Preparation of Nuclear Spin Singlet States Using Spin-Lock Induced Crossing

We introduce a broadly applicable technique to create nuclear spin singlet states in organic molecules and other many-atom systems. We employ a novel pulse sequence to produce a spin-lock induced crossing (SLIC) of the spin singlet and triplet energy levels, which enables triplet-singlet polarization transfer and singlet-state preparation. We demonstrate the utility of the SLIC method by producing a long-lived nuclear spin singlet state on two strongly coupled proton pairs in the tripeptide molecule phenylalanine-glycine-glycine dissolved in D$_2$O and by using SLIC to measure the J couplings, chemical shift differences, and singlet lifetimes of the proton pairs. We show that SLIC is more efficient at creating nearly equivalent nuclear spin singlet states than previous pulse sequence techniques, especially when triplet-singlet polarization transfer occurs on the same time scale as spin-lattice relaxation.Physic

Laser-polarized xenon-129 magnetic resonance spectroscopy and imaging. The development of a method for <italic>in vivo</italic> perfusion measurement.

This thesis presents in vivo nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) studies with laser-polarized 129Xe delivered to living rats by inhalation and transported to tissue via blood flow. The results presented herein include the observation, assignment, and dynamic measurement of 129Xe resonances in the brain and body, the first one- and two-dimensional chemical-shift-resolved images of 129Xe in blood, tissue, and gas in the thorax, and the first images of 129Xe in brain tissue. These results establish that laser-polarized 129Xe can be used as a magnetic resonance tracer in vivo. NMR resonances at 0, 191, 198, and 209 ppm relative to the 129 Xe gas resonance are observed in the rat thorax and assigned to 129Xe in gas, fat, tissue, and blood respectively. Resonances at 189, 192, 195, 198, and 209 ppm are observed in the brain, and the 195 and 209 ppm resonances are assigned to 129Xe in grey matter, and blood, respectively. The design and construction of a laser-polarized 129Xe production and delivery system is described. This system produces liter-volumes of laser-polarized 129Xe by spin-exchange optical-pumping. It represented an order of magnitude increase over previously reported production volumes of polarized 129Xe. At approximately 3--7% polarization, 157 cc-atm of xenon is produced and stored as ice every 5 minutes. This reliable, effective, and simple production method for large volumes of 129Xe can be applied to other areas of research involving the use of laser-polarized noble gases. A model of the in vivo transport of laser polarized 129Xe to tissue under realistic experimental NMR conditions is described. Appropriate control of the NMR parameters is shown to allow tissue perfasion and 129Xe tissue T1 to be extracted from measurement of the steady-state 129Xe tissue signal. In vivo rodent 129Xe NMR results are used to estimate the signal-to-noise ratio of this technique, and an inhaled 30% xenon/70% O2 mixture polarized to 5% is estimated to provide sufficient SNR in rodent grey matter. Application to the measurement of regional cerebral blood flow and neuronal activation is discussed.Ph.D.Atomic physicsPure SciencesUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/123958/2/3001042.pd

Paramagnetic Ion-Doped Nanocrystal as a Voltage-Controlled Spin Filter

A theory of spin injection from a ferromagnetic source into a semiconductor through a paramagnetic ion-doped nanocrystal is developed. Spin-polarized current from the source polarizes the ion; the polarized ion, in turn, controls the spin polarization of the current flowing through the nanocrystal. Depending on voltage, the ion can either enhance the injection coefficient by several times or suppress it. Large ion spins produce stronger enhancement of spin injection.Physic

Probing scalar coupling differences via long-lived singlet states

We probe small scalar coupling differences via the coherent interactions between two nuclear spin singlet states in organic molecules. We show that the spin-lock induced crossing (SLIC) technique enables the coherent transfer of singlet order between one spin pair and another. The transfer is mediated by the difference in syn and anti vicinal or long-range J couplings among the spins. By measuring the transfer rate, we calculate a J coupling difference of 8 ± 2 mHz in phenylalanine–glycine–glycine and 2.57±0.04 Hz in glutamate. We also characterize a coherence between two singlet states in glutamate, which may enable the creation of a long-lived quantum memory.Physic

Dependence of nuclear spin singlet lifetimes on RF spin-locking power

We measure the lifetime of long-lived nuclear spin singlet states as a function of the strength of the RF spin-locking field and present a simple theoretical model that agrees well with our measurements, including the low-RF-power regime. We also measure the lifetime of a long-lived coherence between sin- glet and triplet states that does not require a spin-locking field for preservation. Our results indicate that for many molecules, singlet states can be created using weak RF spin-locking fields: more than two orders of magnitude lower RF power than in previous studies. Our findings suggest that for many endogenous biomolecules, singlets and related states with enhanced lifetimes might be achievable in vivo with safe levels of RF power.Chemistry and Chemical BiologyPhysic

Nuclear spin singlet states as a contrast mechanism for NMR spectroscopy

Nuclear magnetic resonance (NMR) spectra of complex chemical mixtures often contain unresolved or hidden spectral components, especially when strong background signals overlap weaker peaks. In this article we demonstrate a quantum filter utilizing nuclear spin singlet states, which allows undesired NMR spectral background to be removed and target spectral peaks to be uncovered. The quantum filter is implemented by creating a nuclear spin singlet state with spin quantum numbers j = 0, m$_z$ = 0 in a target molecule, applying a continuous RF field to both preserve the singlet state and saturate the magnetization of undesired molecules and then mapping the target molecule singlet state back into an NMR observable state so that its spectrum can be read out unambiguously. The preparation of the target singlet state can be carefully controlled with pulse sequence parameters, so that spectral contrast can be achieved between molecules with very similar structures. We name this NMR contrast mechanism ‘Suppression of Undesired Chemicals using Contrast-Enhancing Singlet States’ (SUCCESS) and we demonstrate it in vitro for three target molecules relevant to neuroscience: aspartate, threonine and glutamine.Physic

