Enhanced spatial resolution in magnetic resonance imaging by dynamic nuclear polarization at 5 K.

Spatial resolution in MRI is ultimately limited by the signal detection sensitivity of NMR, since resolution equal to ρiso in all three dimensions requires the detection of NMR signals from a volume ρiso3. With inductively detected NMR at room temperature, it has therefore proven difficult to achieve isotropic resolution better than ρiso = 3.0 μm, even with radio-frequency microcoils, optimized samples, high magnetic fields, optimized pulse sequence methods, and data acquisition times around 60 h.

Slice selection in low-temperature, DNP-enhanced magnetic resonance imaging by Lee-Goldburg spin-locking and phase modulation.

Large enhancements in nuclear magnetic resonance (NMR) signals provided by dynamic nuclear polarization (DNP) at low temperatures have the potential to enable inductively-detected H magnetic resonance imaging (MRI) with isotropic spatial resolution on the order of one micron, especially when low temperatures and DNP are combined with microcoils, three-dimensional (3D) phase encoding of image information, pulsed spin locking during NMR signal detection, and homonuclear dipolar decoupling by Lee-Goldburg (LG) irradiation or similar methods. However, the relatively slow build-up of nuclear magnetization under DNP leads to very long acquisition times for high-resolution 3D images unless the sample volume or field of view (FOV) is restricted. We have therefore developed a method for slice selection in low-temperature, DNP-enhanced MRI that limits the FOV to about 50 μm in one or more dimensions.

Temperature-Dependent Nuclear Spin Relaxation Due to Paramagnetic Dopants Below 30 K: Relevance to DNP-Enhanced Magnetic Resonance Imaging.

Dynamic nuclear polarization (DNP) can increase nuclear magnetic resonance (NMR) signal strengths by factors of 100 or more at low temperatures. In magnetic resonance imaging (MRI), signal enhancements from DNP potentially lead to enhancements in image resolution. However, the paramagnetic dopants required for DNP also reduce nuclear spin relaxation times, producing signal losses that may cancel the signal enhancements from DNP.

Low-temperature magnetic resonance imaging with 2.8 μm isotropic resolution.

We demonstrate the feasibility of high-resolution H magnetic resonance imaging (MRI) at low temperatures by obtaining an MRI image of 20 μm diameter glass beads in glycerol/water at 28 K with 2.8 μm isotropic resolution. The experiments use a recently-described MRI apparatus (Moore and Tycko, 2015) with minor modifications.

In-Vitro Dissolution Dynamic Nuclear Polarization for Sensitivity Enhancement of NMR with Biological Molecules.

Dissolution dynamic nuclear polarization (D-DNP) is a technique to prepare hyperpolarized nuclear spin states, yielding a signal enhancement of several orders of magnitude for liquid-state NMR. Here, we describe experimental procedures for the application of D-DNP in high-resolution NMR of biochemical compounds, to determine the time evolution of biochemical processes and intermolecular interactions.

Determination of Intermolecular Interactions Using Polarization Compensated Heteronuclear Overhauser Effect of Hyperpolarized Spins.

The nuclear Overhauser effect (NOE) has long been used as a selective indicator for intermolecular interactions. Due to relatively small changes of signal intensity, often on the order of several percent, quantitative NOE measurements can be challenging. Hyperpolarization of nuclear spins can dramatically increase the NOE intensity by increasing population differences, but poses its own challenge in quantifying the original polarization level.

Ultrafast multidimensional Laplace NMR for a rapid and sensitive chemical analysis.

Traditional nuclear magnetic resonance (NMR) spectroscopy relies on the versatile chemical information conveyed by spectra. To complement conventional NMR, Laplace NMR explores diffusion and relaxation phenomena to reveal details on molecular motions. Under a broad concept of ultrafast multidimensional Laplace NMR, here we introduce an ultrafast diffusion-relaxation correlation experiment enhancing the resolution and information content of corresponding 1D experiments as well as reducing the experiment time by one to two orders of magnitude or more as compared with its conventional 2D counterpart.

Implementation and characterization of flow injection in dissolution dynamic nuclear polarization NMR spectroscopy.

