Spectroscopy: shifting light with spin.
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Lasers↗
Biomedical subjects
Warren S Warren
Publications and source records attributed to Warren S Warren.
Ultrafast intermolecular zero quantum spectroscopy.
Clinical magnetic resonance spectroscopy is typically limited by magnetic inhomogeneities which destroy spectral resolution, but intermolecular zero quantum coherences (iZQCs) are insensitive to such inhomogeneities. iZQC resolution in vivo, however, has been hampered by physiological fluctuations over the time scale of the two-dimensional acquisition. A faster iZQC sequence will allow us to average away these fluctuations, and thus we present a new approach to ultrafast two-dimensional spectroscopy. This communication reports iZQC experiments acquiring up to 31 t1-points per scan, as well as extensions to a broad range of other 2D sequences.
Animals↗
Two-photon absorption and self-phase modulation measurements with shaped femtosecond laser pulses.
We show that phase-sensitive detection of spectral hole refilling can yield information about self-phase modulation and two-photon absorption coefficients. We expect that, when applied to tissue microscopy, this technique will allow the study of endogenous molecular markers beneath the surface, even if those markers are nonfluorescent.
Algorithms↗
Structural anisotropy and internal magnetic fields in trabecular bone: coupling solution and solid dipolar interactions.
We investigate the use of intermolecular multiple-quantum coherence to probe structural anisotropy in trabecular bone. Despite the low volume fraction of bone, the bone-water interface produces internal magnetic field gradients which modulate the dipolar field, depending on sample orientation, choice of dipolar correlation length, correlation gradient direction, and evolution time. For this system, the probing of internal magnetic field gradients in the liquid phase permits indirect measurements of the solid phase dipolar field. Our results suggest that measurements of volume-averaged signal intensity as a function of gradient strength and three orthogonal directions could be used to non-invasively measure the orientation of structures inside a sample or their degree of anisotropy. The system is modeled as having two phases, solid and liquid (bone and water), which differ in their magnetization density and magnetic susceptibility. A simple calculation using a priori knowledge of the material geometry and distribution of internal magnetic fields verifies the experimental measurements as a function of gradient strength, direction, and sample orientation.
Anisotropy↗
Multiple-quantum vector field imaging by magnetic resonance.
We introduce a method for non-invasively mapping fiber orientation in materials and biological tissues using intermolecular multiple-quantum coherences. The nuclear magnetic dipole field of water molecules is configured by a CRAZED sequence to encode spatial distributions of material heterogeneities. At any given point r in space, we obtain the spherical coordinates of fiber orientation (theta,phi) with respect to the external field by comparing three signals ||G(X)||, ||(Y)||, and ||G(Z)|| (modulus), acquired with linear gradients applied along the X, Y, and Z axes, respectively. For homogeneous isotropic materials, a subtraction ||G(Z)|| - ||G(X)|| - ||G(Y)|| gives zero. With anisotropic materials, we find an empirical relationship relating ||G(Z)|| - ||G(X)|| - ||G(Y)||/(||G(X)|| + ||G(Y)|| + ||G(Z)||) to the polar angle theta, while ||G(X|| - ||G(Y)||/(||G(X)|| + ||G(Y)|| + ||G(Z)||) is related to the azimuthal angle phi. Experiments in structured media confirm the structural sensitivity. This technique can probe length scales not accessible by conventional MRI and diffusion tensor imaging.
Animals↗
Signal irreproducibility in high-field solution magnetic resonance experiments caused by spin turbulence.
Turbulent spin dynamics arising from the joint action of radiation damping and the distant dipolar field are shown to generate irreproducible measurements in popular high-field, gradient-based magnetic resonance (MR) experiments, undermining the prevailing assumption of essentially predictable observables in MR. Sizeable fluctuations in echo amplitudes are reported and numerically simulated for pulsed gradient spin echo and stimulated echo diffusion measurements. The underlying microscopic dynamical instability is characterized by analysis of the finite-time Lyapunov exponents. Perturbations to the modulated magnetization are shown to render magic-angle gradients ineffective in suppressing signal fluctuations. Alternative approaches are suggested for cancelling out the feedback interactions leading to spin turbulence.
Artifacts↗
Reconstruction of porous material geometry by stochastic optimization based on bulk NMR measurements of the dipolar field.
