The tandem catalytic asymmetric allene diboration/imine allylation and the asymmetric transition-metal-catalyzed conjugate allylation of activated enones

Thesis advisor: James P. MorkenDescribed herein are methods for asymmetric allylation. Chapter 1 describes the scope of the Pd-catalyzed asymmetric diboration of prochiral allenes. The products of this process possess both a chiral allylboronate functional group and a vinylboronate moiety. The allylboronate functionality can subsequently be used for imine allylation, without isolation of the diboron intermediate, resulting in the formation of atypical allylation products through a tandem, one-pot sequence. Furthermore, enantioselection in the catalytic diboration and chirality transfer in the subsequent imine allylation are high; thus, non-racemic, protected homoallylic amines, and other derivatives, are produced in high enantiomeric excess. Chapter 2 describes the discovery and development of a transition-metal-catalyzed asymmetric conjugate allylation of allylboronate ester nucleophiles to activated enones. The scope, utility, and mechanistic aspects of this new reaction are discussed.Thesis (PhD) — Boston College, 2008.Submitted to: Boston College. Graduate School of Arts and Sciences.Discipline: Chemistry

Der Zugang Jugendlicher zur Filmkultur : Schweizer Jugendliche im Umgang mit Medien, mit einem besonderen Fokus auf Film und Kino

Bericht zur Projektphase 2007/08 im Auftrag des Verbands Filmregie und Drehbuch Schweiz (ARF/FDS)Jugendliche wachsen heute mehr denn je in komplexen Medienwelten auf (vgl. Vollbrecht 2002: 1). In ihrer Freizeitgestaltung haben Medien einen hohen Stellenwert und scheinen diese auch zeitlich zu dominieren (vgl. Vollbrecht 2002: 5). Unter allen Medienumgebungen nimmt das Kino für Heranwachsende eine herausragende Stellung ein. Das Kino ist der bei weitem beliebteste Medienort der Jugendlichen (vgl. Vollbrecht 2002: 26). Doch bemerkten Baacke, Schäfer und Vollbrecht, dass es zur Bedeutung des Kinos für Kinder und Jugendliche kaum Literatur gibt, und besonders der Zusammenhang zwischen dem Kino als Versammlungsort und dem Kinofilm bisher so gut wie nicht thematisiert worden ist (vgl. ebd.: 5). Da das Kino für die Jugendlichen aber eine attraktive Medienumgebung und in der Rangreihe der wichtigsten Freizeitorte ganz vorne steht (vgl. Baacke/Schäfer/Vollbrecht 1994: 108), wird der Fokus auf diesen Medienort der Jugendlichen gelegt. Im vorliegenden Bericht stehen demnach der Medienort Kino, das Medium Film und deren Nutzung durch die Jugendlichen im Zentrum des Interesses. In der Literatur findet man die Behauptung, dass die Jugendlichen heute immer weniger das Kino besuchen (vgl. Neckermann 1998: 472f). Dieser Eindruck wird auch von Vertretern der Film- und Kinobranche geteilt. Um den Gründen für das postulierte Fernbleiben dieser Kerngruppe des Kinos auf den Grund zu gehen, hat der Verband Filmregie und Drehbuch Schweiz (ARF/FDS) an der Generalversammlung 2006 beschlossen, den Fokus auf den Zugang von Jugendlichen zur Filmkultur zu legen. Ausgangslage bildet folgende These der Verleih- und Kinoseite: „Dem Kino bricht das jugendliche Publikum weg“. Die Studie zum Schweizer Kinopublikum von Moeschler (2006) hatte nur einen kleinen Anteil an Jugendlichen in der Stichprobe erfasst. Daraus liessen sich zwar bereits gewisse interessante Hypothesen ableiten. Die Datenlage reichte aber noch nicht aus, um ein repräsentatives Bild zum jugendlichen Film- und Kinopublikum zu zeichnen. Um hierfür vertiefte Grundlagen zu haben, initiierte der Verband ARF/FDS ein Projekt zu diesem Thema. Hauptanliegen dieses Projekts ist die Förderung des Zugangs von Jugendlichen zur Filmkultur. Innerhalb dieses Projekts soll es drei Bausteine geben. Der erste Baustein beinhaltet eine Bestandesaufnahme der Filmkultur im Kontext des jugendlichen Medienalltags. Im zweiten Baustein sollen bestehende Modelle und Konzepte der Förderung des Zugangs Jugendlicher zur Filmkultur aufgelistet und diskutiert werden. Im dritten und letzten Baustein soll aufbauend auf die beiden ersten Bausteine ein konkretes Projekt entwickelt und evaluiert werden. Der vorliegende Bericht umfasst die ersten zwei Bausteine, welche zwischen Frühjahr 2007 und Frühjahr 2008 bearbeitet wurden. Um den Zugang von Jugendlichen zur Filmkultur zu fördern, sollen als erstes die Mediengewohnheiten der Jugendlichen empirisch erhoben und analysiert werden. Hierbei wird der Fokus insbesondere auf das Medium Film und den Medienort Kino gelegt

