Dipolar Order Parameters in Large Systems With Fast Spinning

Order parameters are a useful tool for quantifying amplitudes of molecular motions. Here we measure dipolar order parameters by recoupling heteronuclear dipole-dipole couplings under fast spinning. We apply symmetry based recoupling methods to samples spinning under magic angle at 60 kHz by employing a variable flip angle compound inversion pulse. We validate the methods by measuring site-specific 15N-1H order parameters of a microcrystalline protein over a small temperature range and the same protein in a large, precipitated complex with antibody. The measurements of the order parameters in the complex are consistent with the observed protein undergoing overall motion within the assembly.

Correction of field instabilities in biomolecular solid-state NMR by simultaneous acquisition of a frequency reference

With the advent of faster magic-angle spinning (MAS) and higher magnetic fields, the resolution of biomolecular solid-state nuclear magnetic resonance (NMR) spectra has been continuously increasing. As a direct consequence, the always narrower spectral lines, especially in proton-detected spectroscopy, are also becoming more sensitive to temporal instabilities of the magnetic field in the sample volume. Field drifts in the order of tenths of ppm occur after probe insertion or temperature change, during cryogen refill, or are intrinsic to the superconducting high-field magnets, particularly in the months after charging. As an alternative to a field‒frequency lock based on deuterium solvent resonance rarely available for solid-state NMR, we present a strategy to compensate non-linear field drifts using simultaneous acquisition of a frequency reference (SAFR). It is based on the acquisition of an auxiliary 1D spectrum in each scan of the experiment. Typically, a small-flip-angle pulse is added at the beginning of the pulse sequence. Based on the frequency of the maximum of the solvent signal, the field evolu-tion in time is reconstructed and used to correct the raw data after acquisition, thereby acting in its principle as a digital lock system. The general applicability of our approach is demonstrated on 2D and 3D protein spectra during various situations with a non-linear field drift. SAFR with small-flip-angle pulses causes no significant loss in sensitivity or increase in exper-imental time in protein spectroscopy. The correction leads to the possibility of recording high-quality spectra in a typical biomolecular experiment even during non-linear field changes in the order of 0.1 ppm h−1 without the need for hardware solu-tions, such as stabilizing the temperature of the magnet bore. The improvement of linewidths and peak shapes turns out to be especially important for 1H-detected spectra under fast MAS, but the method is suitable for the detection of carbon or other nuclei as well.

Altered saturation pulse with a high flip angle for venous saturation on 7 T time-of-flight magnetic resonance angiography

This study aimed to apply minimum-time variable-rate selective excitation (MinVER) to a presaturation pulse (PSP) with a high flip angle on 7 T time-of-flight magnetic resonance angiography (7T TOF-MRA), to attain a superior vessel-to-tissue contrast (VTCR), short acquisition time, and minor off-resonance effect. An altered PSP modified by using the 90° flip angle (FA)-MinVER was implemented in the 7 T TOF-MRA, and its performance was evaluated with a signal profile and vessel-tissue contrast ratios and compared to the conventional PSP and 45 FA-TOF. The 90 FA-MinVER showed a similar signal profile to that of the conventional PSP and improved the vessel-tissue contrast ratios (0.313 ± 0.80) compared to all conventional types (45 FA-TOF: 0.088 ± 0.84, 90 FA-TOF: 0.203 ± 0.72). Moreover, this noteworthy approach achieved substantially reduced total acquisition time (5 min and 55 s) with a short repeat-to-time (28 ms), indicating that at the 7 T TOF-MRA, the 90 FA-MinVER could be applied by default to suppress the venous signals regardless of individual human status and the specific absorption ratio constraint and with rapid imaging. Ultimately, its application could also help to observe subtle microvascular changes in the early stages and serve as key biomarkers in various vascular diseases.

Optimization of the Image Contrast for the Developing Fetal Brain using 3D Radial VIBE Sequence in 3T Magnetic Resonance Imaging

Background: Faster and motion robust magnetic resonance imaging (MRI) sequences are desirable in fetal brain MRI. T1-weighted images are essential for evaluating fetal brain development. We optimized the radial volumetric interpolated breath-hold examination (VIBE) sequence for qualitative T1-weighted images of the fetal brain with improved image contrast and reduced motion sensitivity. Materials and Methods: This was an institutional review board-approved prospective study. Thirty-two pregnant subjects underwent fetal brain scan at 3 Tesla MRI. T1-weighted images were acquired using a 3D radial VIBE sequence with flip angles of 6º, 9º, 12º, and 15º and turbo FLASH (TFL) sequence. Qualitative assessments including image quality and motion artifact severity were evaluated. The image contrast ratio between gray and white matter were measured. Interobserver reliability and intraobserver repeatability were assessed using intraclass correlation coefficient (ICC).Results: Interobserver reliability and intraobserver repeatability universally revealed almost perfect agreement (ICC > 0.800). Significant differences in image quality were detected in basal ganglia (P < 0.001), central sulcus (P = 0.005), myelination (P < 0.001), lateral fissure (P = 0.008), optic chiasm (P < 0.001), and gray matter (P < 0.001) among radial VIBE with flip angles 6º, 9º, 12º, 15º and TFL groups. Image quality at the 9º flip angle in radial VIBE was generally better than TFL. Radial VIBE sequence with 9º flip angle of gray matter was significantly different by gestational age (GA) before and after 28 weeks (P = 0.036). Quantified image contrast was significantly different among protocols, consistent with qualitative analysis of image quality.Conclusions: Three-dimensional radial VIBE with 9º flip angle provides optimal, stable T1-weighted images of the fetal brain. Fetal brain structure and development can be evaluated using high-quality images obtained using this angle.

Metabolite-Specific Echo-Planar Imaging of Hyperpolarized [1-13C]Pyruvate at 4.7 T

Although hyperpolarization (HP) greatly increases the sensitivity of 13C MR, the usefulness of HP in vivo is limited by the short lifetime of HP agents. To address this limitation, we developed an echo-planar (EPI) sequence with spectral-spatial radiofrequency (SSRF) pulses for fast and efficient metabolite-specific imaging of HP [1-13C]pyruvate and [1-13C]lactate at 4.7 T. The spatial and spectral selectivity of each SSRF pulse was verified using simulations and phantom testing. EPI and CSI imaging of the rat abdomen were compared in the same rat after injecting HP [1-13C]pyruvate. A procedure was also developed to automatically set the SSRF excitation pulse frequencies based on real-time scanner feedback. The most significant results of this study are the demonstration that a greater spatial and temporal resolution is attainable by metabolite-specific EPI as compared with CSI, and the enhanced lifetime of the HP signal in EPI, which is attributable to the independent flip angle control between metabolites. Real-time center frequency adjustment was also highly effective for minimizing off-resonance effects. To the best of our knowledge, this is the first demonstration of metabolite-specific HP 13C EPI at 4.7 T. In conclusion, metabolite-specific EPI using SSRF pulses is an effective way to image HP [1-13C]pyruvate and [1-13C]lactate at 4.7 T.