Laserinduzierte NO Desorption von C60 und Graphitoberflächen

In dieser Dissertation wird die NO Desorption von Fullerenoberflächen und Graphitoberflächen untersucht. Die desorbierenden Moleküle werden mit vollständiger Energieauflösung mittels 1+1 REMPI detektiert. Die Desorption von der untersuchten Fullerenoberfläche erfolgt in zwei Kanälen mit unterschiedlichen Geschwindigkeitsverteilungen. Der schnelle Kanal zeigt eine heiße Rotationsverteilung bei sehr niedriger Vibrationsanregung. Im langsamen Kanal weist eine breite Geschwindigkeitsverteilung bei langen Verzögerungszeiten zwischen Desorptions- und Nachweislaser auf eine verspätete Desorption hin. Die Lebensdauer dieser Anregung kann zu etwa 0,125 ms abgeschätzt werden und wird auf langlebige exzitonische Zustände im Fulleren zurückgeführt. Die Desorption von Graphit erfolgt mit einem femtosekunden Laser bei Photonenenergien bis 57 eV. Bei diesem Halbmetall wird sowohl eine heiße Rotationsverteilung als auch eine heiße Vibrationsverteilung der desorbierenden Moleküle beobachtet

Free electron laser induced processes in thin molecular ice

Intermolecular reactions in and on icy films on silicate and carbonaceous grains constitute a major route for the formation of new molecular constituents in interstellar molecular clouds. In more diffuse regions and in protoplanetary discs, energetic radiation can trigger reaction routes far from thermal equilibrium. As an analog of interstellar icecovered dust grains, highly oriented pyrolytic graphite HOPG covered with D2O, NO, and H atoms is irradiated by ultrashort XUV pulses and the desorbing ionic and neutral products are analysed. The yields of several products show a nonlinear intensity dependence and thus enable the elucidation of reaction dynamics by two pulse correlated desorptio

A new restriction for initially stressed elastic solids

We introduce a fundamental restriction on the strain energy function and stress tensor for initially stressed elastic solids. The restriction applies to strain energy functions W that are explicit functions of the elastic deformation gradient F and initial stress τ⁠, that is W:=W(F,τ)⁠. The restriction is a consequence of energy conservation and ensures that the predicted stress and strain energy do not depend upon an arbitrary choice of reference configuration. We call this restriction initial stress reference independence (ISRI). It transpires that most strain energy functions found in the literature do not satisfy ISRI, and may therefore lead to unphysical behaviour, which we illustrate through a simple example. To remedy this shortcoming, we derive three strain energy functions that do satisfy the restriction. We also show that using initial strain (often from a virtual configuration) to model initial stress leads to strain energy functions that automatically satisfy ISRI. Finally, we reach the following important result: ISRI reduces the number of unknowns in the linear stress tensor for initially stressed solids. This new way of reducing the linear stress may open new pathways for the non-destructive determination of initial stresses through ultrasonic experiments, among others

PEG-Albumin Plasma Expansion Increases Expression of MCP-1 Evidencing Increased Circulatory Wall Shear Stress: An Experimental Study

Treatment of blood loss with plasma expanders lowers blood viscosity, increasing cardiac output. However, increased flow velocity by conventional plasma expanders does not compensate for decreased viscosity in maintaining vessel wall shear stress (WSS), decreasing endothelial nitric oxide (NO) production. A new type of plasma expander using polyethylene glycol conjugate albumin (PEG-Alb) causes supra-perfusion when used in extreme hemodilution and is effective in treating hemorrhagic shock, although it is minimally viscogenic. An acute 40% hemodilution/exchange-transfusion protocol was used to compare 4% PEG-Alb to Ringer’s lactate, Dextran 70 kDa and 6% Hetastarch (670 kDa) in unanesthetized CD-1 mice. Serum cytokine analysis showed that PEG-Alb elevates monocyte chemotactic protein-1 (MCP-1), a member of a small inducible gene family, as well as expression of MIP-1α, and MIP-2. MCP-1 is specific to increased WSS. Given the direct link between increased WSS and production of NO, the beneficial resuscitation effects due to PEG-Alb plasma expansion appear to be due to increased WSS through increased perfusion and blood flow rather than blood viscosity

The Different Function of Single Phosphorylation Sites of Drosophila melanogaster Lamin Dm and Lamin C

Lamins' functions are regulated by phosphorylation at specific sites but our understanding of the role of such modifications is practically limited to the function of cdc 2 (cdk1) kinase sites in depolymerization of the nuclear lamina during mitosis. In our study we used Drosophila lamin Dm (B-type) to examine the function of particular phosphorylation sites using pseudophosphorylated mutants mimicking single phosphorylation at experimentally confirmed in vivo phosphosites (S25E, S45E, T435E, S595E). We also analyzed lamin C (A-type) and its mutant S37E representing the N-terminal cdc2 (mitotic) site as well as lamin Dm R64H mutant as a control, non-polymerizing lamin. In the polymerization assay we could observe different effects of N-terminal cdc2 site pseudophosphorylation on A- and B-type lamins: lamin Dm S45E mutant was insoluble, in contrast to lamin C S37E. Lamin Dm T435E (C-terminal cdc2 site) and R64H were soluble in vitro. We also confirmed that none of the single phosphorylation site modifications affected the chromatin binding of lamin Dm, in contrast to the lamin C N-terminal cdc2 site. In vivo, all lamin Dm mutants were incorporated efficiently into the nuclear lamina in transfected Drosophila S2 and HeLa cells, although significant amounts of S45E and T435E were also located in cytoplasm. When farnesylation incompetent mutants were expressed in HeLa cells, lamin Dm T435E was cytoplasmic and showed higher mobility in FRAP assay

On residual stresses and homeostasis: an elastic theory of functional adaptation in living matter

Living matter can functionally adapt to external physical factors by developing internal tensions, easily revealed by cutting experiments. Nonetheless, residual stresses intrinsically have a complex spatial distribution, and destructive techniques cannot be used to identify a natural stress-free configuration. This work proposes a novel elastic theory of pre-stressed materials. Imposing physical compatibility and symmetry arguments, we define a new class of free energies explicitly depending on the internal stresses. This theory is finally applied to the study of arterial remodelling, proving its potential for the non-destructive determination of the residual tensions within biological materials

Development of a Multigram Synthesis of URB937, a Peripherally Restricted FAAH Inhibitor

A new synthetic approach to URB937 was developed starting from the inexpensive and widely available 4-benzyloxyphenol. A reproducible four-step procedure, requiring no chromatographic purifications, was optimized that allowed the preparation of 100 g of URB937 in 45% overall yield. © 2013 American Chemical Society