Fast Spin Research Articles

Optimal sensitivity for 1H detected relayed DNP of organic solids at fast MAS

Dynamic nuclear polarization (DNP) combined with high magnetic fields and fast magic angle spinning (MAS) has opened up a new avenue for the application of exceptionally sensitive 1H NMR detection schemes to study protonated solids. Recently, it has been shown that DNP experiments at fast MAS rates lead to slower spin diffusion and hence reduced DNP enhancements for impregnated materials. However, DNP enhancements alone do not determine the overall sensitivity of a NMR experiment. Here we measure the overall sensitivity of one-dimensional 1H detected relayed DNP experiments as a function of the MAS rate in the 20–60 kHz regime using 0.7 mm diameter rotors at 21.2 T. Although faster MAS rates are detrimental for the DNP enhancement on the target material, due to slower spin diffusion, we find that with increasing spinning rates the gain in sensitivity due to 1H line-narrowing and the folding-in of sideband intensity compensates a large part of the loss of overall hyperpolarization. We find that sensitivity depends on the atomic site in the molecule, and is maximised at between 40 and 50 kHz MAS for the sample of L-histidine.HCl·H2O studied here. There is a 10–20 % difference in sensitivity between the optimum MAS rate and the fastest rate currently accessible (60 kHz).

Using Abundant 1H Polarization to Enhance the Sensitivity of Solid-State NMR Spectroscopy.

Solid-state NMR spectroscopy has been playing a significant role in elucidating the structures and dynamics of materials and proteins at the atomic level for decades. As an extremely abundant nucleus with a very high gyromagnetic ratio, protons are widely present in most organic/inorganic materials. Thus, this Perspective highlights the advantages of proton detection at fast magic-angle spinning (MAS) and presents strategies to utilize and exhaust 1H polarization to achieve signal sensitivity enhancement of solid-state NMR spectroscopy, enabling substantial time savings and extraction of more structural and dynamics information per unit time. Those strategies include developing sensitivity-enhanced single-channel 1H multidimensional NMR spectroscopy, implementing multiple polarization transfer steps in each scan to enhance low-γ nuclei signals, and making full use of 1H polarization to obtain homonuclear and heteronuclear chemical shift correlation spectra in a single experiment. Finally, outlooks and perspectives are provided regarding the challenges and future for the further development of sensitivity-enhanced proton-based solid-state NMR spectroscopy.

Three-Dimensional Multifrequency MR Elastography for Microvascular Invasion and Prognosis Assessment in Hepatocellular Carcinoma.

Pretreatment identification of microvascular invasion (MVI) in hepatocellular carcinoma (HCC) is important when selecting treatment strategies. To improve models for predicting MVI and recurrence-free survival (RFS) by developing nomograms containing three-dimensional (3D) MR elastography (MRE). Prospective. 188 patients with HCC, divided into a training cohort (n = 150) and a validation cohort (n = 38). In the training cohort, 106/150 patients completed a 2-year follow-up. 1.5T 3D multifrequency MRE with a single-shot spin-echo echo planar imaging sequence, and 3.0T multiparametric MRI (mp-MRI), consisting of diffusion-weighted echo planar imaging, T2-weighted fast spin echo, in-phase out-of-phase T1-weighted fast spoiled gradient-recalled dual-echo and dynamic contrast-enhanced gradient echo sequences. Multivariable analysis was used to identify the independent predictors for MVI and RFS. Nomograms were constructed for visualization. Models for predicting MVI and RFS were built using mp-MRI parameters and a combination of mp-MRI and 3D MRE predictors. Student's t-test, Mann-Whitney U test, chi-squared or Fisher's exact tests, multivariable analysis, area under the receiver operating characteristic curve (AUC), DeLong test, Kaplan-Meier analysis and log rank tests. P < 0.05 was considered significant. Tumor c and liver c were independent predictors of MVI and RFS, respectively. Adding tumor c significantly improved the diagnostic performance of mp-MRI (AUC increased from 0.70 to 0.87) for MVI detection. Of the 106 patients in the training cohort who completed the 2-year follow up, 34 experienced recurrence. RFS was shorter for patients with MVI-positive histology than MVI-negative histology (27.1 months vs. >40 months). The MVI predicted by the 3D MRE model yielded similar results (26.9 months vs. >40 months). The MVI and RFS nomograms of the histologic-MVI and model-predicted MVI-positive showed good predictive performance. Biomechanical properties of 3D MRE were biomarkers for MVI and RFS. MVI and RFS nomograms were established. 2 TECHNICAL EFFICACY: Stage 2.

Exploring the Higher Order Structure and Conformational Transitions in Insulin Microcrystalline Biopharmaceuticals by Proton-Detected Solid-State Nuclear Magnetic Resonance at Natural Abundance.

