Single-Scan Heteronuclear 13C-15N J-Coupling NMR Observations Enhanced by Dissolution Dynamic Nuclear Polarization.

Heteronuclear 13C-15N couplings were measured in single-scan nuclear magnetic resonance (NMR) experiments for a variety of nitrogen-containing chemical compounds with varied structural characteristics, by using a one-dimensional (1D) 13C-15N multiple-quantum (MQ)-filtered experiment. Sensitivity limitations of the MQ filtering were overcome by the combined use of 15N labeling and dissolution dynamic nuclear polarization (dDNP), performed at cryogenic conditions and followed by quick and optimized sample melting and transfer procedures. Coupling information could thus be obtained from nucleotide bases, amino acids, urea, and aliphatic and aromatic amides, including the measurement of relatively small J-couplings directly from the 1D filtered spectra. This experiment could pave the way for NMR-based analytical applications that investigate structural and stereochemical insights into nitrogen-containing compounds, including dipeptides and proteins, while relying on heteronuclear couplings and nuclear hyperpolarization.

Spatiotemporal encoding MRI in a portable low-field system.

PURPOSE: Demonstrate the potential of spatiotemporal encoding (SPEN) MRI to deliver largely undistorted 2D, 3D, and diffusion weighted images on a 110 mT portable system. METHODS: SPEN's quadratic phase modulation was used to subsample the low-bandwidth dimension of echo planar acquisitions, delivering alias-free images with an enhanced immunity to image distortions in a laboratory-built, low-field, portable MRI system lacking multiple receivers. RESULTS: Healthy brain images with different SPEN time-bandwidth products and subsampling factors were collected. These compared favorably to EPI acquisitions including topup corrections. Robust 3D and diffusion weighted SPEN images of diagnostic value were demonstrated, with 2.5 mm isotropic resolutions achieved in 3 min scans. This performance took advantage of the low specific absorption rate and relative long TEs associated with low-field MRI. CONCLUSION: SPEN MRI provides a robust and advantageous fast acquisition approach to obtain faithful 3D images and DWI data in low-cost, portable, low-field systems without parallel acceleration.

Molecular imaging of tumor metabolism: Insight from pyruvate- and glucose-based deuterium MRI studies.

Cancer diagnosis by metabolic MRI proposes to follow the fate of glycolytic precursors such as pyruvate or glucose, and their in vivo conversion into lactate. This study compares the 2H MRI outlooks afforded by these metabolites when targeting a pancreatic cancer model. Exogenously injected [3,3',3″-2H3]-pyruvate was visible only briefly; it generated a deuterated lactate signal throughout the body that faded after ~5 min, showing a minor concentration bias at the rims of the tumors. [6,6'-2H2]-glucose by contrast originated a lactate signal that localized clearly within the tumors, persisting for over an hour. Investigations alternating deuterated and nondeuterated glucose injections revealed correlations between the lactate generation and the glucose available at the tumor, evidencing a continuous and avid glucose consumption generating well-localized lactate signatures as driven by the Warburg effect. This is by contrast to the transient and more promiscuous pyruvate-to-lactate transformation, which seemed subject to transporter and kinetics effects. The consequences of these observations within metabolic MRI are briefly discussed.

Phase-Incremented Steady-State Free Precession as an Alternate Route to High-Resolution NMR.

Pulsed Fourier transform nuclear magnetic resonance (FT-NMR) has reigned supreme in high-resolution, high-field spectroscopy─particularly when targeting complex liquid-state samples involving multiple sharp peaks spread over large spectral bandwidths. It is known, however, that if spectral resolution is not a must, the FT-based approach is not necessarily the optimal route for maximizing NMR sensitivity: if T2 ≈ T1, as often found in solutions, Carr's steady-state free-precession (SSFP) approach can in principle provide a superior signal-to-noise ratio per √(acquisition_time) (SNRt). A rapid train of pulses will then lead to a transverse component that reaches up to 50% of the thermal equilibrium magnetization, provided that pulses are applied at repetition times TR ≪ T2, T1, and that a single suitable offset is involved. It is generally assumed that having to deal with multiple chemical shifts deprives SSFP from its advantages. The present study revisits this assumption by introducing an approach whereby arbitrarily short SSFP-derived free induction decays (FIDs) can deliver high-resolution spectra, without suffering from peak broadenings or phase distortions. To achieve discrimination among nearby frequencies, signals arising from a series of regularly phase-increased excitation pulses are collected. Given SSFP's amplitude and phase sensitivity to the spins' offset, this enables the resolution of sites according to their chemical shift position. In addition, the extreme fold-over associated with SSFP acquisitions is dealt with by a customized discrete FT of the interpulse time-domain signal. Solution-state 13C NMR spectra which compare well with FT-NMR data in terms of sensitivity, bandwidth, and resolution can then be obtained.