The dependence of the bulk signal intensity from a CRAZED NMR pulse sequence on magnetic field gradient strength and direction as a method to probe the geometry of porous materials is investigated. In this article, we report on the reconstruction of three-dimensional media consisting of a void phase and an NMR-observable liquid phase using the bulk intensity of the distant dipolar field. The correlation gradient strength and direction provide the spatial encoding of the material geometry. An integral equation for the total signal intensity is then solved numerically by a simulated annealing algorithm to recover the indicator function of the fluid phase. Results show that cylindrical and spherical structures smaller than the volume contributing to the NMR signal can be resolved using three values of the correlation distance and three orthogonal gradient directions. This is done by minimizing a cost function which measures the distance between the bulk signal dependence on gradient parameters for the simulated configuration and the signal dependence for the target configuration. The algorithm can reconstruct and differentiate their spherical and cylindrical phase-inverted equivalents. It can also differentiate horizontal from vertical cylinders, demonstrating the potential for assessing structural anisotropy and other coarse geometric quantifiers in a porous material.
Algorithms↗
Simultaneous acquisition of multiple orders of intermolecular multiple-quantum coherence images in vivo.
Until recently, NMR imaging with intermolecular multiple-quantum coherences (iMQCs) has been based on the acquisition of a single echo. In vivo studies of iMQC image contrast would greatly benefit from a method that could acquire several orders of quantum coherence during the same acquisition. This would enable comparison of the image contrast for various orders and eliminate image coregistration problems between scans. It has previously been demonstrated that multiple orders of iMQC images can be simultaneously acquired of a simple phantom. Here, we examine the technique and its effect on biological tissue, both in vivo and in vitro. First, we establish the effectiveness of the iMQC sequence in vivo using earthworms as specimens. We then further show that the multi-CRAZED sequence enhances detection of next generation (nanoparticle) contrast agents on excised tumor tissue.
Animals↗
Femtosecond phase-coherent two-dimensional spectroscopy.
Femtosecond phase-coherent two-dimensional (2D) spectroscopy has been experimentally demonstrated as the direct optical analog of 2D nuclear magnetic resonance. An acousto-optic pulse shaper created a collinear three-pulse sequence with well-controlled and variable interpulse delays and phases,which interacted with a model atomic system of rubidium vapor. The desired nonlinear polarization was selected by phase cycling (coadding experimental results obtained with different interpulse phases). This method may enhance our ability to probe the femtosecond structural dynamics of macromolecules.
Chemical Phenomena↗
Isolating quantum coherences in structural imaging using intermolecular double-quantum coherence MRI.
Intermolecular multiple-quantum coherence (iMQC) MR imaging provides a fundamentally different contrast mechanism. It allows probing tissue microstructure by tuning the direction and strength of the correlation gradient. However, iMQC images of a specific quantum-coherence can easily be contaminated by leakage signals from undesired quantum coherences (zero, single, and triple quantum coherence in this work). Using a modified double-quantum CRAZED imaging sequence, we show that signals originating from various coherence orders (M=0, 1, 2, 3) can be predicted in k-space and effectively isolated by means of a four-step phase cycling scheme and judicious choice of flip angles. Finally, preliminary data suggest the method to be able to provide information on trabecular bone architecture such as regional mean trabecular plate separation.
Algorithms↗
Simultaneous acquisition of multiple orders of intermolecular multiple-quantum coherence images.
Recent studies have demonstrated the ability to detect images based on intermolecular multiple-quantum coherences (iMQCs) that correspond to flipping of two or more separated spins simultaneously, as opposed to conventional magnetic resonance where only one spin is flipped at a time. Until now, iMQC imaging has only acquired one coherence signal per pulse sequence. Here we report a new sequence that successfully detects five orders of coherence (2, 1, 0, -1, and -2-quantum coherence images) in one pulse sequence, with each signal having its full intensity. The simultaneous acquisition highlights substantial contrast differences between conventional and iMQC images, and between the different types of iMQC images.
Humans↗
The prospects for high resolution optical brain imaging: the magnetic resonance perspective.
Various analogs of NMR and MRI are now technically possible in optics; specifically, high-resolution laser-pulse shaping and complex pulse sequence generation with well-defined phase shifts has been demonstrated. Here we summarize this technology and discuss the potential for these methods to enhance optical functional imaging, competing with (and surpassing?) what is possible by functional MRI.
Brain↗
Magnetization structure contrast based on intermolecular multiple-quantum coherences.
In vivo and ex vivo MRI based on intermolecular multiple-quantum coherences (iMQC) is predicted to provide a fundamentally different source of contrast for MRI. This article investigates the dependence of image contrast upon the choice of correlation distance for a heterogeneous material. A closely packed array of parallel hollow cylinders was used to demonstrate signal intensity variations when the correlation distance becomes comparable to the gap size between the cylinders. The observed effects agree well with three-dimensional calculations of the time evolution of magnetization under the nonlinear Bloch equations.
Contrast Media↗