The integrity of a higher order structure (HOS) is an essential requirement to ensure the efficacy, stability, and safety of protein therapeutics. Solution-state nuclear magnetic resonance (NMR) occupies a unique niche as one of the most promising methods to access atomic-level structural information on soluble biopharmaceutical formulations. Another major class of drugs is poorly soluble, such as microcrystalline suspensions, which poses significant challenges for the characterization of the active ingredient in its native state. Here, we have demonstrated a solid-state NMR method for HOS characterization of biopharmaceutical suspensions employing a selective excitation scheme under fast magic angle spinning (MAS). The applicability of the method is shown on commercial insulin suspensions at natural isotopic abundance. Selective excitation aided with proton detection and non-uniform sampling (NUS) provides improved sensitivity and resolution. The enhanced resolution enabled us to demonstrate the first experimental evidence of a phenol-escaping pathway in insulin, leading to conformational transitions to different hexameric states. This approach has the potential to serve as a valuable means for meticulously examining microcrystalline biopharmaceutical suspensions, which was previously not attainable in their native formulation states and can be seamlessly extended to other classes of biopharmaceuticals such as mAbs and other microcrystalline proteins.

MR Susceptibility Separation for Quantifying Lesion Paramagnetic and Diamagnetic Evolution in Relapsing-Remitting Multiple Sclerosis.

Multiple sclerosis (MS) lesion evolution may involve changes in diamagnetic myelin and paramagnetic iron. Conventional quantitative susceptibility mapping (QSM) can provide net susceptibility distribution, but not the discrete paramagnetic and diamagnetic components. To apply susceptibility separation (χ separation) to follow lesion evolution in MS with comparison to R2*/R2 '/QSM. Longitudinal, prospective. Twenty relapsing-remitting MS subjects (mean age: 42.5 ± 9.4 years, 13 females; mean years of symptoms: 4.3 ± 1.4 years). Three-dimensional multiple echo gradient echo (QSM and R2* mapping), two-dimensional dual echo fast spin echo (R2 mapping), T2-weighted fluid attenuated inversion recovery, and T1-weighted magnetization prepared gradient echo sequences at 3 T. Data were analyzed from two scans separated by a mean interval of 14.4 ± 2.0 months. White matter lesions on fluid-attenuated inversion recovery were defined by an automatic pipeline, then manually refined (by ZZ/AHW, 3/25 years' experience in MRI), and verified by a radiologist (MN, 25 years' experience in MS). Susceptibility separation yielded the paramagnetic and diamagnetic susceptibility content of each voxel. Lesions were classified into four groups based on the variation of QSM/R2* or separated into positive/negative components from χ separation. Two-sample paired t tests for assessment of longitudinal differences. Spearman correlation coefficients to assess associations between χ separation and R2*/R2 '/QSM. Significant level: P < 0.005. A total of 183 lesions were quantified. Categorizing lesions into groups based on χ separation demonstrated significant annual changes in QSM//R2*/R2 '. When lesions were grouped based on changes in QSM and R2*, both changing in unison yielded a significant dominant paramagnetic variation and both opposing yielded a dominant diamagnetic variation. Significant Spearman correlation coefficients were found between susceptibility-sensitive MRI indices and χ separation. Susceptibility separation changes in MS lesions may distinguish and quantify paramagnetic and diamagnetic evolution, potentially providing additional insight compared to R2* and QSM alone. 2 TECHNICAL EFFICACY: Stage 2.

P067 Volumetric Assessment of Treatment Response in Newly Diagnosed Crohn Disease: A Pilot Study

