Säurekatalysierte Umlagerungen von 1,5-Dimethyl-6-methyliden-tricyclo[3.2.1.02,7]oct-3-en-8endo-olen

Acid Catalysed Rearrangement of 1,5-Dimethyl-6-methyliden-tricyclo[3.2.1.0^2,7]oct-3-en-8endo-ols The tricyclic alcohols 2,3,4 and 6 (Scheme 1) are synthesized by the reaction of the tricyclic ketone 1 with sodiumborohydrid or metalloorganic reagents. Their configuration at C(8) is determined by NMR. in the presence of Eu(fod)₃. The exo-attack of 1 by the nucleophil forming the endo-alcohol is favored, the π-electrons of C(3) = C(4) hindering the endo-attack. On treatment with sulfuric acid in dioxane/water at 25° the tertiary alcohols yield aryl-substituted ketones. 3 gives in 78.5% yield a mixture of the 3-(dimethylphenyl)-2-butanones 12 and 13 , in addition to 16.5% of (2,3,4-trimethylphenyl)-2-propanon ( 14 ) (Scheme 2). The alcohols 4 and 6 yield mixtures of the 2-(dimethylphenyl)-3-pentanones 19 and 20 (72%), and 2-(dimethylphenyl)-propiophenones 21 and 22 (68%), respectively (Scheme 2). In the case of the secondary alcohol 2 mainly products derived from hydration at the C(6), C(9) double bond are formed, namely the mixture of diols 23 and 24 (21%), and the mixture of the isomeric 2-(dimethylphenyl)propanals 25, 26 and 27 (3%) (Scheme 3). - The structures of 12–14, 19/20, 21/22, 23/24 and 25/26/27 were established by spectroscopic data. In the case of 12 and 13 the degradation of their mixture to the known 1-(dimethylphenyl)ethanols 17/18 confirmed the assignment. - The most probable mechanism for the rearrangement of 3 is shown in Schemes 4 and 5. The reaction proceeds from 3 through a, b and g to 12 and 13; 14 is formed via e, f and i . In the case of 4 and 6 only the reaction analogue to 3 → a → b → g ?12/13 takes place. The isomeric aldehyds 25–27 formed from 2 could have the structures s, t , and v . The former two could be generated in a similar way as 12/13 from 3 , the latter one as shown in Scheme 8.     

Eptastigmine,nicotinamide and nicotinic acid determination using an inhibition enzyme sensor; application to pharmaceutical analysis

An enzyme inhibition biosensor, developed in our laboratory and previously used for the analysis of compounds with anticholinesterase activity (e.g. physostigmine, neostigmine, pyridostigmine nicotine and organophosphorus compounds) has now been tested for the analysis of another recently synthesized cholinesterase inhibitor, i.e. eptastigmine. In addition nicotinic acid and nicotinamide, although displaying weaker inhibition properties, were also tested in pharmaceutical products using the same inhibition enzyme sensor. The biosensor consisted of a hydrogen peroxide amperometric electrode coupled to a functionalised nylon membrane chemically bonding both the enzymes butyrylcholinesterase and choline oxidase; a butyrylcholine standard solution in glycine buffer acted as substrate. The response of the system to all the inhibitors considered was characterised completely and the analysis of several pharmaceutical formulations containing nicotinamide or nicotinic acid was also performed.     

Un teorema di Radon-Nikodym per funzioni d’insieme subadditive

Riassunto In questo articolo si danno delle condizioni necessarie e sufficienti affinchè per una fissata coppia di funzioni d’insieme ν, μ crescenti esista una funzionef tale che ν=∫fdμ. Si ottiene cosi una proposizione comprendente il teorema di R-N. classico e dei teoremi di R-N., presentati da altri autori, riguardanti le funzioni d’insieme finitamente additive e le funzioni d’insieme subadditive e continue per successioni crescenti.

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Résumé Soient ν, μ:A→[0,+∞) deux fonctions d’ensemble croissantes sur une σ-algèbre d’ensemblesA⊂T(X), telles que pour chaqueA∈A avec ν(A)=μ(A)=0 on a l’égalité μ(A)=μ(A∪S) ∀S∈A (c’est le cas des fonctions sousadditives!). Dans cet article on démontre qu’il existe une fonctionf A-measurable telle que ν=∫fdμ si et seulement si pour chaquer∈(0, + ∞) il y a un ensembleA _r∈A qui vérifie les trois conditions suivantes: (1) ,B∈A avecB⊂A; (2) A (3) limν(A _r)=0. On déduit ainsi une proposition qui a été donnée parI. Forana: ?Si ν, μ sont simplement additives, il existe une fonctionf telle que ν=∫fdμ si et seulement si ν≪μ et la fonction d’ensemble additive a une decomposition de Hahn pour chaquer∈(0, + ∞), c’est-á-dire il y aA _r∈A tel que ?.

