Synthesis of pseudo-C-nucleosides from β-formyl-α,β-unsaturated ester bearing a β-furanosidic moiety

Abstract  

Pseudo-C-nucleosides have potential biological activity, and an efficient synthesis of new pseudo-C-nucleosides has been developed via the reaction of a β-formyl-α,β-unsaturated ester bearing a β-sugar moiety with hydrazines in neutral and acidic conditions. The preparation of the β-formyl-α,β-unsaturated ester was accomplished by oxidation of the secondary hydroxyl group of 3-O-benzyl-1,2-O-isopropylidene-α-d-glucofuranose, followed by elongation of its carbon chain with (ethoxycarbonylmethylene)triphenylphosphorane and oxidation of the hydroxymethyl group.     

A true random number generator based on the photon arrival time registered in a coincidence window between two single-photon counting modules

True random number generators are essential components for communications to be confidentially secured. In this paper a new method is proposed to generate random sequences of numbers based on the difference of the arrival times of photons detected in a coincidence window between two single-photon counting modules.     

Dynamic quantum revivals in phase space

We explain quantum revivals and fractional revivals in phase space of the Fermi?CUlam accelerator. We derive analytic expressions of the Wigner distribution function for the driven system describing quantum interferences in position and momentum space. We assume that the fractional revival times are nonrecurrent under certain conditions and display randomness in the occurrence of the phenomenon at these times.     

Encapsulation of proteins into tunable and giant mesocage alumina

Protein bioadsorption has rapidly attracted attention partially because of the promising advances in diagnostic assays, sensors, separations, and gene technology. Tunable and giant mesocage alumina cavities (5 nm to 20 nm) show capability in size-selective encapsulation and diffusivity of large proteins into interior pores.     

Unified approach to numerical methods,part II: Finite elements,boundary methods,and their coupling

This is the second in a series of three papers devoted to the presentation of a direct procedure of analysis of numerical methods for partial differential equations. The procedure consists of applying the method of weighted residuals and then interpreting the resulting equations by means of Green's formulas for discontinuous functions. Here, the general Green's formulas for operators defined in discontinuous fields developed in the first article, are applied to formulate the method of weighted residuals for arbitrary linear operators. Finite elements, boundary methods, and general procedures for coupling finite elements and boundary methods are discussed.     

214Po: A γ-γ and γγ(θ) Coincidence study

Extensive γ-γ coincidence measurements have been made on γ rays accompanying theβ ^? decay of²¹⁴Bi using a conventional GeGe coincidence spectrometer. A total of 33 new γ transitions among levels of²¹⁴Po have been established. Twenty-three previously reported but unplaced transitions have now been assigned in the level scheme. In addition to confirming 56 previously proposed levels, four new levels are established at 1015.05, 1712.98, 3003.5 and 3160.5 keV. Directional correlation measurements have been made on six weak cascades which have the first excited state in common. Mixing ratios have been deduced for the transitions concerned.     

A fast radical chain mechanism in the polyfluoroalkoxylation of aromatics through NO2 group displacement. Mechanistic and theoretical studies

Introduction of polyfluoroalkoxy and polyfluoroalkylthio substituents in aromatic rings can be achieved with mild conditions and short times thorough reaction of concentrated solutions of dinitrobenzenes in DMF with polyfluoro alcohols and polyfluoro thiols in moderate excess, in the presence of excess tetrabutylammonium fluoride as a base. Mechanistic studies suggest that under these conditions a fast radical chain mechanism operates. This mechanism is elicited by oxidation of a Meisenheimer complex and proceeds through a radical aromatic substitution with the polyfluoroalkoxy or the polyfluoroalkylthio radicals as key intermediates. At low concentrations, entrainment can be achieved with superoxide anion. A rationale for this effect is discussed. Answers to particular questions about the proposed mechanism are achieved through a theoretical study at the B3LYP/6-31+G(d,p) level. Specifically, the competition between the radical mechanism and the corresponding polar one (classical S(N)Ar reaction) is studied in that way, with the conclusion that the key steps of the radical mechanism in our reaction conditions (polar aprotic solvent) are at least as efficient as the ones of the polar one, thus justifying the observed kinetic advantage for the chain reaction in the conditions where an efficient initiation occurs.     

Dosage spectrographique du gallium dans l'aluminium

Résumé L'auteur a préparé des alliages-types à partir d'aluminium et de gallium purs, puis, les a analysés par la méthode de l'arc intermittent comme contrôle. Application à l'analyse d'un échantillon d'aluminium renfermant 0,01% de gallium.

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Summary The author has prepared standard alloys, starting with aluminum and pure gallium, and then analyzed them by the intermittent arc method as control. Application to the analysis of a sample of aluminum containing 0,01% gallium.

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Zusammenfassung Es wurden Legierungstypen aus reinem Aluminium und Gallium hergestellt und zur Kontrolle spektralanalytisch mit dem Abreißbogen untersucht. Die Anwendung dieses Verfahrens auf eine Aluminiumprobe mit 0,01% Gallium ergab befriedigende Resultate.

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Résumé d'une Thèse soutenue devant la Faculté des Sciences de Paris, le 22 juin 1950.

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Avec 2 figures.     

Tautomer selective photochemistry in 1-(tetrazol-5-yl)ethanol

A combined matrix isolation FTIR and theoretical DFT/B3LYP/6-311++G(d,p) study of the molecular structure and photochemistry of 1-(tetrazol-5-yl)ethanol [1-TE] was performed. The potential energy surface landscapes of the 1H and 2H tautomers of the compound were investigated and the theoretical results were used to help characterize the conformational mixture existing in equilibrium in the gas phase prior to deposition of the matrices, as well as the conformers trapped in the latter. In the gas phase, at room temperature, the compound exists as a mixture of 12 conformers (five of the 1H tautomer and seven of the 2H tautomer). Upon deposition of the compound in an argon matrix at 10 K, only three main forms survive, because the low barriers for conformational isomerization allow extensive conformational cooling during deposition. Deposition of the matrix at 30 K led to further simplification of the conformational mixture with only one conformer of each tautomer of 1-TE surviving. These conformers correspond to the most stable forms of each tautomer, which bear different types of intramolecular H-bonds: 1H-I has an NH···O hydrogen bond, whereas 2H-I has an OH···N hydrogen bond. Upon irradiating with UV light (λ > 200 nm), a matrix containing both 1H-I and 2H-I forms, an unprecedented tautomer selective photochemistry was observed, with the 2H tautomeric form undergoing unimolecular decomposition to azide + hydroxypropanenitrile and the 1H-tautomer being photostable.