Solution-State 2D NMR Spectroscopy of Mixtures HyperpolarizedUsing Optically Polarized Crystals.

The HYPNOESYS method (Hyperpolarized NOE System), which relies on the dissolution of optically polarized crystals, has recently emerged as a promising approach to enhance the sensitivity of NMR spectroscopy in the solution state. However, HYPNOESYS is a single-shot method that is not generally compatible with multidimensional NMR. Here we show that 2D NMR spectra can be obtained from HYPNOESYS-polarized samples, using single-scan acquisition methods.

A Ramsey apparatus for proton spins in flowing water.

We present an apparatus that applies Ramsey's method of separated oscillatory fields to proton spins in water molecules. The setup consists of a water circuit, a spin polarizer, a magnetically shielded interaction region with various radio frequency elements, and a nuclear magnetic resonance system to measure the spin polarization. We show that this apparatus can be used for Rabi resonance measurements and to investigate magnetic and pseudomagnetic field effects in Ramsey-type precision measurements with a sensitivity below 100 pT.

Net Dzyaloshinskii-Moriya interaction in defect-enriched ferromagnet.

The Dzyaloshinskii-Moriya interaction (DMI), which typically occurs in lattices without space inversion symmetry, can also be induced in a highly symmetric lattice by local symmetry breaking due to any lattice defect. We recently presented an experimental study of polarized small angle neutron scattering (SANS) on the nanocrystalline soft magnet Vitroperm (FeSiBNbCu), where the interface between the FeSi nanoparticles and the amorphous magnetic matrix serves as such a defect. The SANS cross sections exhibited the polarization-dependent asymmetric term originating from the DMI.

Long-Lived, Transportable Reservoir of Nuclear Polarization Used to Strongly Enhance Solution-State NMR Signals.

There is a fundamental issue with the use of dynamic nuclear polarization (DNP) to enhance nuclear spin polarization: the same polarizing agent (PA) needed for DNP is also responsible for shortening the lifetime of the hyperpolarization. As a result, long-term storage and transport of hyperpolarized samples is severely restricted and the apparatus for DNP is necessarily located near or integrated with the apparatus using the hyperpolarized spins. In this paper, we demonstrate that naphthalene single crystals can serve as a long-lived reservoir of proton polarization that can be exploited to enhance signals in benchtop and high-field NMR of target molecules in solution at a site 300 km away by a factor of several thousand.

Integrated, Stretched, and Adiabatic Solid Effects.

This paper presents a theory describing the dynamic nuclear polarization (DNP) process associated with an arbitrary frequency swept microwave pulse. The theory is utilized to explain the integrated solid effect (ISE) as well as the newly discovered stretched solid effect (SSE) and adiabatic solid effect (ASE). It is verified with experiments performed at 9.

Hyperpolarized Solution-State NMR Spectroscopy with Optically Polarized Crystals.

Nuclear spin hyperpolarization provides a promising route to overcome the challenges imposed by the limited sensitivity of nuclear magnetic resonance. Here we demonstrate that dissolution of spin-polarized pentacene-doped naphthalene crystals enables transfer of polarization to target molecules via intermolecular cross-relaxation at room temperature and moderate magnetic fields (1.45 T).

Relaxation of nuclear dipolar energy.

Under typical conditions for dynamic nuclear polarization (DNP)-temperature about 1 K or below and magnetic field about 3 T or higher-the polarization agent causes nuclear dipolar order to relax up to four orders of magnitude faster than nuclear polarization. However, as far as we know, this ultra-fast dipolar relaxation has thus far not been explained in a satisfactory way. We report similar ultra-fast dipolar relaxation of proton spins in naphthalene due to the photo-excited triplet spin of pentacene and propose a three-step mechanism that explains such ultra-fast dipolar relaxation by ground state electron spins as well as by photo-excited triplet spins: nuclear spin diffusion transfers nuclear dipolar order-that is nuclear dipolar energy-spatially to near the electron spins.

Impact of the neutron-depolarization effect on polarized neutron scattering in ferromagnets.