Short and long range 2D 15N-15N NMR correlations among peptide groups by novel solid state dipolar mixing schemes.

A recently developed homonuclear dipolar recoupling scheme, Adiabatic Linearly FREquency Swept reCOupling (AL FRESCO), was applied to record two-dimensional (2D) 15N-15N correlations on uniformly 15N-labeled GB1 powders. A major feature exploited in these 15N-15N correlations was AL FRESCO's remarkably low RF power demands, which enabled seconds-long mixing schemes when establishing direct correlations. These 15N-15N mixing schemes proved efficient regardless of the magic-angle spinning (MAS) rate and, being nearly free from dipolar truncation effects, they enabled the detection of long-range, weak dipolar couplings, even in the presence of strong short-range dipolar couplings. This led to a connectivity information that was significantly better than that obtained with spontaneously proton-driven, 15N spin-diffusion experiments. An indirect approach producing long-range 15N-15N correlations was also tested, relying on short (ms-long) 1HN-1HN mixings schemes while applying AL FRESCO chirped pulses along the 15N channel. These indirect mixing schemes produced numerous long-distance Ni-Ni±n (n = 2 - 5) correlations, that might be useful for characterizing three-dimensional arrangements in proteins. Once again, these AL FRESCO mediated experiments proved more informative than variants based on spin-diffusion-based 1HN-1HN counterparts.

Cross polarization from dipolar-order under magic angle spinning: The ADRF-CPMAS NMR experiment.

Techniques for enhancing the signals arising from low-γ, insensitive (I) nuclei are central to solid-state nuclear magnetic resonance. One of the leading and best-established methods to sensitize these unreceptive species is Hartmann-Hahn cross polarization (HH-CP), a polarization transfer mechanism often executed under MAS. Herein, we explore the possibility of utilizing the 1H dipolar order created via adiabatic demagnetization in the rotating frame (ADRF), to enhance the unreceptive spins under MAS. It is found that an efficient polarization transfer via ADRF-CPMAS is not only possible but can exceed, at least in some instances involving plastic crystals, the efficiency of an optimized HH-CPMAS transfer. The experiment requires low radiofrequency nutation fields on both the 1H- and the I-spin channels, and displays unusual matching conditions that are reminiscent of the zero- and double-quantum matching conditions arising under CPMAS, albeit centered at zero frequency and demanding the simultaneous involvement of several spins. The origin of these multi-spin transfer processes is analytically derived and numerically simulated in predictions that compare well with experimental 13C and 15N results collected on model compounds at different spinning speeds. These derivations start from descriptions that depart from traditional thermodynamic arguments, and treat instead the ADRF processes in static and spinning solids on the basis of coherent evolutions. The predictions of these analytical derivations are corroborated by numerical simulations. The effects of additional factors, including chemical shift anisotropies, J-couplings, and radiofrequency inhomogeneities, are also theoretically and experimentally explored.

Relaxation-Diffusion T2-ADC Correlations in Breast Cancer Patients: A Spatiotemporally Encoded 3T MRI Assessment.

Quantitative correlations between T2 and ADC values were explored on cancerous breast lesions using spatiotemporally encoded (SPEN) MRI. To this end, T2 maps of patients were measured at more than one b-value, and ADC maps at several echo time values were recorded. SPEN delivered quality, artifact-free, TE-weighted DW images, from which T2-ADC correlations could be obtained despite the signal losses brought about by diffusion and relaxation. Data confirmed known aspects of breast cancer lesions, including their reduced ADC values vs. healthy tissue. Data also revealed an anticorrelation between the T2 and ADC values, when comparing regions with healthy and diseased tissues. This is contrary to expectations based on simple water restriction considerations. It is also contrary to what has been observed in a majority of porous materials and tissues. Differences between the healthy tissue of the lesion-affected breast and healthy tissue in the contralateral breast were also noticed. The potential significance of these trends is discussed, as is the potential of combining T2- and ADC-weightings to achieve an enhanced endogenous MRI contrast about the location of breast cancer lesions.

