Epidemiologie und Verlauf der Migräne bei Patienten mit Multipler Sklerose

In dieser Studie wurde erstmalig unter Zuhilfenahme der Kriterien der International Headache Society eine Evaluation der Lebenszeit-Prävalenz von Migräne bei MS durchgeführt. Im Rahmen dieser Fall-Kontroll-Studie wurden 512 Patienten mit nach Poser-Kriterien diagnostizierter MS und 512 alters- und geschlechtsgematchte Personen eingeschlossen. Bei 71 der MS-Patienten (13,9%) konnte die Diagnose Migräne gestellt werden, während in der Kontrollgruppe bei 98 Patienten (19,1%) diese Diagnose zutraf. Dieser Unterschied ist statistisch signifikant (p=0,023). Bei der schubförmigen Verlaufsform der MS ließ sich bei 37 Patienten (18,9%), bei der primär chronischen und der sekundär chronischen Verlaufsform bei insgesamt 13 Patienten (9,6%) eine Migräne diagnostizieren. Dieser Unterschied ist ebenfalls statistisch signifikant (p=0,02). Daraus lässt sich folgern, dass für den Unterschied zwischen beiden Gruppen primär die niedrige Prävalenz bei den chronischen Verlaufsformen der MS verantwortlich ist

Silica-magnesium-titanium Ziegler-Natta catalysts. Part 1: Structure of the pre-catalyst at a molecular level

In this paper, which is the first part of a more extended work, we elucidate the molecular level structure of a highly active SiO2-supported Ziegler-Natta precatalyst obtained by reacting a dehydroxylated silica and a solution of an organomagnesium compound with TiCl4. The synergetic combination of Ti K-edge and Ti L3-edge X-ray Absorption spectroscopy (XAS) and diffuse reflectance UV–Vis spectroscopies, complemented by Density Functional Theory (DFT) simulations, indicate that small TiCl3 clusters similar to β-TiCl3 coexist with isolated monomeric Ti(IV) species. Ti K-edge Extended X-ray Absorption Fine Structure (EXAFS) Spectroscopy allows the quantification of these two phases and demonstrates that the Ti(IV) sites are 6-fold coordinated (either by six chlorine ligands or by five chlorine and one oxygen ligands), but highly distorted, similar to what is modelled for TiCl4-capped MgCl2 nanoplatelets. Finally, IR spectroscopy suggests that the MgCl2 phase has a molecular character (Far-IR) and that the only accessible Mg2+ sites are uncoordinated cations acting as Lewis acid sites (IR of CO adsorbed at 100 K). Based on these experimental findings, we propose the co-existence in the precatalyst of small TiCl3 clusters and of mixed oxo-chloride magnesium-titanium structures deposited at the silica surface. The evolution of the precatalyst in the presence of the activator and of the monomer is discussed in the second part of this work

Teaching ultrasound in a curricular course according to certified EFSUMB standards during undergraduate medical education: a prospective study

Background: As a non-invasive and readily available diagnostic tool, ultrasound is one of the most important imaging techniques in medicine. Ultrasound is usually trained during residency preferable according to German Society of Ultrasound in Medicine (DEGUM) standards. Our curriculum calls for undergraduate training in ultrasound of medical students in their 4th year of undergraduate education. An explorative pilot study evaluated the acceptance of this teaching method, and compared it to other practical activities in medical education at Muenster University. Methods: 240 medical students in their 4th year of undergraduate medical education participated in the training and completed a pre- and post-questionnaire for self-assessment of technical knowledge, self-assurance of the procedure, and motivation in performing ultrasound using a Likert scale. Moreover, students were asked about their interest in pursuing a career in internal medicine. To compare this training to other educational activities a standardized online evaluation tool was used. A direct observation of procedural skills assessment (DOPS) for the first time applied on ultrasound aimed to independently assess the success of our teaching method. Results: There was a significant increase in technical knowledge and self-assurance (p < 0.001) of the students’ self-assessments. The clinical relevance and self-motivation of the teaching were evaluated positively. The students’ DOPS results demonstrated proficiency in the understanding of anatomic structures shown in ultrasonographic images, including terminology, machine settings, and transducer frequencies. Conclusions: Training ultrasound according to certified DEGUM standards was successful and should be offered in undergraduate medical education. The evaluation of the course affirmed the necessity, quality and clinical relevance of the course with a top ranking score of hands-on training courses within the educational activities of the Medical Faculty of Muenster.<br

Silica-magnesium-titanium Ziegler–Natta catalysts. Part II. Properties of the active sites and fragmentation behaviour

In this work, which follows Part I that is dedicated to the precatalyst, we investigate the electronic properties and the accessibility of the Ti active sites in a highly active silica-supported Ziegler–Natta catalyst for industrial polyethylene production, applying a multi-scale, multi-technique approach. Complementary electronic spectroscopies (i.e. Ti K-edge XANES, Ti L2,3-edge NEXAFS and DR UV–Vis-NIR) reveal the coexistence of several titanium phases, whose relative amount depends on the concentration of the alkyl aluminum activator. In addition to β-TiCl3-like clusters and monomeric Ti(IV) sites, which are already present in the precatalyst, isolated Ti(III) sites and α-TiCl3-like clusters are formed in the presence of the activator. Two families of alkylated Ti(III) sites characterized by a different electron density are detected by IR spectroscopy of adsorbed CO, and two types of Ti-acyl species are formed upon CO insertion into the Ti-alkyl bond, characterized by a different extent of η2-coordination. The whole set of data suggests that TiCl3 clusters are preferentially formed at the exterior of the catalyst particles, likely as a consequence of Ti(III) mobility in the presence of strong Lewis acids, in most cases hampering the spectroscopic detection of isolated Ti(III) sites. In contrast, only monomeric Ti(III) sites are formed at the interior of the catalyst particles, characterized by a high electron density evocative of the presence of electron donors in the close proximity (e.g. aluminum alkoxide by-products). These sites are less accessible because of diffusion limitations, and only become visible by surface-sensitive spectroscopic methods (such as Ti L2,3-edge TEY-NEXAFS) upon the fragmentation of the catalyst particles

