Egbert Gedat

Pyridine-15N: A mobile NMR sensor for surface acidity and surface defects of mesoporous silica

The hydrogen bond interaction of pyridine with the silanol groups of the inner surfaces of MCM-41 and SBA-15 ordered mesoporous silica has been studied by a combination of solid-state NMR techniques. The pore diameters were varied between 3 and 4 nm for MCM-41 and between 7 and 9 nm for SBA-15. 1 H MAS experiments performed under magic angle spinning (MAS) conditions in the absence and the presence of pyridine-d 5 reveal that the large majority of silanol groups are located in the inner surfaces, isolated from each other but able to form hydrogen bonds with pyridine. On the other hand, low- and room-temperature 1 5 N CPMAS and MAS experiments (CP ≡ cross-polarization) performed on pyridine- 1 5 N show that at low concentrations all pyridine molecules are involved in hydrogen bonds with the surface silanol groups. In the presence of an excess of pyridine, a non-hydrogen-bonded pyridine phase is observed at 120 K in the slow hydrogen bond exchange regime and associates with an inner core phase. From these measurements, the number of pyridine molecules bound to the inner surfaces corresponding to the number of silanol groups could be determined to be n O H 3 nm - 2 for MCM-41 and 3.7 nm - 2 for SBA-15. At room temperature and low concentrations, the pyridine molecules jump rapidly between the hydrogen-bonded sites. In the presence of an excess of pyridine, the hydrogen-bonded binding sites are depleted as compared to low temperatures, leading to smaller apparent numbers n O H . Using a correlation established previously between the 1 5 N and 1 H chemical shifts and the NHO hydrogen bond geometries, as well as with the acidity of the proton donors, the distances in the pyridine-hydroxyl pairs were found to be about r H N = 1.68 A, r O H = 1.01 A, and r O N = 2.69 A. This geometry corresponds in the organic solid state to acids exhibiting in water a pK a of about 4. Roomtemperature 1 5 N experiments on static samples of pyridine- 1 5 N in MCM-41 at low coverage show a residual 1 5 N chemical shift anisotropy, indicating that the jumps of pyridine between different different silanol hydrogen bond sites is accompanied by an anisotropic reorientational diffusion. A quantitative analysis reveals that in this regime the rotation of pyridine around the molecular C 2 axis is suppressed even at room temperature, and that the angle between the Si-O axes and the OH axes of the isolated silanol groups is about 47°. These results are corroborated by 2 H NMR experiments performed on pyridine-4-d 1 . In contrast, in the case of SBA-15 with the larger pore diameters, the hydrogen bond jumps of pyridine are associated with an isotropic rotational diffusion, indicating a high degree of roughness of the inner surfaces. This finding is correlated with the finding by 2 9 Si CPMAS of a substantial amount of Si(OH) 2 groups in SBA-15. in contrast to the MCM-41 materials. The Si(OH) 2 groups are associated with surface defects, exhibiting not only silanol groups pointing into the pore center but also silanol groups pointing into other directions of space including the pore axes, leading to the isotropic surface diffusion. All results are used to develop molecular models for the inner surface structure of mesoporous silica which may be a basis for future simulations of the surfaces of mesoporous silica.

Prospective registration of human head magnetic resonance images for reproducible slice positioning using localizer images

To facilitate assessing brain tumor growth and progression of stroke lesions by reproducible slice positioning in human head magnetic resonance (MR) images, a method for prospective registration is proposed that adjusts the image slice position without moving the patient and with no additional scans.

Post-processing central k-space subtraction for high-resolution arterial peripheral MR angiography

Peripheral MR angiography requires high resolution and arterial contrast. Neither can be obtained simultaneously due to the short arterial phase of the contrast agent. To improve temporal resolution, keyhole imaging was developed, which combines high resolution and arterial k-spaces at the time of image acquisition. Here, a related approach is introduced for image post-processing in the Fourier domain. It is demonstrated that simple substitution of the central k-space with low-resolution data leads to severe distortion. Hence, a dedicated calculation scheme is necessary for composite k-space post-processing. A solution is presented for high-resolution arterial peripheral MR angiography that uses subtraction of venous intensities from the central high-resolution k-space. The calculations in the Fourier domain do not require interpolations between the different resolutions. High-resolution steady-state MR angiography, which exhibits contrast-enhanced arteries and veins at an isotropic resolution of 0.65 mm, and standard resolution arterial first-pass MR angiography were combined to obtain images with the resolution of the steady-state images and arterial contrast. Numerical simulations on software phantoms are presented. The operation of the method is demonstrated in five patients.