Abstract Background Traditionally, mural thickness and disease length have been the radiological standards for assessing Crohn's Disease (CD) severity and treatment response. Our study aimed to evaluate and compare these linear measurements with volumetric ones in newly diagnosed pediatric CD, as well as to assess the concordance between manual and semi-automated volumetric methods. Methods In this single-center, prospective study, 20 children with newly diagnosed ileal CD treated with anti-TNF therapy from Dec 2018 to Oct 2021 (8 females; median age=14.5 years) underwent dedicated research MRI examinations at three timepoints – diagnosis (baseline) as well as 6 weeks and 6 months into therapy. For each exam and using T2-weighted Single Shot Fast Spin Echo (SSFSE) images, a single radiologist measured maximum bowel wall thickness (BWT, mm) and length of disease (cm). The inflamed ileum was manually segmented to measure tissue volume (ml) (Entrolytics; Motilent, London, UK). Semi-automated 3D volumetric measurements of the inflamed ileum (GI Seg tool) were created using the same platform. Estimated maximum BWT also was automatically calculated from manually-edited algorithmically generated masks. Mixed-effects models evaluated measurement changes over time. Intra-class correlation assessed absolute agreement between manual and automated volumetric assessments. Results BWT decreased over time with treatment (0.76 vs. 0.58 vs. 0.45 cm; p&amp;lt;0.0001), with a 24% decrease from baseline to 6 weeks and a 41% decrease from baseline to 6 months. Similarly, there was a significant decrease in length of disease over time (19.2 vs. 12.2 vs. 8.0 cm; p=0.002), with a 36% decrease from baseline to 6 weeks and a 58% decrease from baseline to 6 months. Manual volumetric measurements also showed a significant treatment response (19.8 vs. 11.6 vs. 5.1 ml; p&amp;lt;0.0001), with a 41% decrease from baseline to 6 weeks and a 74% decrease from baseline to 6 months. Using the semi-automated segmentation tool, the volume of inflamed bowel also decreased significantly over time (24.0 vs. 15.1 vs. 9.1 ml; p=0.0007), decreasing 37% between baseline and 6 weeks and 62% between baseline and 6 months. There was good agreement between manual and semi-automated volumetric bowel assessments (ICC=0.78 [95% CI: 0.57-0.88]). ICC between manual and code-estimated Max BWT was 0.60 [95% CI: 0.42, 0.72] with a strong positive correlation (r=0.839; p &amp;lt;0.001) between these two methods as shown in the Figure. Conclusion Volumetric assessments, along with automatic measurements of bowel wall thickness, show promise in accurately assessing treatment response in pediatric CD. These methods might provide more consistent and repeatable measurements, essential for long-term disease monitoring and management.

Associations of Intracranial Artery Length and Branch Number on Time-of-Flight MRA With Cognitive Impairment in Hypertensive Older Males.

Hypertension-induced impairment of the cerebral artery network contributes to cognitive impairment. Characterizing the structure and function of cerebral arteries may facilitate the understanding of hypertension-related pathological mechanisms and lead to the development of new indicators for cognitive impairment. To investigate the associations between morphological features of the intracranial arteries distal to the circle of Willis on time-of-flight MRA (TOF-MRA) and cognitive performance in a hypertensive cohort. Prospective observational study. 189 hypertensive older males (mean age 64.9 ± 7.2 years). TOF-MRA sequence with a 3D spoiled gradient echo readout and arterial spin labeling perfusion imaging sequence with a 3D stack-of-spirals fast spin echo readout at 3T. The intracranial arteries were segmented from TOF-MRA and the total length of distal arteries (TLoDA) and number of arterial branches (NoB) were calculated. The mean gray matter cerebral blood flow (GM-CBF) was extracted from arterial spin labeling perfusion imaging. The cognitive level was assessed with short-term and long-term delay-recall auditory verbal learning test (AVLT) scores, and with montreal cognitive assessment. Univariable and multivariable linear regression were used to analyze the associations between TLoDA, NoB, GM-CBF and the cognitive assessment scores, with P < 0.05 indicating significance. TLoDA (r = 0.314) and NoB (r = 0.346) were significantly correlated with GM-CBF. Multivariable linear regression analyses showed that TLoDA and NoB, but not GM-CBF (P = 0.272 and 0.141), were significantly associated with short-term and long-term delay-recall AVLT scores. These associations remained significant after adjusting for GM-CBF. The TLoDA and NoB of distal intracranial arteries on TOF-MRA are significantly associated with cognitive impairment in hypertensive subjects. 2 TECHNICAL EFFICACY: Stage 3.

A Systematic Review of Cochlear Implant-Related Magnetic Resonance Imaging Artifact: Implications for Clinical Imaging.

To conduct a systematic review of the existing literature with the aim of evaluating and consolidating the present understanding of strategies for mitigating magnetic resonance imaging (MRI) artifacts related to cochlear implants in adult and pediatric patients, covering both in-vivo and ex-vivo investigations. A systematic review of MEDLINE-Ovid, Embase, Google Scholar, The Cochrane Library, and Scopus was performed from inception through April 2022. The protocol was registered with PROSPERO before commencement of data collection (CRD CRD42022319651). The data were screened and collected by two authors independently, and eligibility was assessed according to Cochrane Handbook and Preferred Reporting Items for Systematic Review and Meta-Analysis recommendations, whereas the quality of the articles was evaluated using the NIH Study Quality Assessment. The search yielded 2,354 potentially relevant articles, of which 27 studies were included in the final review. Twelve studies looked at 1.5-T MRI, four studies looked at 3-T MRI, eight studies looked at both 1.5 and 3 T, one study looked at 0.2 and 1.5 T, and one study looked at 3- and 7.0-T MRI. Nineteen studies focused on MRI sequences as a means of artifact reduction, nine studies focused on implant magnet positioning, two studies focused on head positioning, and one study focused on both magnet and head positioning. In terms of MRI sequences, diffusion-weighted imaging produced larger artifacts compared with other sequences, whereas fast spin echo/turbo spin echo sequences and fat suppression techniques produced smaller artifacts. The position of the magnet was also found to be important, with a magnet position more than 6.5 cm posterior to the external auditory canal producing the best images with the least distortion. The angle at which the magnet is placed also affects visibility of different brain structures. Proper head positioning, magnet placement at a distance of over 6.5 cm from the external auditory canal, use of spin echo sequences, and fat suppression techniques reduce the size and shape of MRI artifacts.