     

Ground state rotational spectrum of nitrogen trifluoride: The K = 3 splittings of NF3 and NF3

The ground state rotational spectrum of the ¹⁴NF₃ and ¹⁵NF₃ isotopic species of nitrogen fluoride has been observed in the ∼450-810 GHz frequency range. This investigation allowed us to improve the rotational parameters for both isotopologues. In particular, for the first time the K = 3 line splitting parameter and the sextic centrifugal distortion constants have been determined for ¹⁵NF₃.     

Kerr metric,geodesic motion,and Flyby Anomaly in fourth-order Conformal Gravity

In this paper we analyze the Kerr geometry in the context of Conformal Gravity, an alternative theory of gravitation, which is a direct extension of General Relativity (GR). Following previous studies in the literature, we introduce an explicit expression of the Kerr metric in Conformal Gravity, which naturally reduces to the standard GR Kerr geometry in the absence of Conformal Gravity effects. As in the standard case, we show that the Hamilton–Jacobi equation governing geodesic motion in a space-time based on this geometry is indeed separable and that a fourth constant of motion—similar to Carter’s constant—can also be introduced in Conformal Gravity. Consequently, we derive the fundamental equations of geodesic motion and show that the problem of solving these equations can be reduced to one of quadratures. In particular, we study the resulting time-like geodesics in Conformal Gravity Kerr geometry by numerically integrating the equations of motion for Earth flyby trajectories of spacecraft. We then compare our results with the existing data of the Flyby Anomaly in order to ascertain whether Conformal Gravity corrections are possibly the origin of this gravitational anomaly. Although Conformal Gravity slightly affects the trajectories of geodesic motion around a rotating spherical object, we show that these corrections are minimal and are not expected to be the origin of the Flyby Anomaly, unless conformal parameters are drastically different from current estimates. Therefore, our results confirm previous analyses, showing that modifications due to Conformal Gravity are not likely to be detected at the Solar System level, but might affect gravity at the galactic or cosmological scale.     

Rotational Analysis of the ΔvSiH=3-6 Stretching Vibrational Overtones of HSiD3

The nν₁ SiH stretching overtone transitions of trideuterosilane, HSiD₃, have been recorded by Fourier transform spectroscopy (n=3 and 4) and by intracavity laser absorption spectroscopy (n=5 and 6). The unusually weak 3ν₁ band is affected by considerable intensity and energy perturbations. The 4ν₁ band is also strongly perturbed but the interaction with the dark states is more limited and part of the rotational structure of the v₁=4 upper state could be satisfactorily modeled. Less pronounced perturbations affect the v₁=5 level, newly detected by ICLAS. Its rotational structure is locally perturbed by anharmonic coupling with an unidentified vibrational dark state. The global modeling of the interacting dyad allowed the determination of the perturber parameters and the assignment of extra lines due to an intensity transfer from the v₁=5 bright state to the dark state. In agreement with a previous ICLAS study, the 6ν₁ band near 12 113 cm⁻¹ was found free of perturbation. About six hundred line positions could be reproduced with an rms of 4.6×10⁻³ cm⁻¹, leading to a significantly improved set of rovibrational parameters. The striking evolution of the rotational structure, which exhibits fewer and fewer perturbations when the SiH excitation increases, is discussed.     

A kinematical approach to conformal cosmology

We present an alternative cosmology based on conformal gravity, as originally introduced by H. Weyl and recently revisited by P. Mannheim and D. Kazanas. Unlike past similar attempts our approach is a purely kinematical application of the conformal symmetry to the Universe, through a critical reanalysis of fundamental astrophysical observations, such as the cosmological redshift and others. As a result of this novel approach we obtain a closed-form expression for the cosmic scale factor R(t) and a revised interpretation of the space–time coordinates usually employed in cosmology. New fundamental cosmological parameters are introduced and evaluated. This emerging new cosmology does not seem to possess any of the controversial features of the current standard model, such as the presence of dark matter, dark energy or of a cosmological constant, the existence of the horizon problem or of an inflationary phase. Comparing our results with current conformal cosmologies in the literature, we note that our kinematic cosmology is equivalent to conformal gravity with a cosmological constant at late (or early) cosmological times. The cosmic scale factor and the evolution of the Universe are described in terms of several dimensionless quantitites, among which a new cosmological variable δ emerges as a natural cosmic time. The mathematical connections between all these quantities are described in details and a relationship is established with the original kinematic cosmology by L. Infeld and A. Schild. The mathematical foundations of our kinematical conformal cosmology will need to be checked against current astrophysical experimental data, before this new model can become a viable alternative to the standard theory.