Relaxation-Assisted Magnetization Transfer Phenomena for a Sensitivity-Enhanced 2D NMR.

2D NOESY and TOCSY play central roles in contemporary NMR. We have recently discussed how solvent-driven exchanges can significantly enhance the sensitivity of such methods when attempting correlations between labile and nonlabile protons. This study explores two scenarios where similar sensitivity enhancements can be achieved in the absence of solvent exchange: the first one involves biomolecular paramagnetic systems, while the other involves small organic molecules in natural abundance. It is shown that, in both cases, the effects introduced by either differential paramagnetic shift and relaxation or by polarization sharing among networks of protons can provide a similar sensitivity boost, as previously discussed for solvent exchange. The origin and potential of the resulting enhancements are analyzed, and experiments that demonstrate them in protein and natural products are exemplified. Limitations and future improvements of these approaches are also briefly discussed.

High-sensitivity deuterium metabolic MRI differentiates acute pancreatitis from pancreatic cancers in murine models.

Deuterium metabolic imaging (DMI) is a promising tool for investigating a tumor's biology, and eventually contribute in cancer diagnosis and prognosis. In DMI, [6,6'-2H2]-glucose is taken up and metabolized by different tissues, resulting in the formation of HDO but also in an enhanced formation of [3,3'-2H2]-lactate at the tumor site as a result of the Warburg effect. Recent studies have shown DMI's suitability to highlight pancreatic cancer in murine models by [3,3'-2H2]-lactate formation; an important question is whether DMI can also differentiate between these tumors and pancreatitis. This differentiation is critical, as these two diseases are hard to distinguish today radiologically, but have very different prognoses requiring distinctive treatments. Recent studies have shown the limitations that hyperpolarized MRI faces when trying to distinguish these pancreatic diseases by monitoring the [1-13C1]-pyruvate→[1-13C1]-lactate conversion. In this work, we explore DMI's capability to achieve such differentiation. Initial tests used a multi-echo (ME) SSFP sequence, to identify any metabolic differences between tumor and acute pancreatitis models that had been previously elicited very similar [1-13C1]-pyruvate→[1-13C1]-lactate conversion rates. Although ME-SSFP provides approximately 5 times greater signal-to-noise ratio (SNR) than the standard chemical shift imaging (CSI) experiment used in DMI, no lactate signal was observed in the pancreatitis model. To enhance lactate sensitivity further, we developed a new, weighted-average, CSI-SSFP approach for DMI. Weighted-average CSI-SSFP improved DMI's SNR by another factor of 4 over ME-SSFP-a sensitivity enhancement that sufficed to evidence natural abundance 2H fat in abdominal images, something that had escaped the previous approaches even at ultrahigh (15.2 T) MRI fields. Despite these efforts to enhance DMI's sensitivity, no lactate signal could be detected in acute pancreatitis models (n = 10; [3,3'-2H2]-lactate limit of detection < 100 µM; 15.2 T). This leads to the conclusion that pancreatic tumors and acute pancreatitis may be clearly distinguished by DMI, based on their different abilities to generate deuterated lactate.

Steady state effects introduced by local relaxation modes on J-driven DNP-enhanced NMR.

One of solution-state Nuclear Magnetic Resonance (NMR)'s main weaknesses, is its relative insensitivity. J-driven Dynamic Nuclear Polarization (JDNP) was recently proposed for enhancing solution-state NMR's sensitivity, by bypassing the limitations faced by conventional Overhauser DNP (ODNP), at the high magnetic fields where most analytical research is performed. By relying on biradicals with inter-electron exchange couplings Jex on the order of the electron Larmor frequency ωE, JDNP was predicted to introduce a transient enhancement in NMR's nuclear polarization at high magnetic fields, and for a wide range of rotational correlation times of medium-sized molecules in conventional solvents. This communication revisits the JDNP proposal, including additional effects and conditions that were not considered in the original treatment. These include relaxation mechanisms arising from local vibrational modes that often dominate electron relaxation in organic radicals, as well as the possibility of using biradicals with Jex of the order of the nuclear Larmor frequency ωN as potential polarizing agents. The presence of these new relaxation effects lead to variations in the JDNP polarization mechanism originally proposed, and indicate that triplet-to-singlet cross-relaxation processes may lead to a nuclear polarization enhancement that persists even at steady states. The physics and potential limitations of the ensuing theoretical derivations, are briefly discussed.