Advancing the Compositional Analysis of Olefin Polymerization Catalysts with High-Throughput Fluorescence Microscopy

To optimize the performance of supported olefin polymerization catalysts, novel methodologies are required to evaluate the composition, structure, and morphology of both pristine and prepolymerized samples in a resource-efficient, high-throughput manner. Here, we report on a unique combination of laboratory-based confocal fluorescence microscopy and advanced image processing that allowed us to quantitatively assess support fragmentation in a large number of autofluorescent metallocene-based catalyst particles. Using this approach, significant inter- and intraparticle heterogeneities were detected and quantified in a representative number of prepolymerized catalyst particles (2D: ≥135, 3D: 40). The heterogeneity that was observed over several stages of slurry-phase ethylene polymerization (10 bar) is primarily attributed to the catalyst particles' diverse support structures and to the inhomogeneities in the metallocene distribution. From a mechanistic point of view, the 2D and 3D analyses revealed extensive contributions from a layer-by-layer fragmentation mechanism in synergy with a less pronounced sectioning mechanism. A significant number of catalyst particles were also found to display limited support fragmentation at the onset of the reaction (i.e., at lower polymer yields). This delay in activity or "dormancy" is believed to contribute to a broadening of the particle size distribution during the early stages of polymerization. 2D and 3D catalyst screening via confocal fluorescence microscopy represents an accessible and fast approach to characterize the structure of heterogeneous catalysts and assess the distribution of their fluorescent components and reaction products. The automation of both image segmentation and postprocessing with machine learning can yield a powerful diagnostic tool for future research as well as quality control on industrial catalysts

Elucidating the Sectioning Fragmentation Mechanism in Silica-Supported Olefin Polymerization Catalysts with Laboratory-Based X-Ray and Electron Microscopy

Strict morphological control over growing polymer particles is an indispensable requirement in many catalytic olefin polymerization processes. In catalysts with mechanically stronger supports, e. g., polymerization-grade silicas, the emergence of extensive cracks via the sectioning fragmentation mechanism requires severe stress build-up in the polymerizing catalyst particle. Here, we report on three factors that influence the degree of sectioning in silica-supported olefin polymerization catalysts. Laboratory-based X-ray nano-computed tomography (nanoCT) and focused ion beam-scanning electron microscopy (FIB-SEM) were employed to study catalyst particle morphology and crack propagation in two showcase catalyst systems, i.e., a zirconocene-based catalyst (i.e., Zr/MAO/SiO2, with Zr=2,2’-biphenylene-bis-2-indenyl zirconium dichloride and MAO=methylaluminoxane) and a Ziegler-Natta catalyst (i.e., TiCl4/MgCl2/SiO2), during slurry-phase ethylene polymerization. The absence of extensive macropores in some of the catalysts’ larger constituent silica granulates, a sufficient accessibility of the catalyst particle interior at reaction onset, and a high initial polymerization rate were found to favor the occurrence of the sectioning pathway at different length scales. While sectioning is beneficial for reducing diffusion limitations, its appearance in mechanically stronger catalyst supports can indicate a suboptimal support structure or unfavourable reaction conditions

Numerical convergence of the block-maxima approach to the Generalized Extreme Value distribution

In this paper we perform an analytical and numerical study of Extreme Value distributions in discrete dynamical systems. In this setting, recent works have shown how to get a statistics of extremes in agreement with the classical Extreme Value Theory. We pursue these investigations by giving analytical expressions of Extreme Value distribution parameters for maps that have an absolutely continuous invariant measure. We compare these analytical results with numerical experiments in which we study the convergence to limiting distributions using the so called block-maxima approach, pointing out in which cases we obtain robust estimation of parameters. In regular maps for which mixing properties do not hold, we show that the fitting procedure to the classical Extreme Value Distribution fails, as expected. However, we obtain an empirical distribution that can be explained starting from a different observable function for which Nicolis et al. [2006] have found analytical results.Comment: 34 pages, 7 figures; Journal of Statistical Physics 201

Correlating the Morphological Evolution of Individual Catalyst Particles to the Kinetic Behavior of Metallocene-Based Ethylene Polymerization Catalysts

Kinetics-based differences in the early stage fragmentation of two structurally analogous silica-supported hafnocene- and zirconocene-based catalysts were observed during gas-phase ethylene polymerization at low pressures. A combination of focused ion beam-scanning electron microscopy (FIB-SEM) and nanoscale infrared photoinduced force microscopy (IR PiFM) revealed notable differences in the distribution of the support, polymer, and composite phases between the two catalyst materials. By means of time-resolved probe molecule infrared spectroscopy, correlations between this divergence in morphology and the kinetic behavior of the catalysts' active sites were established. The rate of polymer formation, a property that is inherently related to a catalyst's kinetics and the applied reaction conditions, ultimately governs mass transfer and thus the degree of homogeneity achieved during support fragmentation. In the absence of strong mass transfer limitations, a layer-by-layer mechanism dominates at the level of the individual catalyst support domains under the given experimental conditions