Project description:The forced migration process of German-speaking neurologists and psychiatrists under the Nazis during the 1930s and 40s is often preoccupied solely with "successful" concepts and therapeutic approaches. The case of German-Canadian neurologist Karl Stern (1906-1975) is very instructive, however, since the process of forced migration, for him, proved to be a transitionary process from his former cutting edge work in neuropathology and holist neurology in Germany to clinical psychiatry and the development of the new discipline of geriatric medicine in Canada.
Project description:We present an experimental study on detachment characteristics of hydrogen bubbles during electrolysis. Using a transparent (Pt or Ni) electrode enables us to directly observe the bubble contact line and bubble size. Based on these quantities we determine other parameters such as the contact angle and volume through solutions of the Young-Laplace equation. We observe bubbles without ("pinned bubbles") and with ("spreading bubbles") contact line spreading and find that the latter mode becomes more prevalent if the concentration of HClO4 is ≥0.1 M. The departure radius for spreading bubbles is found to drastically exceed the value predicted by the well-known formula of W. Fritz [Phys. Z. 1935, 36, 379-384] for this case. We show that this is related to the contact line hysteresis, which leads to pinning of the contact line after an initial spreading phase at the receding contact angle. The departure mode is then similar to a pinned bubble and occurs once the contact angle reaches the advancing contact angle of the surface. A prediction for the departure radius based on these findings is found to be consistent with the experimental data.
Project description:Although β-dicarbonyl compounds are regularly employed as Michael donors, intermediates arising from the Michael addition of unsaturated β-ketoesters to α,β-unsaturated aldehydes are susceptible to multiple subsequent reaction pathways. We designed cyclic unsaturated β-ketoester substrates that enabled the development of the first diphenyl prolinol silyl ether catalyzed Michael-Michael cascade reaction initiated by a β-dicarbonyl Michael donor to form cyclohexene products. The reaction conditions we developed for this Michael-Michael cascade reaction were also amenable to a variety of linear unsaturated β-ketoester substrates, including some of the same linear unsaturated β-ketoester substrates that were previously ineffective in Michael-Michael cascade reactions. These studies thus revealed that a change in simple reaction conditions, such as solvent and additives, enables the same substrate to undergo different cascade reactions, thereby accessing different molecular scaffolds. These studies also culminated in the development of a general organocatalyzed Michael-Michael cascade reaction that generates highly functionalized cyclohexenes with up to four stereocenters, in up to 97% yield, 32:1 dr, and 99% ee, in a single step from a variety of unsaturated β-ketoesters.