It has been known for decades that a ferromagnetic sample can depolarize a transmitted neutron beam. This effect was used and developed into the neutron-depolarization technique to investigate the magnetic structure of ferromagnetic materials. Since the polarization evolves continuously as the neutrons move through the sample, the initial spin states on scattering will be different at different depths within the sample.

Defect-induced Dzyaloshinskii-Moriya interaction in a nanocrystalline two-phase alloy.

The Dzyaloshinskii-Moriya interaction (DMI) is believed to be operative in low-symmetry crystal structures lacking space-inversion symmetry. However, already in 1963, Arrott pointed out that even in a high-symmetry lattice, where the DMI would normally vanish, this interaction is present in the vicinity of any lattice defect. Based on these considerations and recent theoretical work, first experimental studies of the impact of the DMI on the spin-polarized magnetic small-angle neutron scattering (SANS) of polycrystalline magnets exhibiting a large density of microstructural defects have been performed.

Visualization and quantification of inhomogeneous and anisotropic magnetic fields by polarized neutron grating interferometry.

The intrinsic magnetic moment of a neutron, combined with its charge neutrality, is a unique property which allows the investigation of magnetic phenomena in matter. Here we present how the utilization of a cold polarized neutron beam in neutron grating interferometry enables the visualization and characterization of magnetic properties on a microscopic scale in macroscopic samples. The measured signal originates from the phase shift induced by the magnetic potential.

Automated transfer and injection of hyperpolarized molecules with polarization measurement prior to in vivo NMR.

Hyperpolarized magnetic resonance via dissolution dynamic nuclear polarization necessitates the transfer of the hyperpolarized molecules from the polarizer to the imager prior to in vivo measurements. This process leads to unavoidable losses in nuclear polarization, which are difficult to evaluate once the solution has been injected into an animal. We propose a method to measure the polarization of the hyperpolarized molecules inside the imager bore, 3 s following dissolution, at the time of the injection, using a precise quantification of the infusate concentration.

An apparatus for pulsed ESR and DNP experiments using optically excited triplet states down to liquid helium temperatures.

In standard Dynamic Nuclear Polarization (DNP) electron spins are polarized at low temperatures in a strong magnetic field and this polarization is transferred to the nuclear spins by means of a microwave field. To obtain high nuclear polarizations cryogenic equipment reaching temperatures of 1 K or below and superconducting magnets delivering several Tesla are required. This equipment strongly limits applications in nuclear and particle physics where beams of particles interact with the polarized nuclei, as well as in neutron scattering science.

Boosting Dissolution Dynamic Nuclear Polarization by Cross Polarization.

The efficiency of dissolution dynamic nuclear polarization can be boosted by Hartmann-Hahn cross polarization at temperatures near 1.2 K. This enables high throughput of hyperpolarized solutions with substantial gains in buildup times and polarization levels.

Ultra high-resolution NMR: sustained induction decays of long-lived coherences.

Long-lived coherences (LLCs) in homonuclear pairs of chemically inequivalent spins can be excited and sustained during protracted radio frequency irradiation periods that alternate with brief windows for signal observation. Fourier transformation of the sustained induction decays recorded in a single scan yields NMR spectra with line-widths in the range 10 < Δν < 100 mHz, even in moderately inhomogeneous magnetic fields. The resulting doublets, which are reminiscent of J-spectra, allow one to determine the sum of scalar and residual dipolar interactions in partly oriented media.

Hyperpolarizing gases via dynamic nuclear polarization and sublimation.

A high throughput method was designed to produce hyperpolarized gases by combining low-temperature dynamic nuclear polarization with a sublimation procedure. It is illustrated by applications to 129Xe nuclear magnetic resonance in xenon gas, leading to a signal enhancement of 3 to 4 orders of magnitude compared to the room-temperature thermal equilibrium signal at 7.05 T.

Long-lived states to sustain hyperpolarized magnetization.