The use of dissolution dynamic nuclear polarization (D-DNP) offers substantially increased signals in liquid-state NMR spectroscopy. A challenge in realizing this potential lies in the transfer of the hyperpolarized sample to the NMR detector without loss of hyperpolarization. Here, the use of a flow injection method using high-pressure liquid leads to improved performance compared to the more common gas-driven injection, by suppressing residual fluid motions during the NMR experiment while still achieving a short injection time.

An ultra-low cost NMR device with arbitrary pulse programming.

Ultra-low cost, general purpose electronics boards featuring microprocessors or field programmable gate arrays (FPGA) are reaching capabilities sufficient for direct implementation of NMR spectrometers. We demonstrate a spectrometer based on such a board, implemented with a minimal need for the addition of custom electronics and external components. This feature allows such a spectrometer to be readily implemented using typical knowledge present in an NMR laboratory.

Hyperpolarized Hadamard spectroscopy using flow NMR.

The emergence of the dissolution dynamic nuclear polarization (D-DNP) technique provides an important breakthrough to overcome inherent sensitivity limitations in nuclear magnetic resonance (NMR) experiments. In dissolution DNP, only a small amount of frozen sample is polarized, dissolved, and injected into an NMR spectrometer. Although substantially enhanced NMR signals can be obtained, the single scan nature of this technique a priori impedes the use of correlation experiments, which represent some of the most powerful applications of NMR spectroscopy.

Genetic incorporation of twelve meta-substituted phenylalanine derivatives using a single pyrrolysyl-tRNA synthetase mutant.

When coexpressed with its cognate amber suppressing tRNACUAPyl(CUA), a pyrrolysyltRNA synthetase mutant N346A/C348A is able to genetically incorporate 12 meta-substituted phenylalanine derivatives into proteins site-specifically at amber mutation sites in Escherichia coli. These genetically encoded noncanonical amino acids resemble phenylalanine in size and contain diverse bioorthogonal functional groups such as halide, trifluoromethyl, nitrile, nitro,ketone, alkyne, and azide moieties. The genetic installation of these functional groups in proteins provides multiple ways to site-selectively label proteins with biophysical and biochemical probes for their functional investigations.

Solution NMR of polypeptides hyperpolarized by dynamic nuclear polarization.

Hyperpolarization of nuclear spins through techniques such as dynamic nuclear polarization (DNP) can greatly increase the signal-to-noise ratio in NMR measurements, thus eliminating the need for signal averaging. This enables the study of many dynamic processes which would otherwise not be amenable to study by NMR spectroscopy. A report of solid- to liquid-state DNP of a short peptide, bacitracin A, as well as of a full-length protein, L23, is presented here.

Spontaneous emission of NMR signals in hyperpolarized proton spin systems.

Hyperpolarization of nuclear spins is gaining increasing interest as a tool for improving the signal-to-noise ratio of NMR and MRI. While in principle, hyperpolarized samples are amenable to the same or similar experiments as are used in conventional NMR, the large spin polarization may give rise to unexpected effects. Here, spontaneous emission of signal was observed from proton spin systems, which were hyperpolarized to negative spin temperature by dynamic nuclear polarization (DNP).

Photodissociation cross sections of ClOOCl at 248.4 and 266 nm.

This study utilized a mass-resolved detection of ClOOCl to determine its photodissociation cross section, which is the product of the absorption cross section and dissociation quantum yield. An effusive molecular beam of ClOOCl was generated and its photodissociation probability was determined through measuring the decrease in the ClOOCl beam intensity upon laser irradiation. By comparing with a reference molecule, the absolute cross sections of ClOOCl were obtained without knowing its absolute concentration.

UV absorption cross sections of ClOOCl are consistent with ozone degradation models.

Recently, discrepancies in laboratory measurements of chlorine peroxide (ClOOCl) absorption cross sections have cast doubt on the validity of current photochemical models for stratospheric ozone degradation. Whereas previous ClOOCl absorption measurements all suffered from uncertainties due to absorption by impurities, we demonstrate here a method that uses mass-selected detection to circumvent such interference. The cross sections of ClOOCl were determined at two critical wavelengths (351 and 308 nanometers).

Dynamics of the F2 reaction with propene: the effect of methyl substitution.

The reaction of F2 + C3H6 has been investigated with the crossed molecular beam technique. The only observed primary product channel is F + C3H6F while the HF + C3H5F channel cannot be found. The reaction cross section was measured as a function of collision energy and the reaction threshold was determined to be 2.