Empirical determination of convection parameters in white dwarfs. I. Whole earth telescope obsevations of EC14012-1446

We report on an analysis of 308.3 hr of high-speed photometry targeting the pulsating DA white dwarf EC14012-1446. The datawere acquiredwith theWhole Earth Telescope during the 2008 international observing run XCOV26. The Fourier transform of the light curve contains 19 independent frequencies and numerous combination frequencies. The dominant peaks are 1633.907, 1887.404, and 2504.897μHz. Our analysis of the combination amplitudes reveals that the parent frequencies are consistent with modes of spherical degree l=1. The combination amplitudes also provide m identifications for the largest amplitude parent frequencies. Our seismology analysis, which includes 2004–2007 archival data, confirms these identifications, provides constraints on additional frequencies, and finds an average period spacing of 41 s. Building on this foundation, we present nonlinear fits to high signal-to-noise light curves from the SOAR 4.1 m, McDonald 2.1 m, and KPNO 2 m telescopes. The fits indicate a time-averaged convective response timescale of τ0 = 99.4 ± 17 s, a temperature exponent N = 85±6.2, and an inclination angle of θi = 32. ◦ 9 ± 3° 2. We present our current empirical map of the convective response timescale across the DA instability strip

The pulsation modes of the pre-white dwarf PG 1159-035

Context. PG 1159-035, a pre-white dwarf with Teff ~_140 000 K, is the prototype of both two classes: the PG 1159 spectroscopic class and the DOV pulsating class. Previous studies of PG 1159-035 photometric data obtained with the Whole Earth Telescope (WET) showed a rich frequency spectrum allowing the identification of 122 pulsation modes. Analyzing the periods of pulsation, it is possible to measure the stellar mass, the rotational period and the inclination of the rotation axis, to estimate an upper limit for the magnetic field, and even to obtain information about the inner stratification of the star. Aims. We have three principal aims: to increase the number of detected and identified pulsation modes in PG 1159-035, study trapping of the star’s pulsation modes, and to improve or constrain the determination of stellar parameters. Methods. We used all available WET photometric data from 1983, 1985, 1989, 1993 and 2002 to identify the pulsation periods. Results. We identified 76 additional pulsation modes, increasing to 198 the number of known pulsation modes in PG 1159-035, the largest number of modes detected in any star besides the Sun. From the period spacing we estimated a mass M/Mʘ = 0.59 ± 0.02 for PG 1159-035, with the uncertainty dominated by the models, not the observation. Deviations in the regular period spacing suggest that some of the pulsation modes are trapped, even though the star is a pre-white dwarf and the gravitational settling is ongoing. The position of the transition zone that causes the mode trapping was calculated at rc/R. = 0.83 ± 0.05. From the multiplet splitting, we calculated the rotational period Prot = 1.3920 ± 0.0008 days and an upper limit for the magnetic field, B < 2000 G. The total power of the pulsation modes at the stellar surface changed less than 30% for l = 1 modes and less than 50% for l = 2 modes. We find no evidence of linear combinations between the 198 pulsation mode frequencies. PG 1159-035 models have not significative convection zones, supporting the hypothesis that nonlinearity arises in the convection zones in cooler pulsating white dwarf stars

The pulsation modes of the pre-white dwarf PG 1159-035

Context. PG 1159-035, a pre-white dwarf with Teff ~_140 000 K, is the prototype of both two classes: the PG 1159 spectroscopic class and the DOV pulsating class. Previous studies of PG 1159-035 photometric data obtained with the Whole Earth Telescope (WET) showed a rich frequency spectrum allowing the identification of 122 pulsation modes. Analyzing the periods of pulsation, it is possible to measure the stellar mass, the rotational period and the inclination of the rotation axis, to estimate an upper limit for the magnetic field, and even to obtain information about the inner stratification of the star. Aims. We have three principal aims: to increase the number of detected and identified pulsation modes in PG 1159-035, study trapping of the star’s pulsation modes, and to improve or constrain the determination of stellar parameters. Methods. We used all available WET photometric data from 1983, 1985, 1989, 1993 and 2002 to identify the pulsation periods. Results. We identified 76 additional pulsation modes, increasing to 198 the number of known pulsation modes in PG 1159-035, the largest number of modes detected in any star besides the Sun. From the period spacing we estimated a mass M/Mʘ = 0.59 ± 0.02 for PG 1159-035, with the uncertainty dominated by the models, not the observation. Deviations in the regular period spacing suggest that some of the pulsation modes are trapped, even though the star is a pre-white dwarf and the gravitational settling is ongoing. The position of the transition zone that causes the mode trapping was calculated at rc/R. = 0.83 ± 0.05. From the multiplet splitting, we calculated the rotational period Prot = 1.3920 ± 0.0008 days and an upper limit for the magnetic field, B < 2000 G. The total power of the pulsation modes at the stellar surface changed less than 30% for l = 1 modes and less than 50% for l = 2 modes. We find no evidence of linear combinations between the 198 pulsation mode frequencies. PG 1159-035 models have not significative convection zones, supporting the hypothesis that nonlinearity arises in the convection zones in cooler pulsating white dwarf stars