Generalised Jeffery's equations for rapidly spinning particles. Part 1. Spheroids

The observed behaviour of passive objects in simple flows can be surprisingly intricate, and is complicated further by object activity. Inspired by the motility of bacterial swimmers, in this two-part study we examine the three-dimensional motion of rigid active particles in shear Stokes flow, focusing on bodies that induce rapid rotation as part of their activity. In Part 1 we develop a multiscale framework to investigate these emergent dynamics and apply it to simple spheroidal objects. In Part 2 (Dalwadi et al., J. Fluid Mech., vol. 979, 2024, A2) we apply our framework to understand the emergent dynamics of more complex shapes; helicoidal objects with chirality. Via a multiple scales asymptotic analysis for nonlinear systems, we systematically derive emergent equations of motion for long-term trajectories that explicitly account for the strong (leading-order) effects of fast spinning. Supported by numerical examples, we constructively link these effective dynamics to the well-known Jeffery's orbits for passive spheroids, deriving an explicit closed-form expression for the effective shape of the active particle, broadening the scope of Jeffery's seminal study to spinning spheroids.

Experimental aspects of 14N overtone RESPDOR solid-state NMR spectroscopy under MAS beyond 60 kHz

Nitrogen-14 (14N) overtone (OT) spectroscopy under fast magic angle spinning (MAS) conditions (>60 kHz) has emerged as a powerful technique for observing correlations and distances between 14N and 1H, owing to the absence of the first-order quadrupolar broadenings. In addition, 14NOT allows selective manipulation of 14N nuclei for each site. Despite extensive theoretical and experimental studies, the spin dynamics of 14NOT remains under debate. In this study, we conducted experimental investigations to assess the spin dynamics of 14NOT using the rotational-echo saturation-pulse double-resonance (RESPDOR) sequence, which monitors population transfer induced by a14NOT pulse. The 14NOT spin dynamics is well represented by a model of a two-energy-level system. Unlike spin-1/2, the maximum excitation efficiency of 14NOT coherences of powdered solids, denoted by p, depends on the radiofrequency field (rf-field) strength due to orientation dependence of effective nutation fields even when pulse lengths are optimized. It is also found that the p factor, contributing to the 14NOT spin dynamics, is nearly independent of the B0 field. Consequently, the filtering efficiency of RESPDOR experiments exhibits negligible dependence on B0 when the 14NOT pulse length is optimized. The study also identifies the optimal experimental conditions for 14NOT/1H RESPDOR correlation experiments.

A solid-state NMR method for characterization of pharmaceutical eutectics.

Pharmaceutical eutectics are extremely useful for designing formulations, and currently, there are no techniques other than differential scanning calorimetry (DSC) that can confirm their formation. In this study, we demonstrate that 1H fast magic angle spinning (MAS) solid-state NMR (SSNMR) experiments can confirm the formation of eutectics by detecting their intermolecular hydrogen bonding interactions.

