We describe a robust screening technique that correlates the surface area of metal-organic frameworks to the proton T2 relaxation behavior of imbibed solvent at low field (13 MHz). In frameworks with small pore sizes (<1 nm) or strong solvent-framework interactions, diffusional exchange between the pore-confined and inter-particle solvent populations remains slow compared to the T2 of the pore-confined solvent, allowing for a direct porosity analysis of the T2 spectrum obtained from Laplace inversions. Increases in framework pore-size (>1 nm) lead to corresponding increases in the rate of solvent exchange, as confirmed by T2 relaxation exchange (REXSY) experiments; increases in the pore size also increases the T2 of the pore-confined solvent. The combination of these two effects results in comparable rates of relaxation and exchange, which precludes the direct analysis of Laplace inversions. Thus, two- and three-site kinetics models were applied to extract porosity from relaxation decays, thereby improving the utility of the porosity screening tool.

Molecular simulations and NMR relaxometry experiments demonstrate that pure benzene or xylene confined in isoreticular metal-organic frameworks (IRMOFs) exhibit true vapor-liquid phase equilibria where the effective critical point may be reduced by tuning the structure of the MOF. Our results are consistent with vapor and liquid phases extending over many MOF unit cells. These results are counterintuitive since the MOF pore diameters are approximately the same length scale as the adsorbate molecules. As applications of these materials in catalysis, separations, and gas storage rely on the ability to tune the properties of adsorbed molecules, we anticipate that the ability to systematically control the critical point, thereby preparing spatially inhomogeneous local adsorbate densities, could add a new design tool for MOF applications.

Cardiovascular side effects of cancer therapeutics are the leading causes of morbidity and mortality in cancer survivors. Anthracyclines (AC) serve as the backbone of many anti-cancer treatment strategies, but dose-dependent myocardial injury limits their use. Cumulative AC exposure can disrupt the dynamic equilibrium of the myocardial microarchitecture while repeated injury and repair leads to myocyte loss, interstitial myocardial fibrosis, and impaired contractility. Although children are assumed to have greater myocardial plasticity, AC exposure at a younger age portends worse prognosis. In older patients, there is lower overall survival once they develop cardiovascular disease. Because aberrations in the myocardial architecture predispose the heart to a decline in function, early detection with sensitive imaging tools is crucial and the implications for resource utilization are substantial. As a comprehensive imaging modality, cardiac magnetic resonance (CMR) imaging is able to go beyond quantification of ejection fraction and myocardial deformation to characterize adaptive microstructural and microvascular changes that are important to myocardial tissue health. Herein, we describe CMR as an established translational imaging tool that can be used clinically to characterize AC-associated myocardial remodeling.

Background

Quantitative ventricular volumetry and function are important in the management of congenital heart disease (CHD). Ferumoxytol-enhanced (FE) 4D multiphase, steady state imaging with contrast enhancement (MUSIC) enables high-resolution, 3D cardiac phase-resolved magnetic resonance imaging (MRI) of the beating heart and extracardiac vessels in a single acquisition and without concerns about renal impairment. We aim to evaluate the semi-automatic quantification of ventricular volumetry and function of 4D MUSIC MRI using 2D and 3D software platforms.

Methods

This HIPAA-compliant and IRB-approved study prospectively recruited 50 children with CHD (3 days to 18 years) who underwent 4D MUSIC MRI at 3.0T between 2013-2017 for clinical indications. Each patient was either intubated in the neonatal intensive care unit (NICU) or underwent general anesthesia at MRI suite. For 2D analysis, we reformatted MUSIC images in Digital Imaging and Communications in Medicine (DICOM) format into ventricular short-axis slices with zero interslice gap. For 3D analysis, we imported DICOMs into a commercially available 3D software platform. Using semi-automatic thresholding, we quantified biventricular volume and ejection fraction (EF). We assessed the bias between MUSIC-derived 2D vs. 3D measurements and correlation between MUSIC vs. conventional 2D balanced steady-state free precession (bSSFP) cine images. We evaluated intra- and inter-observer agreement.

Results

There was a high degree of correlation between MUSIC-derived volumetric and functional measurements using 2D vs. 3D software (r=0.99, P<0.001). Volumes derived using 3D software platforms were larger than 2D by 0.2 to 2.0 mL/m² whereas EF measurements were higher by 1.2-3.0%. MUSIC volumetric and functional measures derived from 2D and 3D software platforms corresponded highly with those derived from multi-slice SSFP cine images (r=0.99, P<0.001). The mean difference in volume for reformatted 4D MUSIC relative to bSSFP cine was 1.5 to 3.9 mL/m². Intra- and inter-observer reliability was excellent.

Conclusions

Accurate and reliable ventricular volumetry and function can be derived from FE 4D MUSIC MRI studies using commercially available 2D and 3D software platforms. If fully validated in multicenter studies, the FE 4D-MUSIC pulse sequence may supercede conventional multislice 2D cine cardiovascular MRI acquisition protocols for functional evaluation of children with complex CHD.

Taking a relaxed approach: The NMR relaxation behavior of imbibed solvent has been used to estimate the surface area of a variety of microporous metal-organic frameworks and zeolites. This NMR technique is amenable to automation and can expedite the characterization of microporous materials by identifying any nonporous or low-surface-area structures. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.