Hybride Multi-Resolutions k-Raum Nachbearbeitung für Gadofosveset-verstärkte hochaufgelöste arterielle periphere MR-Angiographie

Periphere MR-Angiographien mit hoher ortlicher Aufl osung und arteriellem Kontrast wurden mit einer vor kurzem vorgestellten Computer-Methode erzeugt. Steady-State und First-Pass MRAngiographien der Unterschenkel von 10 Patienten wurden zu hoch aufgel osten arteriellen MR-Angiographien kombiniert. Die Bildqualitat wurde sehr gut bewertet. Die Ergebnisse einer Befundung von Stenosen waren sehr nah an denen der Steady-State MR Angiographien, die den Standard darstellten.

Prospective registration of inter-examination MR images

The monitoring of the development of cerebral diseases such as stroke or brain tumors with MRI requires high-precision comparison of initial and follow-up images. Retrospective registration often produces artifacts, especially at boundariesbetween different tissue structures. However, by manipulating the gradients, MRI scanners offer the possibility of shifting and rotating image planes fast and without removing the patient. Two approaches for prospective registration were implemented and tested on phantoms and healthy volunteers. To speed up calculation, both registration algorithms used the three orthogonal two-dimensional localizer images that were acquired prior to each measurement. In the first approach, the image is projected onto one axis to determine the rotation between initial and follow-up examination. The second algorithm uses cross-correlation for rotational correction. Both algorithms maximize the cross-correlation for correction of the shifts. After 2-D registration in each orientation, the gradients of the tomograph are adapted according to the calculated transformation matrix. The results were evaluated with a 3-D rigid-body registration using Automated Image Registration. The cross-correlation method was found to be very robust, while the 1-D projection algorithm was sufficiently fast but registration results depended on the shape of the head.

15N-pyridine—a mobile NMR sensor for surface acidity and surface defects of mesoporous silica

experiments performed under magic angle spinning (MAS) conditions in the absence and the presence of pyridine-d5 reveal that the large majority of silanol groups are located in the inner surfaces, isolated from each other but able to form hydrogen bonds with pyridine. On the other hand, low- and room-temperature 15 N CPMAS and MAS experiments (CP cross-polarization) performed on pyridine- 15 N show that at low concentrations all pyridine molecules are involved in hydrogen bonds with the surface silanol groups. In the presence of an excess of pyridine, a non-hydrogen-bonded pyridine phase is observed at 120 K in the slow hydrogen bond exchange regime and associates with an inner core phase. From these measurements, the number of pyridine molecules bound to the inner surfaces corresponding to the number of silanol groups could be determined to be nOH 3n m -2 for MCM-41 and 3.7 nm -2 for SBA-15. At room temperature and low concentrations, the pyridine molecules jump rapidly between the hydrogen-bonded sites. In the presence of an excess of pyridine, the hydrogen-bonded binding sites are depleted as compared to low temperatures, leading to smaller apparent numbers nOH. Using a correlation established previously between the 15 N and 1 H chemical shifts and the NHO hydrogen bond geometries, as well as with the acidity of the proton donors, the distances in the pyridine-hydroxyl pairs were found to be about rHN ) 1.68 A,rOH ) 1.01 A, andrON ) 2.69 A. This geometry corresponds in the organic solid state to acids exhibiting in water a pKa of about 4. Roomtemperature 15 N experiments on static samples of pyridine- 15 N in MCM-41 at low coverage show a residual 15 N chemical shift anisotropy, indicating that the jumps of pyridine between different different silanol hydrogen bond sites is accompanied by an anisotropic reorientational diffusion. A quantitative analysis reveals that in this regime the rotation of pyridine around the molecular C2 axis is suppressed even at room temperature, and that the angle between the Si-O axes and the OH axes of the isolated silanol groups is about 47°. These results are corroborated by 2 H NMR experiments performed on pyridine-4-d1. In contrast, in the case of SBA-15 with the larger pore diameters, the hydrogen bond jumps of pyridine are associated with an isotropic rotational diffusion, indicating a high degree of roughness of the inner surfaces. This finding is correlated with the finding by 29 Si CPMAS of a substantial amount of Si(OH)2 groups in SBA-15, in contrast to the MCM-41 materials. The Si(OH)2 groups are associated with surface defects, exhibiting not only silanol groups pointing into the pore center but also silanol groups pointing into other directions of space including the pore axes, leading to the isotropic surface diffusion. All results are used to develop molecular models for the inner surface structure of mesoporous silica which may be a basis for future simulations of the surfaces of mesoporous silica.