Total Syntheses of Two Self-polymerizable Carbocyclic Analogues of 2′-deoxyribonucleosides

A short regio- and stereoselective synthesis of two carbocyclic 3′-deoxynucleoside analogues is described, the key step of which consists in the photosensitized addition of MeOH to a cyclopent-2-enone derivative. As in both cases functional groups capable to react with each other are present in the same molecule, the synthetic compounds can form polymers similar to oligonucleotides.     

Comparisons between model equations for long waves

Summary Considered here are model equations for weakly nonlinear and dispersive long waves, which feature general forms of dispersion and pure power nonlinearity. Two variants of such equations are introduced, one of Korteweg-de Vries type and one of regularized long-wave type. It is proven that solutions of the pure initial-value problem for these two types of model equations are the same, to within the order of accuracy attributable to either, on the long time scale during which nonlinear and dispersive effects may accumulate to make an order-one relative difference to the wave profiles.This research was supported in part by the National Science Foundation. A considerable portion of the project was completed while the first author was resident at the Institute for Mathematics and Its Applications, University of Minnesota.     

A novel synthesis of 5-perfluorophenyl 4,5-dihydro-1H-pyrazoles in THF or water

5-Perfluorophenyl 4,5-dihydro-1H-pyrazoles were synthesized from 1,3-dipolar cycloaddition reaction of perfluorobenyl 2,4,6-triisopropylbenzenesulfonylhydrazone and α,β-unsaturated carbonyl compounds or acrylonitrile in THF or water. It was worthy to note that better results were obtained when water was employed as the solvent, which was considered as an effective, economic and environmentally friendly method to synthesize these pyrazole derivatives.     

Yellow‐light‐emitting cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative: Its synthesis and optical properties

A soluble cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative ( 9 ) was synthesized and characterized. Comparison between 9 and its model compound ( 10 ) showed that the chromophore in 9 remained to be well defined as a result of a π‐conjugation interruption at adjacent m‐phenylene units. The attachment of a cyano substituent only at the β position of the vinylene allowed the maximum electronic impact of the cyano group on the optical properties of the poly(p‐phenylene vinylene) material. At a low temperature (?108 or ?198 °C), the vibronic structures of 9 and 10 were partially resolved. The absorption and emission spectra of a film of 9 were less temperature‐dependent than those of a film of 10 , indicating that the former had a lower tendency to aggregate. A light‐emitting diode (LED) based on 9 emitted yellow light (λ_max ≈ 578 nm) with an external quantum efficiency of 0.03%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3149–3158, 2003     

Synthesis and gas barrier characterization of poly(ethylene isophthalate)

Poly(ethylene isophthalate) (PEI) was synthesized for this research with essentially a condensation polymerization of isophthalic acid and ethylene glycol catalyzed by zinc acetate and antimony trioxide. Several samples were obtained, and their characteristics were observed and compared with poly(ethylene terephthalate) (PET). The synthesized PEI samples were chemically identified by ¹H NMR. Thermal analysis with differential scanning calorimetry (DSC) yielded results that indicate the samples were primarily amorphous, with a glass‐transition temperature of 55–60 °C. Molecular weights of these PEI samples were also obtained through intrinsic viscosity measurements (Mark–Houwink equation). Molecular weights varied with conditions of the polymerization, and the highest molecular weight achieved was 21,000 g/mol. Finally, the diffusion coefficient, solubility, and permeability of CO₂ gas in PEI were measured and found to be substantially lower than in PET, as anticipated from their isomeric chemical structures. This is because in PET the phenyl rings are substituted in the para (1,4) positions, which allows for their facile flipping, effectively permitting gases to pass through. However, the meta‐substituted phenyl rings in PEI do not permit such ring flipping, and thus PEI may be more suitable for barrier applications. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4247–4254, 2004     

Elektrische Charakterisierung von Hochfrequenz-Niederdruck-Gasentladungen

In recent years there has emerged significant interest in low pressure radio frequency (rf) glow discharges which are used widely particulary in IC fabrication. Various parameters of the rf glow discharge have been found to be useful for its electrical characterization; however, there is no uniformity and agreement. Extensive experimental investigations on various discharge systems have shown, that the self-bias on the rf driven electrode, the complex conductivity and the breakdown characteristic are preferable parameters of rf discharges. Advantageously the self-bias and the complex conductivity should be presented in dependence on the pressure and the applied rf voltage. The discharge current cannot be measured quite accurately due to currents via leaky capacitors and the deviations from a sinusoidal form of the current due to nonlinearities.     

Local self-similarity and the Hausdorff dimension

Let X be a locally self-similar stochastic process of index 0<H<1 whose sample paths are a.s. C^H?ε for all ε>0. Then the Hausdorff dimension of the graph of X is a.s. 2?H. To cite this article: A. Benassi et al., C. R. Acad. Sci. Paris, Ser. I 336 (2003).     

Fluctuations of an Evaporating Black Hole from Back Reaction of Its Hawking Radiation: Questioning a Premise in Earlier Work

This paper delineates the first steps in a systematic quantitative study of the spacetime fluctuations induced by quantum fields in an evaporating black hole. We explain how the stochastic gravity formalism can be a useful tool for that purpose within a low-energy effective field theory approach to quantum gravity. As an explicit example we apply it to the study of the spherically-symmetric sector of metric perturbations around an evaporating black hole background geometry. For macroscopic black holes we find that those fluctuations grow and eventually become important when considering sufficiently long periods of time (of the order of the evaporation time), but well before the Planckian regime is reached. In addition, the assumption of a simple correlation between the fluctuations of the energy flux crossing the horizon and far from it, which was made in earlier work on spherically-symmetric induced fluctuations, is carefully analyzed and found to be invalid. Our analysis suggests the existence of an infinite amplitude for the fluctuations of the horizon as a three-dimensional hypersurface. We emphasize the need for understanding and designing operational ways of probing quantum metric fluctuations near the horizon and extracting physically meaningful information. Dedicated to Rafael Sorkin on the occasion of his 60th birthday.