An automated multi-order phase correction routine for processing ultra-wideline NMR spectra.

Efficient acquisition of wideline solid-state nuclear magnetic resonance (NMR) spectra with patterns affected by large inhomogeneous broadening is accomplished with the use of broadband pulse sequences. These specialized pulse sequences often use frequency-swept pulses, which feature time-dependent phase and amplitude modulations that in turn deliver broad and uniform excitation across large spectral bandwidths. However, the resulting NMR spectra are often affected by complex frequency-dependent phase dispersions, owing to the interplay between the frequency-swept excitations and anisotropic resonance frequencies. Such phase distortions necessitate the use of multi-order non-linear corrections in order to obtain absorptive, distortion-free patterns with uniform phasing. Performing such corrections is often challenging due to the complex interdependence of the linear and non-linear phase contributions, and how these may affect the NMR signal. Hence, processing of these data usually involves calculating the spectra in magnitude mode wherein the phase information is discarded. Herein, we present a fully automated phasing routine that is capable of processing and phase correcting such wideline NMR spectra. Its performance is corroborated via processing of NMR data acquired using both the WURST-CPMG (Wideband, Uniform-Rate, Smooth Truncation with Carr-Purcell Meiboom-Gill acquisition) and BRAIN-CP (BRoadband Adiabatic Inversion Cross Polarization) pulse sequences for a variety of nuclei (i.e., 119Sn, 195Pt, 35Cl, 87Rb, and 14N). Based on both simulated and experimental NMR datasets, it is demonstrated that automatic phase corrections up to and including second order can be readily achieved without a priori information regarding the nature of the phase-distorted NMR datasets, and independently of the exact manner in which time-domain NMR data are collected and subsequently processed. In addition, it is shown that NMR spectra acquired at both single and multiple transmitter frequencies that are processed with this automated phasing routine have improved signal-to-noise properties than those processed with conventional magnitude calculations, along with powder patterns that better match those of ideal NMR spectra, even for datasets possessing low signal-to-noise ratios and/or affected by spectral artifacts.

Functional MRI of murine olfactory bulbs at 15.2T reveals characteristic activation patters when stimulated by different odors.

Thanks to its increased sensitivity, single-shot ultrahigh field functional MRI (UHF fMRI) could lead to valuable insight about subtle brain functions such as olfaction. However, UHF fMRI experiments targeting small organs next to air voids, such as the olfactory bulb, are severely affected by field inhomogeneity problems. Spatiotemporal Encoding (SPEN) is an emerging single-shot MRI technique that could provide a route for bypassing these complications. This is here explored with single-shot fMRI studies on the olfactory bulbs of male and female mice performed at 15.2T. SPEN images collected on these organs at a 108 µm in-plane resolution yielded remarkably large and well-defined responses to olfactory cues. Under suitable T2* weightings these activation-driven changes exceeded 5% of the overall signal intensity, becoming clearly visible in the images without statistical treatment. The nature of the SPEN signal intensity changes in such experiments was unambiguously linked to olfaction, via single-nostril experiments. These experiments highlighted specific activation regions in the external plexiform region and in glomeruli in the lateral part of the bulb, when stimulated by aversive or appetitive odors, respectively. These strong signal activations were non-linear with concentration, and shed light on how chemosensory signals reaching the olfactory epithelium react in response to different cues. Second-level analyses highlighted clear differences among the appetitive, aversive and neutral odor maps; no such differences were evident upon comparing male against female olfactory activation regions.

Cross-Polarization Schemes for Improved Heteronuclear Transfers Involving Labile Protons in Biomolecular Solution NMR.

INEPT-based experiments are widely used for 1 H→15 N transfers, but often fail when involving labile protons due to solvent exchanges. J-based cross polarization (CP) strategies offer a more efficient alternative to perform such transfers, particularly when leveraging the Hwater ↔ ${ \leftrightarrow }$ HN exchange process to boost the 1 H→15 N transfer process. This leveraging, however, demands the simultaneous spin-locking of both Hwater and HN protons by a strong 1 H RF field, while fulfilling the γH B1,H =γN B1,N Hartmann-Hahn matching condition. Given the low value of γN /γH , however, these demands are often incompatible-particularly when experiments are executed by the power-limited cryogenic probes used in contemporary high field NMR. The present manuscript discusses CP alternatives that can alleviate this limitation, and evaluates their performance on urea, amino acids, and intrinsically disordered proteins. These alternatives include new CP variants based on frequency-swept and phase-modulated pulses, designed to simultaneously fulfill the aforementioned conflicting conditions. Their performances vis-à-vis current options are theoretically analyzed with Liouville-space simulations, and experimentally tested with double and triple resonance transfer experiments.