Inter-scanner comparability of Z-scores for native myocardial T1 and T2 mapping

BackgroundCardiovascular Magnetic Resonance (CMR) native T1 and T2 mapping serve as robust, contrast-agent-free diagnostic tools, but hardware- and software-specific sources of variability limit the generalizability of data across CMR platforms, consequently limiting the interpretability of patient-specific parametric data. Z-scores are used to describe the relationship of observed values to the mean results as obtained in a sufficiently large normal sample. They have been successfully used to describe the severity of quantifiable abnormalities in medicine, specifically in children and adolescents. The objective of this study was to observe whether z-scores can improve the comparability of T1 and T2 mapping values across CMR scanners, field strengths, and sequences from different vendors in the same participant rather than different participants (as seen in previous studies). MethodsFifty-one healthy volunteers (26 men/25 women, mean age = 43 ± 13.51) underwent three CMR exams on three different scanners, using a Modified Look-Locker Inversion Recovery (MOLLI) 5-(3)− 3 sequence to quantify myocardial T1. For T2 mapping, a True Fast Imaging with steady-state free precession (TRUFI) sequence was used on a 3 T Skyra™ (Siemens), and a T2 Fast Spin Echo (FSE) sequence was used on 1.5 T Artist™ (GE) and 3.0 T Premier™ (GE) scanners. The averages of basal and mid-ventricular short axis slices were used to derive means and standard deviations of global mapping values. We used intra-class comparisons (ICC), repeated measures ANOVA, and paired Student’s t-tests for statistical analyses. ResultsThere was a significant improvement in intra-subject comparability of T1 (ICC of 0.11 (95% CI= −0.018, −0.332) vs 0.78 (95% CI= 0.650, 0.866)) and T2 (ICC of 0.35 (95% CI= −0.053, 0.652) vs 0.83 (95% CI= 0.726, 0.898)) when using z-scores across all three scanners. While the absolute global T1 and T2 values showed a statistically significant difference between scanners (p < 0.001), no such differences were identified using z-scores (T1z: p = 0.771; T2z: p = 0.985). Furthermore, when images were not corrected for motion, T1 z-scores showed significant inter-scanner variability (p < 0.001), resolved by motion correction. ConclusionEmploying z-scores for reporting myocardial T1 and T2 removes the variation of quantitative mapping results across different MRI systems and field strengths, improving the clinical utility of myocardial tissue characterization in patients with suspected myocardial disease.

Comparative Analysis of FSE T2 Weighted, Chemical Shift and Dynamic Contrast-Enhanced MR Imaging in the Characterization of Adrenal Masses Based on Qualitative and Quantitative Parameters.

The purpose of our study was to investigate the role of different magnetic resonance imaging (MRI) parameters in the characterization of adrenal masses. A total of 150 patients who presented with 186 adrenal tumors were retrospectively evaluated in this study. Final patient cohort consisted of 17 pheochromocytomas, 3 adrenocortical carcinomas, 24 metastases, 31 lipid-poor adenomas and 111 lipid-rich adenomas. We carried out a visual assessment on FSE (Fast spin echo)T2 weighted images and also calculated T2 signal intensity ratio of all adrenal masses and also performed a qualitative assessment on chemical shift imaging (CSI) together with quantitative calculation using Adrenal to spleen signal intensity (si) ratio and Adrenal si index formulas. On dynamic contrast-enhanced sequences, visual assessment based on enhancement patterns on late-arterial phase images was performed and also mean signal intensity measurements were carried out. All examinations were interpreted by two abdominal radiologists in consensus who were blinded to the clinical and pathological findings. Statistical analysis was performed. On FSE T2 weighted imaging, isointense to liver and slightly hyperintense than liver was found higher in benign cases, however, in malignant cases moderately and strikingly hyperintense than liver was higher than in benign cases (p=0.001, p<0.01). There was a statistically significant difference between the T2 signal intensity ratio values of adrenal tumor groups (p=0.001, p<0.01). In lipid-rich and lipid-poor adenoma groups, T2 signal intensity ratio values was significantly lower than in pheochromocytoma and metastasis cases. In malignant group, T2 signal intensity ratio values were found statistically significantly higher than in the benign group (p=0.001, p<0.01). There was a statistically significant difference between CSI visual assessment of adrenal tumor groups (p=0.001, p<0.01). Although moderate and significant signal intensity loss was usually detected in lipid-rich adenoma group, never detected in other tumor groups. There was also a statistically significant difference between benign and malignant adrenal tumor groups (p=0.001, p<0.01). In the malignant group, Adrenal to spleen si ratio values were found significantly higher whereas, Adrenal si index values were significantly lower compared to benign tumors (p=0.001, p<0.01). Based on malignancy, there was a statistically significant difference between adrenal tumor groups (p=0.001, p<0.01). Although capillary blush and homogenous type enhancement were more common in benign cases than in malignant ones, peripheral-patchy and strikingly capillary blush type enhancement was more frequent in malignant tumors. Based on malignancy, mean arterial signal intensity values of malignant tumors were statistically higher than benign tumors (p=0.001; p<0.01). Dynamic contrast-enhanced MRI protocol including CSI aids in the characterization of indeterminate adrenal masses. Herein, the combined use of qualitative and quantitative parameters enables more tumors to be recognized that otherwise would be indeterminate.

Comparison of 3D Gradient-Echo Versus 2D Sequences for Assessing Shoulder Joint Image Quality in MRI.

