Synthesis and chemistry of N-benzoyl-O- [N'-benzoyl-l-phenylalanyl]-l-phenylalaninol,the major mycelial metabolite of penicillium canadense

The structure of the title compound was established by evidence including total and partial hydrolyses and a stereospecific synthesis. Debenzoylation using triethyloxonium fluoroborate was accompanied by rearrangement to the amidoalcohol 12 (desacetylasperglaucide).     

The black flash model of QSOs

A model for QSOs and the nuclei of Seyfert Galaxies is proposed in which mass lost from stars in a galactic nucleus repeatedly builds to a critical density and then collapses to the center where it accretes onto a massive black hole (10⁸ M ), emitting great luminosity. This model describes a means of starting with an ordinary nucleus and developing conditions found in QSOs. By invoking intermittent flashes we overcome a difficulty previously encountered in similar models in which plausible sources of mass in reasonable galactic nuclei fail by a factor of 10^–2 in fueling a black hole at QSO luminosities.This essay was awarded the fifth prize for 1977 by the Gravity Research Foundation.     

Negative ion effects in CO2 convection laser discharges

Negative ions are computed to be formed on a time scale and in quantities such that they may be a cause of plasma instability observed in low pressure electrical discharge convection CO₂ lasers. In a typical CO₂?N₂?He?H₂O laser mixture the principal ions are CO ₃ ^? , CO ₄ ^? and H^? with the total negative ion densityn _? given by 0.1n _e <n _?<n _e , wheren _e is the electron density: but if the gases are re-cycled or if there is an air leak NO ₂ ^? and NO ₃ ^? are formed in significant amounts andn _? can become greater thann _e in a time considerably less than the gas dwell time in the electrical excitation discharge. CO is effective in reducingn _? in a system without re-cycling, but is ineffective in a re-cycled system with the oxides of nitrogen present.     

FREE RADICALS FROM THE PHOTODECOMPOSITION OF BLEOMYCIN

Abstract— Irradiation of bleomycin with light (λ > 320 nm) leads to a decrease in absorbance at 290 nm, which is suppressed by metal ions and by oxygen. Light-induced oxygen consumption is diminished by the enzymes superoxide dismutase and catalase, implying that toxic reduced species of oxygen (O₂ and H₂O₂) are formed during irradiation. Spin-trapping measurements with 5,5-dimethyl-1-pyrroline-1-oxide and 2-methyl-2-nitrosopropane demonstrated that hydroxyl radical and methyl radical adducts also are generated in the system. In addition, direct ESR measurements have shown that methyl radicals are produced during irradiation of bleomycin solutions at low temperatures, together with radicals probably derived from the bithiazole moiety of the bleomycin. The latter are also produced from irradiation of the model compound bithia. Radical production is diminished by complexation of bleomycin with metal ions.     

Effects of melt‐processing conditions on the quality of poly(ethylene terephthalate) montmorillonite clay nanocomposites

Organically modified montmorillonite was synthesized with a novel 1,2‐dimethyl‐3‐N‐alkyl imidazolium salt or a typical quaternary ammonium salt as a control. Poly(ethylene terephthalate) montmorillonite clay nanocomposites were compounded via melt‐blending in a corotating mini twin‐screw extruder operating at 285 °C. The nanocomposites were characterized with thermal analysis, X‐ray diffraction, and transmission electron microscopy to determine the extent of intercalation and/or exfoliation present in the system. Nanocomposites produced with N,N‐dimethyl‐N,N‐dioctadecylammonium treated montmorillonite (DMDODA‐MMT), which has a decomposition temperature of 250 °C, were black, brittle, and tarlike resulting from DMDODA degradation under the processing conditions. Nanocomposites compounded with 1,2‐dimethyl‐3‐N‐hexadecyl imidazolium treated MMT, which has a decomposition temperature of 350 °C, showed high levels of dispersion and delamination. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2661–2666, 2002     

First-principle studies of intermolecular and intramolecular catalysis of protonated cocaine

We have performed a series of first-principles electronic structure calculations to examine the reaction pathways and the corresponding free energy barriers for the ester hydrolysis of protonated cocaine in its chair and boat conformations. The calculated free energy barriers for the benzoyl ester hydrolysis of protonated chair cocaine are close to the corresponding barriers calculated for the benzoyl ester hydrolysis of neutral cocaine. However, the free energy barrier calculated for the methyl ester hydrolysis of protonated cocaine in its chair conformation is significantly lower than for the methyl ester hydrolysis of neutral cocaine and for the dominant pathway of the benzoyl ester hydrolysis of protonated cocaine. The significant decrease of the free energy barrier, approximately 4 kcal/mol, is attributed to the intramolecular acid catalysis of the methyl ester hydrolysis of protonated cocaine, because the transition state structure is stabilized by the strong hydrogen bond between the carbonyl oxygen of the methyl ester moiety and the protonated tropane N. The relative magnitudes of the free energy barriers calculated for different pathways of the ester hydrolysis of protonated chair cocaine are consistent with the experimental kinetic data for cocaine hydrolysis under physiologic conditions. Similar intramolecular acid catalysis also occurs for the benzoyl ester hydrolysis of (protonated) boat cocaine in the physiologic condition, although the contribution of the intramolecular hydrogen bonding to transition state stabilization is negligible. Nonetheless, the predictability of the intramolecular hydrogen bonding could be useful in generating antibody-based catalysts that recruit cocaine to the boat conformation and an analog that elicited antibodies to approximate the protonated tropane N and the benzoyl O more closely than the natural boat conformer might increase the contribution from hydrogen bonding. Such a stable analog of the transition state for intramolecular catalysis of cocaine benzoyl-ester hydrolysis was synthesized and used to successfully elicit a number of anticocaine catalytic antibodies.     

Cancellation of fine-structure splitting in quantum dots by a magnetic field

We demonstrate control of the fine-structure splitting of the exciton emission lines in single InAs quantum dots by the application of an in-plane magnetic field. The composition of the barrier material and the size and symmetry of the quantum dot are found to determine decrease or increase in the linear polarization splitting of the dominant exciton emission lines with increasing magnetic field. This enables the selection of dots for which the splitting can to be tuned to zero, within the resolution of our experiments. General differences in the g-factors and exchange splittings are found for different types of dot.