Ionization potentials and geometrical structure of pure and oxygenated barium clusters

In this article, we present results obtained on structures of small bare and oxygenated barium clusters produced by the laser vaporization technique. Contrary to the very weak Ba—Ba binding (0.202 eV), the Ba—O binding is rather strong (5.8 eV). As a consequence, extremely small amounts of oxygen in the cluster source are sufficient to induce the nucleation of oxygenated barium clusters. Surprisingly, at least for substoechiometric systems, Ba_nO_m clusters exhibit the same icosahedral structure as bare clusters do. Mass spectra seem to indicate that replacing a barium atom with a strongly polar BaO molecule does not affect the geometrical structure of the cluster. This aspect is more easily understandable if we assume that the oxygen atom takes place inside the structure of the Ba_n cluster without significant distortions. Ab-initio calculations have been undertaken in order to give a satisfactory account of this hypothesis.     

Optimal pricing for a heterogeneous portfolio for a given risk factor and convex distance measure

Consider a portfolio containing heterogeneous risks. The premiums of the policyholders might not cover the amount of the payments which an insurance company pays the policyholders. When setting the premium, this risk has to be taken into consideration. On the other hand the premium that the insured pays has to be fair. This fairness is measured by a function of the difference between the risk and the premium paid—we call this function a distance function. For a given small probability of insolvency, we find the premium for each class, such that the distance function is minimized. Next we formulate and solve the dual problem, which is minimizing the insolvency probability under the constraint that the distance function does not exceed a given level. This paper generalizes a previous paper [Zaks, Y., Frostig, E., Levikson, B., 2006. Optimal pricing of a heterogeneous portfolio for a given risk level. Astin Bull. 36 (1), 161–185] where only a square distance function was considered.     

Correct structures of Diels-Alder adducts from the natural cyclolignan thuriferic acid and its 8-epimer

A detailed analysis of one- and two-dimensional ¹H and ¹³C NMR data for the endo and the exo adducts, obtained by Diels-Alder reaction of thuriferic and epithuriferic acids with cyclopentadiene is described. The unequivocal spectral data assignment of the endo and exo structures was complemented with molecular modelling studies and confirmed through X-ray diffraction studies.     

High yield synthesis and reactivity of a phosphinidene bridged dimolybdenum complex

Protonation of [Mo2Cp2(mu-H)(mu-PHR*)(CO)4] (Cp = eta5-C5H5, R* = 2,4,6-C6H2tBu3) with HBF4.OEt2 gives the hydridophosphinidene complex [Mo2Cp2(mu-H)(mu-PR*)(CO)4]BF4, which is easily deprotonated with H2O to give the known phosphinidene complex [Mo2Cp2(mu-PR*)(CO)4] in 95% yield. Reaction of the latter with I2 gives the unsaturated phosphinidene complex [Mo2Cp2I2(mu-PR*)(CO)2], which exhibits an intermetallic distance of 2.960(2) A. Irradiation of solutions of [Mo2Cp2(mu-PR*)(CO)4] with UV light gives a mixture of the triply bonded [Mo2Cp2(mu-PR*)(mu-CO)2] and the hydridophosphido derivative [Mo2Cp2(mu-H){mu-P(CH2CMe2)C6H2tBu2}(CO)4] as major species. The latter complex results from an intramolecular C-H bond cleavage from a tBu group and has been characterized by spectroscopy and an X-ray study. Irradiation in the presence of HCC(p-tol) results in the insertion of the alkyne into the Mo-P bond to give [Mo2Cp2{mu-eta1:eta2,kappa-C(p-tol)CHPR*}(CO)4] structurally characterized through an X-ray study.     

Substituent effects on the photophysical properties of pterin derivatives in acidic and alkaline aqueous solutions

Pterins are heterocyclic compounds with important biological functions, and most of them may exist in two acid-base forms in the pH range between 3 and 13 in aqueous solution. In this work, the photophysical properties of acid and basic forms of six compounds of the pterin family (6-hydroxymethylpterin [HPT], 6-methylpterin [MPT], 6,7-dimethylpterin [DPT], rhamnopterin [RPT], N-methylfolic acid [MFA], and pteroic acid [PA]) have been studied. The effects of the chemical nature of the substituents at position 6 of the pterin moiety and the effects of the pH on the absorption and emission properties are analyzed. The fluorescence characteristics (spectra, quantum yields, lifetimes) of these compounds have been investigated using the single-photon-counting technique. Results obtained for pterin derivatives containing small substituents with 1 carbon atom (HPT, MPT, DPT) and short hydrocarbon chain (4 carbon atoms) (RPT) are different from those found for pterin derivatives containing a p-aminobenzoic acid (PABA) moiety in the substituent (MFA and PA). Fluorescence quantum yields (Phi(F)) of the first group of compounds are relatively high (>/=0.4), whereas MFA and PA exhibit very small Phi(F) values (相似文献   

Design and synthesis of aromatic inhibitors of anthranilate synthase

Aromatic analogues of chorismate were synthesised as potential inhibitors of anthranilate synthase. Molecular modelling using GOLD2.1 showed that these analogues docked into the active site of Serratia marcescens anthranilate synthase in the same conformation as chorismate. Most compounds were found to be micromolar inhibitors of S. marcescens anthranilate synthase. The most potent analogue, 3-(1-carboxy-ethoxy)-4-hydroxybenzoate (K(I) 3 microM), included a lactyl ether side chain. This appears to be a good replacement for the enol-pyruvyl side chain of chorismate.     