Effect of dietary alpine butter rich in conjugated linoleic acid on milk fat composition of lactating sows

Multiparous sows (n 17) were included in a controlled cross-over-study in order to investigate the influence of a natural source of conjugated linoleic acid (CLA) (alpine butter) on the milk fatty acid composition of lactating sows (as an animal model for lactating women) and on the growth performance of their progeny. The usual fat source of a standard lactation diet was replaced by either CLA-rich alpine butter or margarine (control diet). Compared with the margarine diet, feeding the alpine butter-supplemented diet increased (P0·05) affected. Growth performance of the progeny was similar for both dietary treatments. In summary, the findings show that adding alpine butter to the diet does not provoke a milk fat depression and does not alter the composition of total SFA, MUFA and PUFA in sow milk but increases its CLA concentratio

Determination of the strong coupling constant using inclusive jet cross section data from multiple experiments

Abstract Inclusive jet cross section measurements from the ATLAS, CDF, CMS, D0, H1, STAR, and ZEUS experiments are explored for determinations of the strong coupling constant $$\alpha _{\text {s}} (M_{\text {Z}})$$ αs(MZ) . Various jet cross section data sets are reviewed, their consistency is examined, and the benefit of their simultaneous inclusion in the $$\alpha _{\text {s}} (M_{\text {Z}})$$ αs(MZ) determination is demonstrated. Different methods for the statistical analysis of these data are compared and one method is proposed for a coherent treatment of all data sets. While the presented studies are based on next-to-leading order in perturbative quantum chromodynamics (pQCD), they lay the groundwork for determinations of $$\alpha _{\text {s}} (M_{\text {Z}})$$ αs(MZ) at next-to-next-to-leading order

Maternal dietary alpine butter intake affects human milk: Fatty acids and conjugated linoleic acid isomers

Consumption of CLA by lactating women affects the composition of their milk, but the pattern of the different CLA isomers is still unknown. We determined the effects of short maternal supplementation with CLA-rich Alpine butter on the occurrence of FA and CLA isomers in human milk. In an open randomized controlled study with a two-period cross-over design, milk FA and CLA isomer concentrations were measured on postpartum days >-20 in two parallel groups of lactating women before, during, and after consumption of defined quantities of Alpine butter or margarine with comparable fat content (10 d of butter followed by 10 d of margarine for one group, and vice versa in the other). In the 16 women who completed the study (8/group), Alpine butter supplementation, increased the C16 and C18 FA, the sum of saturated FA, the 18∶1 trans FA, and the trans FA with CLA. The CLA isomer 18∶2 c9, t11 increased by 19.7%. Significant increases were also found for the isomers t9,t111, t7,c9,t11,c13, and t8,c10 18∶2. The remaining nine of the total 14 detectable isomers showed no changes, and concentrations were <5 mg/100g fat. A breastfeeding mother can therefore modulate the FA/CLA supply of her child by consuming Alpine butter. Further studies will show whether human milk containing this FA and CLA isomer pattern acts as a functional food for newborn

The semiclassical continuity equation for open chaotic systems

We consider the continuity equation for open chaotic quantum systems in the semiclassical limit. First we explicitly calculate a semiclassical expansion for the probability current density using an expression based on classical trajectories. The current density is related to the survival probability via the continuity equation, and we show that this relation is satisfied within the semiclassical approximation to all orders. For this we develop recursion relation arguments which connect the trajectory structures involved for the survival probability, which travel from one point in the bulk to another, to those structures involved for the current density, which travel from the bulk to the lead. The current density can also be linked, via another continuity equation, to a correlation function of the scattering matrix whose semiclassical approximation is expressed in terms of trajectories that start and end in the lead. We also show that this continuity equation holds to all orders.Comment: Refereed version: Minor changes in presentation (especially in the Introduction) and minor corrections to the start of section 6. 21 pages, 1 figure in two part

Loschmidt echo for local perturbations: non-monotonous cross-over from the Fermi-golden-rule to the escape-rate regime

We address the sensitivity of quantum mechanical time evolution by considering the time decay of the Loschmidt echo (LE) (or fidelity) for local perturbations of the Hamiltonian. Within a semiclassical approach we derive analytical expressions for the LE decay for chaotic systems for the whole range from weak to strong local perturbations and identify different decay regimes which complement those known for the case of global perturbations. For weak perturbations a Fermi-golden-rule (FGR) type behavior is recovered. For strong perturbations the escape-rate regime is reached, where the LE decays exponentially with a rate independent of the perturbation strength. The transition between the FGR regime and the escape-rate regime is non-monotonic, i.e. the rate of the exponential time-decay of the LE oscillates as a function of the perturbation strength. We further perform extensive quantum mechanical calculations of the LE based on numerical wave packet evolution which strongly support our semiclassical theory. Finally, we discuss in some detail possible experimental realizations for observing the predicted behavior of the LE.Comment: 27 pages, 7 figures; important changes throughout the pape