Abstract:The longitudinal proton relaxation rates R(1) of water diffusing inside synthetic aluminium silicate imogolite nanotubes are measured by fast field-cycling NMR for frequencies between 0.02 and 35 MHz at 25, 37 and 50 degrees C. We give analytical expressions of the dominant intermolecular dipolar spin-spin contribution to R(1) and to the transverse relaxation rate R(2). A remarkable variation of R(1) by more than two orders of magnitude is observed and shown to be close to the theoretical law, inversely propor… Show more
“…However, the signature of diffusion inside a nanotube, i.e., 1-dimensional diffusion, is a power law in the Larmor frequency and not the observed dependence on the logarithm of the Larmor frequency. 35 Thus, we must conclude that the effect of 1-dimensional water diffusion inside the nanotubes does not make a dominant contribution to the observed water proton SLR profile. For the GNTs, if the Gd 3+ ions were well inside the nanotubes, one would expect to see the effects of 1-dimensional diffusion reflected strongly in the relaxation dispersion profile.…”
The Gadonanotubes (GNTs) are the highest-performing T 1 -weighted MRI contrast agent material known with a relaxivity of ∼160 mM −1 s −1 per Gd 3+ ion at 1.5 T. In this work, the contribution of carbon-based free radicals at defect sites on the sidewalls of the ultra-short carbon nanotube (US-tube) component of the GNTs to the T 1 relaxation time has been investigated by Nuclear Magnetic Resonance Dispersion (NMRD) and Electron Paramagnetic Resonance (EPR) studies. The NMRD results indicate that carbon-based radicals of the US-tube structure substantially shorten water proton spin-lattice relaxation times at low frequencies (< 1 MHz) and that the high water proton relaxation rate for the GNTs at these fields does not result from the Gd 3+ ion alone. Furthermore, a computational study suggests that the defect sites of the US-tube structure increase nanotube strain and create new interband electronic states. While the presence of Gd 3+ ions at the defect sites for the GNTs do not induce new electronic states, they do introduce a shift in the Fermi level to higher energy (0.4 eV).
“…However, the signature of diffusion inside a nanotube, i.e., 1-dimensional diffusion, is a power law in the Larmor frequency and not the observed dependence on the logarithm of the Larmor frequency. 35 Thus, we must conclude that the effect of 1-dimensional water diffusion inside the nanotubes does not make a dominant contribution to the observed water proton SLR profile. For the GNTs, if the Gd 3+ ions were well inside the nanotubes, one would expect to see the effects of 1-dimensional diffusion reflected strongly in the relaxation dispersion profile.…”
The Gadonanotubes (GNTs) are the highest-performing T 1 -weighted MRI contrast agent material known with a relaxivity of ∼160 mM −1 s −1 per Gd 3+ ion at 1.5 T. In this work, the contribution of carbon-based free radicals at defect sites on the sidewalls of the ultra-short carbon nanotube (US-tube) component of the GNTs to the T 1 relaxation time has been investigated by Nuclear Magnetic Resonance Dispersion (NMRD) and Electron Paramagnetic Resonance (EPR) studies. The NMRD results indicate that carbon-based radicals of the US-tube structure substantially shorten water proton spin-lattice relaxation times at low frequencies (< 1 MHz) and that the high water proton relaxation rate for the GNTs at these fields does not result from the Gd 3+ ion alone. Furthermore, a computational study suggests that the defect sites of the US-tube structure increase nanotube strain and create new interband electronic states. While the presence of Gd 3+ ions at the defect sites for the GNTs do not induce new electronic states, they do introduce a shift in the Fermi level to higher energy (0.4 eV).
“…This implies that one is able to probe, in a single experiment, dynamical processes on the time scales from ms tons [ 10 , 12 , 13 ]. Moreover, the shape of the relaxation dispersion profile (spin–lattice relaxation rate versus the resonance frequency) unambiguously reveals the mechanism of motion [ 14 , 15 , 16 , 17 ], also allowing to differentiate between the translation diffusion pathways of different dimensionality: 3D, 2D, 1D [ 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 ]. Relaxation rates are given as linear combinations of spectral density functions being Fourier transforms of the corresponding time correlation functions, characterising the motion associated with the relaxation process [ 3 , 4 , 5 , 6 , 7 ].…”
1H and 19F spin–lattice relaxation studies for 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide in bulk and mesoporous MCM-41 silica matrix confinement were performed under varying temperatures in a broad range of magnetic fields, corresponding to 1H resonance frequency from 5Hz to 30MHz.A thorough analysis of the relaxation data revealed a three-dimensional translation diffusion of the ions in the bulk liquid and two-dimensional diffusion in the vicinity of the confining walls in the confinement. Parameters describing the translation dynamics were determined and compared. The rotational motion of both kinds of ions in the confinement was described by two correlation times that might be attributed to anisotropic reorientation of these species.
“…[28] For instance, almost ideal 1D diffusion has been inferred from the profile of hydrated imogolite nanotubes. [29] In recent work [20] we have rationalised the r 1 profiles of the lipid 1 H fraction in diamagnetic liposomes. Collective membrane motions, which were treated as quasi-spherical fluctuations, were found to dominate the relaxation at low frequency.…”
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