Major breakthroughs have recently been reported that can help overcome two inherent drawbacks of NMR: the lack of sensitivity and the limited memory of longitudinal magnetization. Dynamic nuclear polarization (DNP) couples nuclear spins to the large reservoir of electrons, thus making it possible to detect dilute endogenous substances in magnetic resonance spectroscopy (MRS) and magnetic resonance imaging (MRI). We have designed a method to preserve enhanced ("hyperpolarized") magnetization by conversion into long-lived states (LLS).

Quantitative radiography of magnetic fields using neutron spin phase imaging.

We report on a novel neutron radiography technique that uses the Ramsey principle, a method similar to neutron spin echo. For the first time quantitative imaging measurements of magnetic objects and fields could be performed. The strength of the spin-dependent magnetic interaction is detected by a change in the Larmor precession frequency of the neutron spins.

Hyperpolarized lithium-6 as a sensor of nanomolar contrast agents.

Lithium is widely used in psychotherapy. The (6)Li isotope has a long intrinsic longitudinal relaxation time T(1) on the order of minutes, making it an ideal candidate for hyperpolarization experiments. In the present study we demonstrated that lithium-6 can be readily hyperpolarized within 30 min, while retaining a long polarization decay time on the order of a minute.

A 140 GHz prepolarizer for dissolution dynamic nuclear polarization.

Apart from their very classical use to build polarized targets for particle physics, the methods of dynamic nuclear polarization (DNP) have more recently found application for sensitivity enhancement in high-resolution NMR, both in the solid and in the liquid state. It is often thought that the possible signal enhancement in such applications deteriorates when the DNP is performed at higher fields. We show that for a dissolution-DNP method that uses conventional (2,2,6,6-tetramethylpiperidine 1-oxyl) radicals as the paramagnetic agent, this is not the case for fields up to 5 T.

Producing over 100 ml of highly concentrated hyperpolarized solution by means of dissolution DNP.

New low-temperature inserts compatible with an existing hyperpolarizer were developed to dynamically polarize nuclei in large samples. The performance of the system was tested on 8 ml glassy frozen solutions containing 13C-labeled molecules and doped with nitroxyl free radicals. The obtained 13C low-temperature polarization was comparable to the one measured on 20 times smaller sample volume with only 3-4 times higher microwave power.

Cold neutron energy dependent production of ultracold neutrons in solid deuterium.

A measurement of the production of ultracold neutrons from velocity-selected cold neutrons on gaseous and solid deuterium targets is reported. The expected energy dependence for two-particle collisions with well defined neutron and Maxwell-Boltzmann distributed molecular velocities is found for the gas target. The solid target data agree in shape with the phonon density-of-states curve and provide strong evidence for the phonon model including multiphonon excitations.

Measured total cross sections of slow neutrons scattered by solid deuterium and implications for ultracold neutron sources.

The total scattering cross sections for slow neutrons with energies in the range 100 neV to 3 meV for solid ortho-2H2 at 18 and 5 K, frozen from the liquid, have been measured. The 18 K cross sections are found to be in excellent agreement with theoretical expectations and for ultracold neutrons dominated by thermal up scattering. At 5 K the total scattering cross sections are found to be dominated by the crystal defects originating in temperature induced stress but not deteriorated by temperature cycles between 5 and 10 K.

Measured total cross sections of slow neutrons scattered by gaseous and liquid 2H(2).

The total scattering cross sections for slow neutrons with energies E in the range 300 neV to 3 meV for gaseous and liquid ortho-2H2 have been measured. The cross sections for 2H2 gas are found to be in excellent agreement with both the Hamermesh and Schwinger and the Young and Koppel models. For liquid 2H(2), we confirm the existing experimental data in the cold neutron range and the discrepancy with the gas models.

Investigation of Solid D 2 for UCN Sources.

Solid deuterium (sD2) will be used for the production of ultra-cold neutrons (UCN) in a new generation of UCN sources. Scattering cross sections of UCN in sD2 determine the source yield but until now have not been investigated. We report first results from transmission and scattering experiments with cold, very cold and ultra-cold neutrons on sD2 along with light transmission and Raman scattering studies showing the influence of the sD2 crystal properties.