Background: Three-dimensional gradient-echo (3D-GRE) sequences provide isotropic or nearly isotropic 3D images, leading to better visualization of smaller structures, compared to two-dimensional (2D) sequences. The aim of this study was to prospectively compare 2D and 3D-GRE sequences in terms of key imaging metrics, including signal-to-noise ratio (SNR), contrast-to-noise ratio (CNR), glenohumeral joint space, image quality, artifacts, and acquisition time in shoulder joint images, using 1.5-T MRI scanner. Methods: Thirty-five normal volunteers with no history of shoulder disorders prospectively underwent a shoulder MRI examination with conventional 2D sequences, including T 1- and T 2-weighted fast spin echo (T1/T2w FSE) as well as proton density-weighted FSE with fat saturation (PD-FS) followed by 3D-GRE sequences including VIBE, TRUEFISP, DESS, and MEDIC techniques. Two independent reviewers assessed all images of the shoulder joints. Pearson correlation coefficient and intra-RR were used for reliability test. Results: Among 3D-GRE sequences, TRUEFISP showed significantly the best CNR between cartilage-bone (31.37 ± 2.57, p < 0.05) and cartilage-muscle (13.51 ± 1.14, p < 0.05). TRUEFISP also showed the highest SNR for cartilage (41.65 ± 2.19, p < 0.01) and muscle (26.71 ± 0.79, p < 0.05). Furthermore, 3D-GRE sequences showed significantly higher image quality, compared to 2D sequences (p < 0.001). Moreover, the acquisition time of the 3D-GRE sequences was considerably shorter than the total acquisition time of PD-FS sequences in three orientations (p < 0.01). Conclusions: 3D-GRE sequences provide superior image quality and efficiency for evaluating articular joints, particularly in shoulder imaging. The TRUEFISP technique offers the best contrast and signal quality, making it a valuable tool in clinical practice.

Synthesis and photoinduced behavior of DPP-anchored nitronyl nitroxides: a multifaceted approach.

Understanding and controlling spin dynamics in organic dyes is of significant scientific and technological interest. The investigation of 2,5-dihydropyrrolo[4,3-c]pyrrolo-1,4-dione derivatives (DPPs), one of the most widely used dyes in many fields, has so far been limited to closed-shell molecules. We present a comprehensive joint experimental and computational study of DPP derivatives covalently linked to two nitronyl nitroxide radicals (DPPTh-NN2). Synthesis, single crystal X-ray diffraction study, photophysical properties, magnetic properties established using steady-state and pulse EPR, fast spin dynamics, and computational modelling using density functional theory and ab initio methods of electronic structure and spectroscopic properties of DPPTh-NN2 are presented. The single-crystal X-ray diffraction analysis of DPPTh-NN2 and computational modeling of its electronic structure suggest that effective conjugation along the backbone leads to noticeable spin-polarization transfer. Calculations using ab initio methods predict a weak exchange interaction of radical centers through a singlet ground state of DPPTh with a small singlet-triplet splitting (ΔEST) of about 25 cm-1 (∼0.07 kcal mol-1). In turn, a strong ferromagnetic exchange interaction between the triplet state of DPPTh chromophore and nitronyl nitroxides (with J ∼ 250 cm-1) was predicted.

Aliphatic and Olefinic Fat Suppression in the Orbit Using Polarity-altered Spectral and Spatial Selective Acquisition (PASTA) with Opposed Phase.

Fatty acid composition of the orbit makes it challenging to achieve complete fat suppression during orbit MR imaging. Implementation of a fat suppression technique capable of suppressing signals from saturated (aliphatic) and unsaturated (olefinic or protons at double-bonded carbon sites) fat would improve the visualization of an optical nerve. Furthermore, the ability to semi-quantify the fractions of aliphatic and olefinic fat may potentially provide valuable information in assessing orbit pathology. A phantom study was conducted on various oil samples on a clinical 3 Tesla scanner. The imaging protocol included three 2D fast spin echo (FSE) sequences: in-phase, polarity-altered spectral and spatial selective acquisition (PASTA), and a combination of PASTA with opposed phase in olefinic and aliphatic chemical shift. The results were validated against high-resolution 11.7T NMR and compared with images acquired with spectral attenuated inversion recovery (SPAIR) and chemical shift selective (CHESS) fat suppression techniques. In-vivo data were acquired on eight healthy subjects and were compared with the prior histological studies. PASTA with opposed phase achieved complete suppression of fat signals in the orbits and provided images of well-delineated optical nerves and muscles in all subjects. The olefinic fat fraction in the olive, walnut, and fish oil phantoms at 3T was found to be 5.0%, 11.2%, and 12.8%, respectively, whereas 11.7T NMR provides the following olefinic fat fractions: 6.0% for olive, 11.5% for walnut, and 12.6% for fish oils. For the in-vivo study, on average, olefinic fat accounted for 9.9% ± 3.8% of total fat while the aliphatic fat fraction was 90.1% ± 3.8%, in the normal orbits. We have introduced a new fat suppression technique using PASTA with opposed phase and applied it to human orbits. The purposed method achieves an excellent orbital fat suppression and the quantification of aliphatic and olefinic fat signals.