Deuterium imaging of the Warburg effect at sub-millimolar concentrations by joint processing of the kinetic and spectral dimensions.

Deuterium metabolic imaging (DMI) is a promising molecular MRI approach, which follows the administration of deuterated substrates and their metabolization. [6,6'-2 H2 ]-glucose for instance is preferentially converted in tumors to [3,3'-2 H2 ]-lactate as a result of the Warburg effect, providing a distinct resonance whose mapping using time-resolved spectroscopic imaging can diagnose cancer. The MR detection of low-concentration metabolites such as lactate, however, is challenging. It has been recently shown that multi-echo balanced steady-state free precession (ME-bSSFP) increases the signal-to-noise ratio (SNR) of these experiments approximately threefold over regular chemical shift imaging; the present study examines how DMI's sensitivity can be increased further by advanced processing methods. Some of these, such as compressed sensing multiplicative denoising and block-matching/3D filtering, can be applied to any spectroscopic/imaging methods. Sensitivity-enhancing approaches were also specifically tailored to ME-bSSFP DMI, by relying on priors related to the resonances' positions and to features of the metabolic kinetics. Two new methods are thus proposed that use these constraints for enhancing the sensitivity of both the spectral images and the metabolic kinetics. The ability of these methods to improve DMI is evidenced in pancreatic cancer studies carried at 15.2 T, where suitable implementations of the proposals imparted eightfold or more SNR improvement over the original ME-bSSFP data, at no informational cost. Comparisons with other propositions in the literature are briefly discussed.

Prostate lesions characterization using diffusion-weighted spatiotemporal encoded MRI: Feasibility and initial assessment.

PURPOSE: To assess the feasibility and reliability of a DWI protocol based on spatiotemporally encoding (SPEN), to target prostate lesions along guidelines normally used in EPI-based DWI clinical practice. METHODS: Prostate Imaging-Reporting and Data System recommendations underlying clinical prostate scans were used to develop a SPEN-based DWI protocol, which included a novel, local, low-rank regularization algorithm. These DWI acquisitions were run at 3 T under similar nominal spatial resolutions and diffusion-weighting b-values as used in EPI-based clinical studies. Prostates of 11 patients suspected of clinically significant prostate cancer lesions were therefore scanned using the two methods, with the same number of slices, same slice thickness, and same interslice gaps. RESULTS: Of the 11 patients scanned, SPEN and EPI provided comparable information in 7 of the cases, whereas EPI was deemed superior in a case for which SPEN images had to be acquired with a shorter effective TR owing to scan-time constraints. SPEN provided reduced susceptibility to field-derived distortions in 3 of the cases. CONCLUSIONS: SPEN's ability to provide prostate lesion contrast was most clearly evidenced for DW images acquired with b ≥ 900 s/mm2 . SPEN also succeeded in decreasing occasional image distortions in regions close to the rectum, affected by field inhomogeneities. EPI advantages arose when using short effective TRs, a regime in which SPEN-based DWI was handicapped by its use of nonselective spin inversions, leading to the onset of an additional T1 weighting.

Microwave-free J-driven dynamic nuclear polarization: A proposal for enhancing the sensitivity of solution-state NMR.

J-driven dynamic nuclear polarization (JDNP) was recently proposed for enhancing the sensitivity of solution-state nuclear magnetic resonance (NMR), while bypassing the limitations faced by conventional (Overhauser) DNP at magnetic fields of interest in analytical applications. Like Overhauser DNP, JDNP also requires saturating the electronic polarization using high-frequency microwaves known to have poor penetration and associated heating effects in most liquids. The present microwave-free JDNP (MF-JDNP) proposal seeks to enhance solution NMR's sensitivity by shuttling the sample between higher and lower magnetic fields, with one of these fields providing an electron Larmor frequency that matches the interelectron exchange coupling J_{ex}. If spins cross this so-called JDNP condition sufficiently fast, we predict that a sizable nuclear polarization will be created without microwave irradiation. This MF-JDNP proposal requires radicals whose singlet-triplet self-relaxation rates are dominated by dipolar hyperfine relaxation, and shuttling times that can compete with these electron relaxation processes. This paper discusses the theory behind the MF-JDNP, as well as proposals for radicals and conditions that could enable this new approach to NMR sensitivity enhancement.

