Synthesis and cell cycle inhibition of the peptide enamide natural products terpeptin and the aspergillamides

Total syntheses of the peptide enamide natural products terpeptin and aspergillamides A and B are reported. An oxidative decarboxylation-elimination protocol is employed to construct the indolic enamide moiety. Unambiguous stereochemical assignment of (−)-terpeptin is accomplished by synthesis of all possible stereochemical analogues. Select compounds have been evaluated in cell cycle inhibitor assays which show that the natural amino acid configuration of terpeptin has the most potent inhibitory activity.     

Free radical-mediated vinyl amination: a mild, general pyrrolidinyl enamine synthesis

The complete scope of free radical-mediated vinyl amination is described, using 5-exo-trig cyclizations of vinyl radicals to the nitrogen of azomethines. The focus is primarily on N,N-dialkyl enamines since their nucleophilicity renders them the most challenging enamines to synthesize using redox conditions. These studies establish several encouraging precedents for the broader application of this strategy.     

A short synthesis of koniamborine, a naturally occurring pyrano[3,2-b]indole

An expedient synthesis of the alkaloid koniamborine, the only to date isolated naturally occurring pyrano[3,2-b]indole is presented. The key pyrano[3,2-b]indole forming step is a palladium-catalyzed reductive N-heteroannulation of 2-(4-methoxy-2-nitrophenyl)-(4H)-pyrane-4-one.     

Critical evaluation of gas standards based on hydrogen

Summary Six commercial hydrogen standards containing helium, oxygen, nitrogen, methane and carbon dioxide at trace levels were analyzed by gas chromatography, for periods up to 105 days. The concentrations, in the range of 0–120 μmol mol⁻¹, were stable (with the exception of oxygen) but often significantly different from the certified values provided by the suppliers, especially for helium, oxygen and nitrogen. Concurrently, some experiments were carried out to verify the stability of gas mixtures based on hydrogen stored in cylinders submitted to different chemical and physical treatments. The causes that led to the deviations observed, as well as the decreases in oxygen, are discussed. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996.     

On-line nuclear orientation study of184Au

The¹⁸⁴Au→¹⁸⁴Pt decay, studied on-line with the UNISOR facility at HHIRF, is discussed. Gamma-ray and conversion-electron spectroscopy of¹⁸⁴Pt as well as on-line nuclear orientation measurements of¹⁸⁴Au were done. A new low-lying level scheme of¹⁸⁴Pt is proposed. Two coexisting bands with different deformations and their respective γ-vibrational bands are established. Internal conversion coefficients for interband transitions between states with the same spin are extracted from the spectroscopy measurements. The relative E0 contents of the transitions are determined by combining internal conversion coefficients with E2/M1 mixing ratios deduced from gamma-ray anisotropies measured from oriented nuclei.     

Mechanosynthesis of YIG and GdIG: A Structural and Mössbauer Study

We have investigated the mechanosynthesis of gadolinium and yttrium iron garnets by high-energy ball-milling of α-Fe₂O₃ and Gd₂O₃ or α-Fe₂O₃ and Y₂O₃, respectively, followed by short thermal annealings conducted at moderate temperatures. The samples were characterized by X-ray diffraction and Mössbauer spectroscopy, in order to determine the influence of the milling time and annealing conditions on the final products. For as-milled samples of each rare-earth system, the results revealed the formation of perovskite phases, in relative amounts that depend on the milling time. The formation of garnet phases was observed in as-annealed samples treated at 1000°C for 2 h or 1100°C for 3 h, i.e., at very modest annealing requirements when compared with ordinary solid-state-reaction processes performed without previous high-energy milling. Also, the occurrence was verified of a milling time for which the relative amount of garnet phases formed by annealing was maximized. This time depends on the rare-earth composing the garnet phase and on the annealing temperature.     

Radiative characteristics of pulsed power driven Z-pinch aluminumplasmas

In this paper, we study the dynamics of a massive aluminum Z-pinch plasma load and evaluate its performance as a soft X-ray radiator. A radiation hydrodynamic model self-consistently driven by a circuit describes the dynamics. Comparisons are made for the K- and L-shell soft X-ray emission as a function of the ionization dynamic model. The ionization dynamic models are represented by: 1) a time-dependent nonequilibrium (NEQ) model, 2) a collisional radiative equilibrium (CRE) model, and 3) a local thermodynamic equilibrium (LTE) model. For all three scenarios the radiation is treated 1) in the free streaming optically thin approximation where the plasma is treated as a volume emitter and 2) in the optically thick regime where the opacity for the lines and continuum is self-consistently calculated online and the radiation is transported through the plasma. Each simulation is carried out independently to determine the sensitivity of the implosion dynamics to the ionization and radiation model, i.e., how the ionization dynamic model affects the radiative yield and emission spectra. Results are presented for the L- and K-shell radiation yields and emission spectra as a function of photon energy from 10 eV to 10 keV. Also, departure coefficients from LTE are presented for selected levels and ionization stages     

Facets with fewest vertices

Forv>d≧3, letm(v, d) be the smallest numberm, such that every convexd-polytope withv vertices has a facet with at mostm vertices. In this paper, bounds form(v, d) are found; in particular, for fixedd≧3, $$\frac{{r - 1}}{r} \leqslant \mathop {\lim \inf }\limits_{\upsilon \to \infty } \frac{{m(\upsilon ,d)}}{\upsilon } \leqslant \mathop {\lim \sup }\limits_{\upsilon \to \infty } \frac{{m(\upsilon ,d)}}{\upsilon } \leqslant \frac{{d - 3}}{{d - 2}}$$ , wherer=[1/3(d+1)].     

Rectangular convexity of convex domains of constant width

An E R ² is r-convex if for every x, y E there exists a closed rectangle R such that x, y R and R E. Several results about r-convexity appeared in [1]. Its authors formulated a conjecture about conditions for a compact, convex set in R ² to be r-convex. We prove this conjecture in the case of convex domains of constant width.