton polyethylene oxide in water. The velocity profiles reveal a significant velocity gradient in the vertical direction as well as a transition from near-Poiseuille flow at the pipe entrance to plug flow far from the pipe entrance towards the base of the tubeless siphon.

Feasibility Studies↗

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↗