Residual entropy of glasses and their relation with the crystallization behaviour

For the alloy of eutectic composition in the quasibinary GeSe₂-Sb₂Se₃ system the heat capacities of the glass, undercooled and stable liquid and crystalline phases have been measured using differential scanning calorimetry. Enthalpy, entropy and Gibbs free energy differences of vitreous and crystalline forms have been deduced for this alloy. The kinetic parameters of crystallization for glasses of nearby composition have been obtained by continuous heating experiments. The effective activation energy obtained has a value that accounts for the activation energy for nucleation calculated using simple nucleation theory formulae.

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Zusammenfassung Die Wärmekapazitäten von Glas, unterkühlter und stabiler Flüssigkeit und kristallinen Phasen von Mischungen der eutektischen Zusammensetzung des quasibinären Systems GeSe₂-Sb₂Se₃ werden mittels DSC gemessen. Aus den Ergebnissen werden Enthalpie, Entropie und freie Enthalpie der glasartigen und kristallinen Formen dieser Mischung abgeleitet. Die kinetischen Parameter der Kristallisation von Gläsern benachbarter Zusammensetzungen wurden durch temperaturprogrammierte Untersuchungen ermittelt. Die erhaltenen effektiven Aktivierungsenergien entsprechen dem für die Keimbildung nach einfachen theoretischen Formeln berechneten Wert.

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, , GeSe₂-Sb₂Se₃. , . . , .

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This research was supported by the Comisión Asesora de Investigatión Cientifica y Técnica (CAICYT) project no. 759-84 which is gratefully acknowledged.     

Crystallization kinetic studies: A means to evaluate time-temperature-transformation curves. Application to metallic glasses

It is shown that the study of the kinetics of crystallization of an amorphous alloy may be used to obtain the correct form of the low temperature part of the time-temperature-transformation (T-T-T) curves. A unified review of the current kinetics of crystallization studies is presented and the general kinetic equation which gives the reaction rate as a function of temperature and crystalline fraction is shown to contain information related to theT-T-T-curves. Finally examples of application to two metallic glasses, Nd₃Fe₇₇B₂₀ and Fe_67.5Co₁₅Nb_1.5B₁₆, obtained by rapid solidification techniques are presented. The comparison between theory and experiment is satisfactory.

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Zusammenfassung Es wird gezeigt, daß die Untersuchung der Kristallisationskinetik von amorphen Legierungen genutzt werden kann, die korrekte Form des Niedertemperaturbereiches der Zeit-Temperatur-Transformation (T-T-T) Kurven zu erhalten. Es wird ein einheitlicher Überblick über die jüngsten Untersuchungen von Kristallisationskinetiken gegeben und an der allgemeinen Gleichung der Reaktionsgeschwindigkeit als eine Funktion von Temperatur und Kristallanteil wird gezeigt, daß sie Informationen bezüglich der T-T-T-Kurven beinhaltet. Letztlich wird eine Anwendung an zwei, durch schnelles Erstarren gewonnenen metallischen Gläsern Nd₃Fe₇₇B₂₀ und Fe_67.5Co₁₅Nb_1.5B₁₆ dargelegt. Zwischen Theorie und Praxis konnte eine ausreichende Übereinstimmung festgestellt werden.

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Dedicated to Professor Dr. H. J. Seifert on the occasion of his 60^th birthday

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This work was supported by the Comision Interdepartamental de Cienca y Tecnologia, CICYT (project No. MAT88-0439) which are acknowledged.     

Evaluation of micellar liquid chromatography and capillary zone electrophoresis for dope control in sport

Micellar liquid chromatography (MLC) and capillary zone electrophoresis (CZE) have been evaluated for the analysis of twelve banned drugs in sport including diuretics and -blockers. In MLC, a sodium dodecylsulphate aqueous solution has been used as mobile phase using an octadecylsilica column. In CZE, a pH 8 buffer solution and a silica capillary have been employed. Parameters of retention and efficiency have been compared. Limits of detection with UV detection at 254 nm and relative standard deviations for atenolol, furosemide, nadolol, spironolactone and triamterene were established and compared in both techniques. Examples of direct urine injection into the separation systems are presented. Drugs overlapping in MLC are well resolved in CZE, while the opposite is true for a limited number of drugs. Some interferences from urine may arise in CZE. The selectivity of analysis would be greatly enhanced by using both techniques, which require only filtration as pre-treatment.