Integral equation formulation for buoyancy-driven convection problems

An integral equation formulation for buoyancy-driven convection problems is developed and illustrated. Buoyancy-driven convection in a bounded cylindrical geometry with a free surface is studied for a range of aspect ratios and Nusselt numbers. The critical Rayleigh number, the nature of the cellular motion, and the heat transfer enhancement are computed using linear theory. Green's functions are used to convert the linear problem into linear Fredholm integral equations. Theorems are proved which establish the properties of the eigenvalues and eigenfunctions of the linear integral operator which appears in these equations.     

Muonium formation in xenon and argon up to 60 atmospheres

Results of muon polarization studies in xenon and argon up to 60 atm are reported. In argon for pressures up to 10 atm, the muon polarization is best explained by an epithermalcharge exchange model. Above this pressure, the decrease inP _D and increase inP _L are ascribed to charge neutralization and spin exchange reactions, respectively, in the radiolysis track. Measurements with Xe/He mixtures with a xenon pressure of 1 atm indicate that the lost polarization in the pure xenon at this pressure is due to inefficient moderation of the muon. As the pressure in pure xenon is increased above 10 atm, we find thatP _L remains roughly constant andP _D begins to increase. The lost fraction may be due to the formation of a XeMu Van der Waals type complex, whileP _D is ascribed to XeMu⁺ formation. This suggests that spur processes appear to be less important in xenon than in argon.     

Thermal boundary condition effects on heat transfer in turbulent rough-wall boundary layers

Measurements and predictions are presented which investigate the effects of thermal boundary condition on heat transfer in the turbulent rough-wall boundary layer. Stanton number measurements are reported for the turbulent flow of air over rough plates with a variety of thermal boundary conditions on two separate rough surfaces. The cases considered are constant wall temperature, constant wall heat flux, step wall temperature, and piecewise linear wall temperature distributions. These measurements and data from other sources are compared with predictions using finite difference solutions of the discrete element roughness model and with superposition solutions. The predictions and the measurements are in good to excellent agreement.In dieser Arbeit werden Messungen und Berechnungen gezeigt, die den Einfluß der thermischen Randbedingungen auf die Wärmeübertragung in turbulenten Grenzschichten an rauhen Wänden untersuchen. Es werden Messungen der Stanton Zahl für turbulente Luftströmung über rauhe Platten an zwei separaten Oberflächen unter einer Reihe von thermischen Randbedingungen dargestellt. Die betrachteten Fälle sind konstante Wandtemperatur, konstanter Wärmestrom durch die Wand, abgestufte Wandtemperatur und stückweise konstante Wandtemperatur. Diese Messungen, sowie Daten anderer Untersuchungen, werden mit Berechnungen durch Finite-Differenzen Lösungen des Diskrete-Elemente-Rauhheits-Modells und Superpositionslösungen verglichen. Berechnungen und Messungen liegen in guter bis ausgezeichneter Übereinstimmung.     

Telomestatin: formal total synthesis and cation-mediated interaction of its seco-derivatives with G-quadruplexes

The structurally unique natural product telomestatin incorporates seven oxazole rings and one sulfur-containing thiazoline in a macrocyclic arrangement. The compound is a potent inhibitor of the enzyme telomerase and therefore provides a structural framework for developing new potential therapeutic agents for cancer. An efficient formal total synthesis of telomestatin is reported in which the key steps are the use of dirhodium(II)-catalyzed reactions of diazocarbonyl compounds to generate six oxazole rings, demonstrating the power of rhodium carbene methodology in organic chemical synthesis. CD spectroscopy establishes that seco-derivatives of telomestatin are potent stabilizers of G-quadruplex structures derived from the human telomeric repeat sequence. Mass spectrometry studies, confirmed by molecular dynamics simulations, provide the first evidence that high affinity binding to terminal G-tetrads in both 1:1 and 2:1 ligand complexes is mediated through the macrocycle coordinating a monovalent cation, with selectivity for the antiparallel structure.     

Aziridine-mediated ligation and site-specific modification of unprotected peptides

A synthesis of aziridine-containing peptides via the Cu(II)-promoted coupling of unprotected peptide thioacids and N-H aziridine-2-carbonyl peptides is reported. The unique reactivity of the resulting N-acylated aziridine-2-carbonyl peptides facilitates their subsequent regioselective and stereoselective nucleophilic ring-opening to give unprotected peptides that are specifically modified at the ligation site. The aziridine-mediated peptide ligation concept is exemplified using H(2)O as the nucleophile, producing a Xaa-Thr linkage (where Xaa can be an epimerizable and hindered amino acid). The overall process is compatible with a variety of unprotected amino acid functionality, most notably the N-terminal and Lys side chain amines.     

Cartesian Differential Categories as Skew Enriched Categories

We exhibit the cartesian differential categories of Blute, Cockett and Seely as a particular kind of enriched category. The base for the enrichment is the category of commutative monoids—or in a straightforward generalisation, the category of modules over a commutative rig k. However, the tensor product on this category is not the usual one, but rather a warping of it by a certain monoidal comonad Q. Thus the enrichment base is not a monoidal category in the usual sense, but rather a skew monoidal category in the sense of Szlachányi. Our first main result is that cartesian differential categories are the same as categories with finite products enriched over this skew monoidal base. The comonad Q involved is, in fact, an example of a differential modality. Differential modalities are a kind of comonad on a symmetric monoidal k-linear category with the characteristic feature that their co-Kleisli categories are cartesian differential categories. Using our first main result, we are able to prove our second one: that every small cartesian differential category admits a full, structure-preserving embedding into the cartesian differential category induced by a differential modality (in fact, a monoidal differential modality on a monoidal closed category—thus, a model of intuitionistic differential linear logic). This resolves an important open question in this area.

     

Elektrometrie

Ohne Zusammenfassung     

Photoemission studies of the electronic structure of III–V semiconductor surfaces

The photoemission technique using synchroton radiation in the photon energy range 5–450 eV has been applied to the study of the electronic structure of some III–V semiconductor surfaces, prepared by cleavage in situ under ultrahigh vacuum conditions, ? 10^?11 Torr. For p-type GaAs(110), the Fermi level is pinned at the top of the valence band and thus no filled surface states extend into the band-gap. The situation is more complicated for n-type GaAs(110), where band bending easily can be introduced by extrinsic effects (impurities, cleavage quality, etc.) and push the Fermi level down to about midgap. Chemical shifts of inner core levels (3d for Ga and As) are used to obtain information on the bonding site of oxygen on the (110) surface. GaAs(110) can be exposed to atmospheric pressure of molecular oxygen without breaking the bonds between the surface atoms and the bulk. Oxygen is predominantly bonded to the As atoms on the surface. The oxidation behavior is strikingly different for GaSb(110) with formation of gallium and antimony oxides on the surface directly upon oxygen exposure. Heavier oxidation of GaAs(110) and breaking of the surface bonds will also be reported.