Structural factors controlling the spin-spin exchange coupling: EPR spectroscopic studies of highly asymmetric trityl-nitroxide biradicals

Highly asymmetric exchange-coupled biradicals, like the trityl-nitroxides (TN), possess particular magnetic properties opening new possibilities for their application in biophysical, physicochemical and biological studies. In the present work, we investigated the effect of the linker length on the spin-spin coupling interaction in TN biradicals using the newly synthesized biradicals CT02-GT, CT02-AT, CT02-VT and CT02-PPT as well as the previously reported biradicals TNN14 and TN1. Results show that the magnitude of the spin-spin interaction (J) can be easily tuned from ~ 4 G (conformer 1 in CT02-PPT) to over 1200 G (in TNN14) using various linkers separating the two radical moieties and with varying temperature. Computer simulation of EPR spectra was carried out to directly estimate J values of the TN biradicals. In addition to the spin-spin coupling interaction of TN biradicals, their g, hyperfine splitting and zero-field splitting interactions were explored at low temperature (220 K). Our present study clearly shows that the spin-spin interaction variation as a function of linker distance and temperature provides an effective strategy to develop new TN biradicals which can find wide applications in relevant fields

Mesoporous Silica Nanoparticles Loaded with Surfactant: Low Temperature Magic Angle Spinning 13C and 29Si NMR Enhanced by Dynamic Nuclear Polarization

We show that dynamic nuclear polarization (DNP) can be used to enhance NMR signals of13C and 29Si nuclei located in mesoporous organic/inorganic hybrid materials, at several hundreds of nanometers from stable radicals (TOTAPOL) trapped in the surrounding frozen disordered water. The approach is demonstrated using mesoporous silica nanoparticles (MSN), functionalized with 3-(N-phenylureido)propyl (PUP) groups, filled with the surfactant cetyltrimethylammonium bromide (CTAB). The DNP-enhanced proton magnetization is transported into the mesopores via 1H–1H spin diffusion and transferred to rare spins by cross-polarization, yielding signal enhancements εon/off of around 8. When the CTAB molecules are extracted, so that the radicals can enter the mesopores, the enhancements increase to εon/off ≈ 30 for both nuclei. A quantitative analysis of the signal enhancements in MSN with and without surfactant is based on a one-dimensional proton spin diffusion model. The effect of solvent deuteration is also investigated

Macroscopic nuclear spin diffusion constants of rotating polycrystalline solids from first-principles simulation

A method for quantitatively calculating nuclear spin diffusion constants directly from crystal structures is introduced. This approach uses the first-principles low-order correlations in Liouville space (LCL) method to simulate spin diffusion in a box, starting from atomic geometry and including both magic-angle spinning (MAS) and powder averaging. The LCL simulations are fit to the 3D diffusion equation to extract quantitative nuclear spin diffusion constants. We demonstrate this method for the case of H-1 spin diffusion in ice and L-histidine, obtaining diffusion constants that are consistent with literature values for H-1 spin diffusion in polymers and that follow the expected trends with respect to magic-angle spinning rate and the density of nuclear spins. In addition, we show that this method can be used to model C-13 spin diffusion in diamond and therefore has the potential to provide insight into applications such as the transport of polarization in non-protonated systems. (C) 2015 Elsevier Inc. All rights reserved

COPALZ: A Computational Model of Pathological Appraisal Biases for an Interactive Virtual Alzheimer Patient

International audienc

COPALZ: A Computational Model of Pathological Appraisal Biases for an Interactive Virtual Alzheimer Patient

International audienc

COPALZ: A Computational Model of Pathological Appraisal Biases for an Interactive Virtual Alzheimer Patient

International audienc