Identifying and Overcoming Artifacts in 1 H-Based Saturation Transfer NOE NMR Experiments.

Magnetization transfer experiments are versatile nuclear magnetic resonance (NMR) tools providing site-specific information. We have recently discussed how saturation magnetization transfer (SMT) experiments could leverage repeated repolarizations arising from exchanges between labile and water protons to enhance connectivities revealed via the nuclear Overhauser effect (NOE). Repeated experience with SMT has shown that a number of artifacts may arise in these experiments, which may confound the information being sought - particularly when seeking small NOEs among closely spaced resonances. One of these pertains to what we refer to as "spill-over" effects, originating from the use of long saturation pulses leading to changes in the signals of proximate peaks. A second, related but in fact different effect, derives from what we describe as NOE "oversaturation", a phenomenon whereby the use of overtly intense RF fields overwhelms the cross-relaxation signature. The origin and ways to avoid these two effects are described. A final source of potential artifact arises in applications where the labile 1Hs of interest are bound to 15N-labeled heteronuclei. SMT's long 1H saturation times will then be usually implemented while under 15N decoupling based on cyclic schemes leading to decoupling sidebands. Although these sidebands usually remain invisible in NMR, they may lead to a very efficient saturation of the main resonance when touched by SMT frequencies. All of these phenomena are herein experimentally demonstrated, and solutions to overcome them are proposed.

Understanding aliasing effects and their removal in SPEN MRI: A k-space perspective.

PURPOSE: To characterize the mechanism of formation and the removal of aliasing artifacts and edge ghosts in spatiotemporally encoded (SPEN) MRI within a k-space theoretical framework. METHODS: SPEN's quadratic phase modulation can be described in k-space by a convolution matrix whose coefficients derive from Fourier relations. This k-space model allows us to pose SPEN's reconstruction as a deconvolution process from which aliasing and edge ghost artifacts can be quantified by estimating the difference between a full sampling and reconstructions resulting from undersampled SPEN data. RESULTS: Aliasing artifacts in SPEN MRI reconstructions can be traced to image contributions corresponding to high-frequency k-space signals. The k-space picture provides the spatial displacements, phase offsets, and linear amplitude modulations associated to these artifacts, as well as routes to removing these from the reconstruction results. These new ways to estimate the artifact priors were applied to reduce SPEN reconstruction artifacts on simulated, phantom, and human brain MRI data. CONCLUSION: A k-space description of SPEN's reconstruction helps to better understand the signal characteristics of this MRI technique, and to improve the quality of its resulting images.

Indirectly detected satellite-transition quadrupolar NMR via progressive saturation of the proton reservoir.

Static satellite-transitions (ST) NMR line shapes from half-integer quadrupolar nuclei could be very informative: they can deliver insight about local motions over a wide range of timescales, and can report on small changes in the local electronic environments as reflected by variations in the quadrupolar parameters. Satellite transitions, however, are typically "invisible" for half-integer quadrupolar nuclei due to their sheer breadth, leading to low signal-to-noise ratio -especially for unreceptive low-gamma or dilute quadrupolar nuclei. Very recently we have introduced a method for enhancing the NMR sensitivity of unreceptive X nuclei in static solids dubbed PROgressive Saturation of the Proton Reservoir (PROSPR), which opens the possibility of magnifying the signals from such spins by repeatedly imprinting frequency-selective X-driven depolarizations on the much more sensitive 1H NMR signal. Here, we show that PROSPR's efficacy is high enough for enabling the detection of static ST NMR for challenging species like 35Cl, 33S and even 17O -all at natural-abundance. The ensuing ST-PROSPR NMR experiment thus opens new approaches to probe ultra-wideline (6-8 MHz wide) spectra. These highly pronounced anisotropies can in turn deliver new vistas about dynamic changes in solids, as here illustrated by tracking ST line shapes as a function of temperature during thermally-driven events.