Characterization of anomeric differences of ammonium-bound monomeric and dimeric complex ions of 1α- and 1β-azido-pentofuranosyl derivates by kinetic method

Relative stabilities (ΔG^c) of ammonium-bound monomers and dimers of anomeric β- -pentofuranosyl 1α- and 1β-azide derivates are determinate using the kinetic method by measuring relative rates of competitive collision-induced dissociations of dimeric [ANH₄B]⁺ and trimeric [A₂NH₄B]⁺ or [ANH₄B₂]⁺ cluster ions. Comparison between calculated ammonium affinities (AAs) and relative stabilities (ΔG^c) of ammonium-bound monomers shows qualitative correlations between both thermochemical quantities, but in two examples the activation barrier differences of competitive fragmentation channels cause a large disparity between both thermochemical data. Therefore, the most stable ammonium-bound monomers of the anomeric lα- and lβ-2,3,5-tri-O-benzyl-β- -arabino-pento-furanosyl azides possess the lowest ammonium affinities and the highest relative stabilities. Two different relative stabilities measured for the same ammonium-bound homo- or hetero-dimers indicate dissimilar activated barriers of trimers transition states for dimer formations. The activated barriers of trimers depend on the relative stabilities of ammonium-bound monomer within the trimeric cluster ions.     

A theoretical study of the beta decay transitions 0− → 2+ and 0− → 0+ of the Ho166 nucleus

The theoretical beta decay observables are compared with the experimental values for the 0^? → 2⁺ and 0^? → 2⁺ transitions. By considering a Ho¹⁶⁶ ground state configuration infered from (d, p) reaction experiments, and using all the matrix elements, satisfactory results are obtained for the 0^? → 2⁺ transition. For the 0^? → 2⁺ transition an important cancellation effect has been found which determines the failure of the ξ approximation and an energy dependent spectrum shape.     

Stereochemical correlation of diastereomeric 3-amino- with 3-arylamino acids,and their derivatives via stereospecific N-phenylation by diphenylhalonium salts

Diphenylhalonium salts were used in stereospecific N-phenylation of racemic and optically active 3-amino-2,3-diphenyl-1-propanols leading to 3-anilino-2,3-diphenyl-1-propanols. The absolute configurations of the latter and of genetically related compounds were established.

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Stereochemische Korrelation von diastereomeren 3-Amino- mit 3-Arylaminosäuren bzw. ihrer Derivate durch stereospezifische N-Phenylierung mit DiphenylhaloniumsalzenKurze Mitteilung

Zusammenfassung Durch stereospezifische N-Phenylierung mit Hilfe von Diphenylhaloniumsalzen werden racemische sowie optische aktive 3-Amino-2,3-diphenyl-1-propanole in die entsprechenden 3-Anilino-2,3-diphenyl-1-propanole übergeführt. Auf Grund dieser Umwandlung wird die absolute Konfiguration der Aminoalkohole und davon abgeleiteter Derivate ermittelt.

     

Polarization effects on theft values of the beta transitions to155Gd

A good agreement between theory and experiment is achieved if besides the Coriolis force effect, the centrifugal and spin-spin polarization effects are considered in the calculation of the absoluteft values for the ΔN=2 beta transitions¹⁵⁵Eu→¹⁵⁵Gd. An important improvement is also obtained for the first forbidden transitions if the spin-spin polarization effects are taken into account.     

Zur Frage des Ansprechens eines offenen Geiger-Zählers auf Oberflächenladungen deformierter organischer Isolatoren

Ohne Zusammenfassung

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Thermal decomposition of complexes of antimony(III) bromide with hydrobromides of some aromatic amines

Thermal studies have been carried out on crystalline complexes formed between antimony(III) bromide and hydrobromides of some aromatic amines in concentrated hydrobromic acid solutions. Thermal analysis curves of the compounds under study are presented. Kinetic parameters of the thermal decomposition reactions were calculated from the TG curves using the Horowitz—Metzger method. A comparison of the thermal stabilities of the complexes was made.     

Mechanism of adsorption in cylindrical nanopores: the roles of fluctuations and correlations in stabilizing the adsorbed phase

The mechanism of the adsorption in nanometric cylindrical pores has been studied using grand canonical Monte Carlo simulations. The results have been analyzed from the point of view of microscopic correlations. It has been shown that the correlations between the energy components and between the energy and the number of adsorbed particles provide crucial information concerning the microscopic mechanism of the formation of adsorbed layers. Typical susceptibility functions have been calculated. They give the relations between the statistical correlations and the stability of the adsorbed system in different stages of adsorption. The numerical calculations have been carried out for Kr atoms adsorbed in an MCM-41 model porous material with pores of diameter d = 4 nm. The smooth-wall model as well as the model of a wall with micropores have been discussed.     

A facile synthesis of 1,1-bis(silyl)ethenes

Symmetrical 1,1-bis(silyl)ethenes have been easily prepared via ruthenium complex-catalyzed silylative coupling cyclization of 1,2-bis(dimethylvinylsiloxy)ethane to give 2,2,4,4-tetramethyl-3-methylene-1,5-dioxa-2,4-disilacycloheptane with excellent selectivity and good yield, followed by its reaction with Grignard reagents. The cyclic product can also be effectively transformed into cyclic carbosiloxane, 2,2,4,4,6,6,8,8-octamethyl-3,7-dimethylene-1,5-dioxa-2,4,6,8-tetrasilacyclooctane.     

Master equation simulations of bistable and excitable dynamics in a model of a thermochemical system

The effect of fluctuations on the dynamics of a model of a bistable thermochemical system is studied by means of the master equation. The system has three stationary states and exhibits two types of bistability: the coexistence of two stable focuses and the coexistence of a stable focus with a stable limit cycle separated by a saddle point. Stochastic effects are important when the system is close to the bifurcation, in which the stable limit cycle disappears through a homoclinic orbit. In this case the distribution of the first passage time from the stable limit cycle to the stable focus has a multipeak form. The dependence of this distribution on the number of particles is presented. Near the homoclinic orbit bifurcation, the system also exhibits excitability due to a particular shape of the basin of attraction of the stable focus.     

New catalytic route to functionalized vinylboronates

Vinylsubstituted boronates i.e. vinyldioxaborolane and vinyldioxaborinane react regioselectively with olefins in the presence of RuHCl(CO)(PCy3)2 with the formation of functionalized vinylboron derivatives. The reaction opens a new catalytic route for preparation of organoboranes.