Research on the aromas. On the aroma of coffee. I

The analysis of a coffee concentrate is described: 202 constituents have been identified, 154 of which for the first time. Some of these compounds are new chemicals; their synthesis is described. Most identifications are based upon mass spectrometry combined in many cases with IR. spectrometry and comparison with reference compounds. MS. and IR. data are given in detail. The analysis shows that a large number of minor constituents is present, many of which could not be identified.     

Synthese de diterpenes tetracycliques du type hibane

Hibaone has been synthesized from manool through a photochemical cycloaddition of Δ⁸⁽¹⁴⁾ podocarpene-13-one to ethylene or 1,2 dichloroethylene.     

Perturbative solution of the RPA equation. An application to the calculation of rotational strengths

The RPA equation is solved by perturbation in Møller-Plesset (MP) and Epstein-Nesbet (EN) partitions, which are first compared on a specific example. To still accelerate the faster one (EN), a third scheme is proposed, which involves preliminary diagonalization within a limited subset , followed by usual EN perturbation between and the rest of the whole configuration space. Criteria for the choice of are given.     

Activite optique de la methyl-3 cyclopentenanone; un calcul ab initio

Ab initio calculations for two conformers of 3-methyl cyclopentanone, with and without 3d orbitals, show that inclusion of d orbitals on the carbonyl group lower energies and is thus necessary, as follows from the variation principle; it also markedly affects rotatory strengths of the n→π^* and π→π^* transitions, but conformational equilibria of the cyclic skeleton and the methyl group are almost independent of the basis chosen. Internal rotation of the methyl group exerts a negligible influence on the rotatory strength of the n→π^* transition, so that this group can be considered as a sphere in this respect.     

Force field for platinum binding to adenine

The antitumor drug cis-diamminedichloroplatinum(II) (cisplatin) binds preferentially to GpG and ApG sequences of DNA, forming N7,N7 intrastrand chelates. Molecular modeling of the intrastrand adducts have been handicapped, so far, by the lack of force-field data describing the Pt–guanine and Pt–adenine binding. We used ab initio calculations with relativistic pseudopotentials to evaluate three important parameters for the platinum–adenine model complex [Pt(NH₃)₃(Ade)]²⁺: (1) the force constant for the Pt? N7 bond bending out of the adenine plane; (2) the energy profile for the torsion about Pt? N7; (3) a set of fractional atomic charges that reproduce the ab initio potential for a number of space points placed around the adduct. A population analysis and comparative study on the tetrammine complex [Pt(NH₃)₄]²⁺ have shown that for platinum adenine is a better σ-donor than NH₃, but its capacity as a π-acceptor is weak. © 1993 John Wiley & Sons, Inc.     

Electron irradiation-enhanced core/shell organization of Al(Cr,Fe, Mn)Si dispersoids in Al–Mg–Si alloys

The age hardening 6061-T6 aluminium alloy has been chosen as structural material for the core vessel of the material testing Jules Horowitz nuclear reactor. The alloy contains incoherent Al(Cr, Fe, Mn)Si dispersoids whose characterization by energy-filtered transmission electron microscopy (EFTEM) analysis shows a core/shell organization tendency where the core is (Mn, Fe) rich, and the shell is Cr rich. The present work studies the stability of this organization under irradiation. TEM characterization on the same particles, before and after 1 MeV electron irradiation, reveals that the core/shell organization is enhanced after irradiation. It is proposed that the high level of point defects, created by irradiation, ensures a radiation-enhanced diffusion process favourable to the unmixing forces between (Fe, Mn) and Cr. Shell formation may result in the low-energy interface segregation of Cr atoms within the (Fe, Mn) system combined with the unmixing of Cr, Fe and Mn components.     

Recherches sur les arǒmes, 18e communication Sur l'arǒme de viande de boeuf grillée,I. Pyrazines

A combined gas chromatography-mass spectrometry analysis of roasted meat flavor prepared by pyrolysis of water-soluble components of fresh beef has yielded 17 alkylpyrazines (5 already found in heated beef fat), one being a new flavor compound. The mass spectrum of this compound is given.     

Undulation instability in two-dimensional foams of magnetic fluid

Two-dimensional magnetic fluid foams are cellular structures whose framework is made of magnetic fluid. The features of these equilibrated patterns are driven by a control parameter: the amplitude of the applied magnetic field. When the latter is rapidly increased, an instability occurs: the walls between cells undulate. Such an instability has also been observed in other 2D cellular structures, which exist for instance in Langmuir monolayers or in magnetic garnets thin films. In this paper we give a theoretical analysis of this instability, the issues of which are shown to be well confirmed by experiments and numerical simulations. Received: 13 October 1997 / Received in final form: 28 January 1998 / Accepted: 9 March 1998     

Determination of contracted atomic basis sets for the study of CN; application to the MCSCF calculations of its spectroscopic constants

Contracted atomic basis sets have been constructed from ANOs in order to describe the ground and excited states of C and N and their anions. Application is given with the MCSCF calculation of the vibration frequency of CN⁻ and of other spectroscopic constants. A procedure is proposed to do MCSCF calculations when some problems of convergence arise.