Identification of the Distal Dural Ring Using Three-dimensional Motion-sensitized Driven-equilibrium Prepared T1-weighted Fast Spin Echo Imaging: Application to Paraclinoid Aneurysms.

This study investigated the ability of three-dimentional motion-sensitized driven-equilibrium prepared T1-weighted fast spin echo (3D MSDE-FSE) imaging to identify distal dural rings (DDRs) and paraclinoid aneurysms (ParaC-ANs) and differentiate between intradural and extradural ParaC-ANs and compared it with that of established MR cisternography-based techniques. 3D MSDE-FSE images were acquired along with fast imaging employing steady state acquisition (FIESTA), and time-of-flight magnetic resonance angiography (TOF-MRA) on a 3T MRI system in 53 patients with unruptured and untreated ParaC-ANs. Two radiologists applied a 3-point scale to rate the clarity with which the DDR (53 left and 53 right) and ParaC-ANs (total of 55) were depicted in the 3D MSDE-FSE and FIESTA images. The clarity scores, which were determined by averaging the scores of the 2 assessors, on the 3D MSDE-FSE and FIESTA images were compared using the Wilcoxon signed-rank test. Furthermore, the same radiologists classified the ParaC-ANs as intradural, extradural, or transitional on 3D MSDE-FSE images. A third radiologist independently classified the ParaC-ANs as intradural, extradural, or transitional based on the FIESTA and MRA fusion images. The kappa coefficient was used to compare this classification with that based on 3D MSDE-FSE images. The Wilcoxon signed-rank test revealed no significant difference between 3D MSDE-FSE images and FIESTA images in the scores for the clarity of depiction of the DDRs (P = 0.119). However, the scores for the clarity of the depiction of the ParaC-ANs were significantly greater for the 3D MSDE-FSE images than for the FIESTA images (P < 0.001). The kappa coefficient for comparison of classification based on 3D MSDE-FSE images and FIESTA and MRA fusion images was 0.82. 3D MSDE-FSE imaging has the potential to differentiate between intradural and extradural ParaC-ANs by directly recognizing the DDR.

Impact of deep learning-based reconstruction and anti-peristaltic agent on the image quality and diagnostic performance of magnetic resonance enterography comparing single breath-hold single-shot fast spin echo with and without anti-peristaltic agent.

While anti-peristaltic agents are beneficial for high quality magnetic resonance enterography (MRE), their use is constrained by potential side effects and increased examination complexity. We explored the potential of deep learning-based reconstruction (DLR) to compensate for the absence of anti-peristaltic agent, improve image quality and reduce artifact. This study aimed to evaluate the need for an anti-peristaltic agent in single breath-hold single-shot fast spin-echo (SSFSE) MRE and compare the image quality and artifacts between conventional reconstruction (CR) and DLR. We included 45 patients who underwent MRE for Crohn's disease between October 2021 and September 2022. Coronal SSFSE images without fat saturation were acquired before and after anti-peristaltic agent administration. Four sets of data were generated: SSFSE CR with and without an anti-peristaltic agent (CR-A and CR-NA, respectively) and SSFSE DLR with and without an anti-peristaltic agent (DLR-A and DLR-NA, respectively). Two radiologists independently reviewed the images for overall quality and artifacts, and compared the three images with DLR-A. The degree of distension and inflammatory parameters were scored on a 5-point scale in the jejunum and ileum, respectively. Signal-to-noise ratio (SNR) levels were calculated in superior mesenteric artery (SMA) and iliac bifurcation level. In terms of overall quality, DLR-NA demonstrated no significant difference compared to DLR-A, whereas CR-NA and CR-A demonstrated significant differences (P<0.05, both readers). Regarding overall artifacts, reader 1 rated DLR-A slightly better than DLR-NA in four cases and rated them as identical in 41 cases (P=0.046), whereas reader 2 demonstrated no difference. Bowel distension was significantly different in the jejunum (Reader 1: P=0.046; Reader 2: P=0.008) but not in the ileum. Agreements between the images (Reader 1: ĸ=0.73-1.00; Reader 2: ĸ=1.00) and readers (ĸ=0.66 for all comparisons) on inflammation were considered good to excellent. The sensitivity, specificity, and accuracy in diagnosing inflammation in the terminal ileum were the same among DLR-NA, DLR-A, CR-NA and CR-A (94.42%, 81.83%, and 89.69 %; and 83.33%, 90.91%, and 86.21% for Readers 1 and 2, respectively). In both SMA and iliac bifurcation levels, SNR of DLR images exhibited no significant differences. CR images showed significantly lower SNR compared with DLR images (P<0.001). SSFSE without anti-peristaltic agents demonstrated nearly equivalent quality to that with anti-peristaltic agents. Omitting anti-peristaltic agents before SSFSE and adding DLR could improve the scanning outcomes and reduce time.

