Magnetic Resonance Pore Imaging, a new tool for porous media research

<p>Porous media are highly prevalent in nature and span a wide range of systems including biological tissues, chemical catalysts or rocks in oil reservoirs. Imaging of the structure of the constituent pores is therefore highly desirable for life sciences and technological applications. This thesis presents the new development and application of a nuclear magnetic resonance (NMR) technique to acquire high resolution images of closed pores. The technique is a further development of diffusive-diffraction Pulsed Gradient Spin Echo (PGSE) NMR, which has been shown to image the pore auto-correlation function averaged over all pores. Until recently it was conventional wisdom that diffusive-diffraction PGSE NMR can only measure the magnitude of the form factor, due to its similarity to diffraction techniques such as x-ray and neutron scattering. In diffraction applications the loss of phase information is commonly referred to as the “phase problem”, which prevents the reconstruction of images of the pore space by inverse Fourier transform. My work is based on a recently suggested modification of the diffusive-diffraction PGSE NMR method, which creates a hybrid between Magnetic Resonance Imaging (MRI) and PGSE NMR. Therefore, we call this approach Magnetic Resonance Pore Imaging (MRPI). We provide experimental confirmation that MRPI does indeed measure the diffractive signal including its phase and thus the “phase problem” is lifted. We suggest a two-dimensional version of MRPI and obtain two-dimensional average pore images of cylindrical and triangular pores with an unprecedented resolution as compared to state of the art MRI. Utilizing a laser machined phantom sample we present images of microscopic pores with triangular shape even in the presence of wall relaxation effects. We therefore show that MRPI is able to reconstruct the pore shape without any prior knowledge or assumption about the porous system under study. Furthermore, we demonstrate that the MRPI approach integrates seamlessly with known MRI concepts. For instance we introduce “MRPI mapping” which acquires the MRPI signal for each pixel in an MRI image. This enables one to resolve pore sizes and shapes spatially, thus expanding the application of MRPI to samples with heterogeneous distributions of pores.</p>

Magnetic Resonance Pore Imaging, a new tool for porous media research

<p>Porous media are highly prevalent in nature and span a wide range of systems including biological tissues, chemical catalysts or rocks in oil reservoirs. Imaging of the structure of the constituent pores is therefore highly desirable for life sciences and technological applications. This thesis presents the new development and application of a nuclear magnetic resonance (NMR) technique to acquire high resolution images of closed pores. The technique is a further development of diffusive-diffraction Pulsed Gradient Spin Echo (PGSE) NMR, which has been shown to image the pore auto-correlation function averaged over all pores. Until recently it was conventional wisdom that diffusive-diffraction PGSE NMR can only measure the magnitude of the form factor, due to its similarity to diffraction techniques such as x-ray and neutron scattering. In diffraction applications the loss of phase information is commonly referred to as the “phase problem”, which prevents the reconstruction of images of the pore space by inverse Fourier transform. My work is based on a recently suggested modification of the diffusive-diffraction PGSE NMR method, which creates a hybrid between Magnetic Resonance Imaging (MRI) and PGSE NMR. Therefore, we call this approach Magnetic Resonance Pore Imaging (MRPI). We provide experimental confirmation that MRPI does indeed measure the diffractive signal including its phase and thus the “phase problem” is lifted. We suggest a two-dimensional version of MRPI and obtain two-dimensional average pore images of cylindrical and triangular pores with an unprecedented resolution as compared to state of the art MRI. Utilizing a laser machined phantom sample we present images of microscopic pores with triangular shape even in the presence of wall relaxation effects. We therefore show that MRPI is able to reconstruct the pore shape without any prior knowledge or assumption about the porous system under study. Furthermore, we demonstrate that the MRPI approach integrates seamlessly with known MRI concepts. For instance we introduce “MRPI mapping” which acquires the MRPI signal for each pixel in an MRI image. This enables one to resolve pore sizes and shapes spatially, thus expanding the application of MRPI to samples with heterogeneous distributions of pores.</p>

The Palladium(II) Complex of Aβ4−16 as Suitable Model for Structural Studies of Biorelevant Copper(II) Complexes of N-Truncated Beta-Amyloids

The Aβ4−42 peptide is a major beta-amyloid species in the human brain, forming toxic aggregates related to Alzheimer’s Disease. It also strongly chelates Cu(II) at the N-terminal Phe-Arg-His ATCUN motif, as demonstrated in Aβ4−16 and Aβ4−9 model peptides. The resulting complex resists ROS generation and exchange processes and may help protect synapses from copper-related oxidative damage. Structural characterization of Cu(II)Aβ4−x complexes by NMR would help elucidate their biological function, but is precluded by Cu(II) paramagneticism. Instead we used an isostructural diamagnetic Pd(II)-Aβ4−16 complex as a model. To avoid a kinetic trapping of Pd(II) in an inappropriate transient structure, we designed an appropriate pH-dependent synthetic procedure for ATCUN Pd(II)Aβ4−16, controlled by CD, fluorescence and ESI-MS. Its assignments and structure at pH 6.5 were obtained by TOCSY, NOESY, ROESY, 1H-13C HSQC and 1H-15N HSQC NMR experiments, for natural abundance 13C and 15N isotopes, aided by corresponding experiments for Pd(II)-Phe-Arg-His. The square-planar Pd(II)-ATCUN coordination was confirmed, with the rest of the peptide mostly unstructured. The diffusion rates of Aβ4−16, Pd(II)-Aβ4−16 and their mixture determined using PGSE-NMR experiment suggested that the Pd(II) complex forms a supramolecular assembly with the apopeptide. These results confirm that Pd(II) substitution enables NMR studies of structural aspects of Cu(II)-Aβ complexes.

Relationship between Li+ diffusion and ion conduction for single-crystal and powder garnet-type electrolytes studied by 7Li PGSE NMR spectroscopy

Li-diffusion constants of single-crystal and powder garnets were determined and plotted versus ionic conductivity. Estimated NE carrier numbers were larger than atomic Li numbers for metal containing garnets and insensitive to temperature.

Synthesis and Characterization of Isosorbide-Based Polyurethanes Exhibiting Low Cytotoxicity Towards HaCaT Human Skin Cells

The synthesis of four samples of new polyurethanes was evaluated by changing the ratio of the diol monomers used, poly(propylene glycol) (PPG) and D-isosorbide, in the presence of aliphatic isocyanates such as the isophorone diisocyanate (IPDI) and 4,4′-methylenebis(cyclohexyl isocyanate) (HMDI). The thermal properties of the four polymers obtained were determined by DSC, exhibiting Tg values in the range 55–70 °C, and their molecular structure characterized by FTIR, 1H, and 13C NMR spectroscopies. The diffusion coefficients of these polymers in solution were measured by the Pulse Gradient Spin Echo (PGSE) NMR method, enabling the calculation of the corresponding hydrodynamic radii in diluted solution (1.62–2.65 nm). The molecular weights were determined by GPC/SEC and compared with the values determined by a quantitative 13C NMR analysis. Finally, the biocompatibility of the polyurethanes was assessed using the HaCaT keratinocyte cell line by the MTT reduction assay method showing values superior to 70% cell viability.