Structural and Dynamical Insights of Cu-Coordinated Cellulose Nanofibers for Li+ Battery by NMR Spectroscopy

In the quest of novel sustainable research to meet the global surge of clean energy demand, cellulose nanofibers (CNF) derived from natural wood materials offer exceptional properties for safe, cost-effective, efficient Li+ batteries. A new strategy has been established via introducing Cu2+ into the CNF to achieve a greater mobility of Li+, where Cu2+ opens up one-dimensional nanofibrils and creates molecular channels.1 Various experimental methods and molecular dynamic simulations have been used to characterize these materials. In this context, Nuclear Magnetic Resonance (NMR), a highly sensitive technique plays a significant role in providing new insights into the structure and dynamics of Li-Cu-CNF materials. In collaboration with Prof. Liangbing Hu, University of Maryland, current research focusses on studying highly conductive Li-Cu-CNF materials prepared with different Li-salt via different synthetic approaches in the ARPA-E project. Fast magic angle spinning (MAS) detecting 1H helps in estimating the residual solvent/H2O present in Li-Cu-CNF materials, which is crucial to determine the Li+ transport mechanism. Pulsed Field Gradient (PFG) NMR has been used to measure the diffusivity of Li+ and anion and to estimate the Li+ transference number (t Li+). We found that the estimated t Li+ of studied Li-Cu-CNF materials is much greater as compared to the other polymer-based electrolytes. Additionally, the anisotropic diffusion of Li+ and anion in aligned cellulose wood materials have been well-established through PFG NMR. Lastly, the local structure of cellulose fibers and their spatial interactions with ionic species are probed through multi-dimensional (1D and 2D) solid state NMR detecting 1H, 7Li, 19F, 13C nuclei. Reference. Yang, Q. Wu, W. Xie, X. Zhang, A. Brozena, J. Zheng, M. N. Garaga, B. H. Ko, Y. Mao, S. He, Y. Gao, P. Wang, M. Tyagi, F. Jiao, R. Briber, P. Albertus, C. Wang, S. Greenbaum, Y.-Y. Hu, A. Isogai, M. Winter, K. Xu, Y. Qi, and L. Hu, Copper-coordinated cellulose ion conductors for solid-state batteries. Nature (2021) 598, 590–596.

Functional MRI assessment of the lungs in fetuses that deliver very Preterm: An MRI pilot study

ObjectivesTo compare mean pulmonary T2* values and pulmonary volumes in fetuses that subsequently spontaneously delivered before 32 weeks with a control cohort with comparable gestational ages and to assess the value of mean pulmonary T2* as a predictor of preterm birth < 32 weeks’ gestation. MethodsMRI datasets scanned at similar gestational ages were selected from fetuses who spontaneously delivered < 32 weeks of gestation and a control group who subsequently delivered at term with no complications. All women underwent a fetal MRI on a 3 T MRI imaging system. Sequences included T2-weighted single shot fast spin echo and T2* sequences, using gradient echo single shot echo planar sequencing of the fetal thorax. Motion correction was performed using slice-to-volume reconstruction and T2* maps generated using in-house pipelines. Lungs were manually segmented and volumes and mean T2* values calculated for both lungs combined and left and right lung separately. Linear regression was used to compare values between the preterm and control cohorts accounting for the effects of gestation. Receiver operating curves were generated for mean T2* values and pulmonary volume as predictors of preterm birth < 32 weeks’ gestation. ResultsDatasets from twenty-eight preterm and 74 control fetuses were suitable for analysis. MRI images were taken at similar fetal gestational ages (preterm cohort (mean ± SD) 24.9 ± 3.3 and control cohort (mean ± SD) 26.5 ± 3.0). Mean gestational age at delivery was 26.4 ± 3.3 for the preterm group and 39.9 ± 1.3 for the control group. Mean pulmonary T2* values remained constant with increasing gestational age while pulmonary volumes increased. Both T2* and pulmonary volumes were lower in the preterm group than in the control group for all parameters (both combined, left, and right lung (p < 0.001 in all cases). Adjusted for gestational age, pulmonary volumes and mean T2* values were good predictors of premature delivery in fetuses < 32 weeks (area under the curve of 0.828 and 0.754 respectively). ConclusionThese findings indicate that mean pulmonary T2* values and volumes were lower in fetuses that subsequently delivered very preterm. This may suggest potentially altered oxygenation and indicate that pulmonary morbidity associated with prematurity has an antenatal antecedent. Future work should explore these results correlating antenatal findings with long term pulmonary outcomes.