Biosynthesis of aglajnes, polypropionate allomones of the opisthobranch mollusc Bulla striata

The biogenesis of aglajnes, polypropionate allomones of the cephalaspidean mollusc Bulla striata, has been investigated in vivo by feeding experiments. Incorporation of the committed precursor, [1-¹⁴C]-propionate, into aglajne-1 (1) and -3 (3) established the de novo origin of these compounds in B. striata. In the letter we also discuss briefly the ecological meaning of the origin of polypropionates in B. striata and in other cephalaspidean molluscs.     

The behaviour of stereoisomeric ions in the gas phase: 2—Negative and positive chemical ionization of cyclohexanehexacarboxylic methyl esters

The positive ion chemical ionization (CI (isobutane)), negative ion chemical ionization (NICI) electron attachment (CH₄, He) and NICI (OH^?) spectra of the title compounds have been studied in detail with the aid of deuterium-labelled derivatives. The obtained results show that under CI conditions the stereospecificity is retained. Interesting correlations with the condensed phase epimerization yields are emphasized.     

Carbometallate: Komplexe Anionenverbände [MoC4/26—] in der Kristallstruktur von Pr[MoIIC2]

Carbometalates: Complex Anions equation/tex2gif-stack-4.gif [MoC_4/2^6—] in the Crystal Structure of Pr equation/tex2gif-stack-5.gif [Mo^IIC₂] Criteria for the existence of carbometalates are established and discussed in a broader context. The concept is then applied to the novel compound Pr₂[MoC₂], which is characterized by chemical analyses, X‐ray diffraction and metallography. The crystal structure (tetragonal, P4₂/mnm, Z = 4, a = 581.29(8) pm, c = 1032.53(14) pm) consists of layered polyanions equation/tex2gif-stack-6.gif[MoC_4/2^6—] of distorted vertex and edge sharing MoC₄ tetrahedra. Praseodymium is also in a distorted tetrahedral coordination by carbon. The physical properties show “bad metal” behaviour and localized magnetic 4f‐moments in agreement with the existence of Pr³⁺‐species. A detailed bonding analysis using both the electron localization function ELF and the COHP method justifies the interpretation of the title compound as a carbomolybdate(II).     

Synthesis and properties of new glucocationic surfactants: model structures for marking cationic surfactants with carbohydrates

[reaction: see text] In this work, we report the synthesis of a new series of glucocationic surfactants, a class of surfactants we introduced very recently. The preparation of the surfactants is based on the synthesis of the 2-bromoethyl-2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside, whose preparation was studied in order to improve yields and stereoselectivity of this key intermediate. These glucocationic amphiphiles were prepared and studied as a model of cationic surfactants marked with a carbohydrate moiety. The use of carbohydrates as markers on cationic lipids was recently introduced to induce recognition by specific receptors, present on the surface of cell membranes. The chemicophysical characterization of these model structures can give more insight on the aggregation behavior. Conductivity and surface tension measurements were performed in order to characterize the compounds from the amphiphilic point of view. The results showed a different effect of the glucosidic moiety on the cmc value with respect to the glucopyridinium cationic surfactants. The surfactants also showed the tendency to form premicellar aggregates in solution when the hydrophobicity is raised.     

Ab initio SCF Calculation of the Fluoronium Ion: Geometry,electronic structure and vibrational constants

An ab initio SCF calculation of 42 points of the energy hypersurface of the fluoronium ion is presented using a contracted F(5s/3p), H(2s) gaussian basis set. In its equilibrium structure a bond length of 1.812 a.u. and a HFH bond angle of 127.2° are predicted. The calculated vibrational frequencies for H₂F⁺, HDF⁺, and D₂F⁺ are in good agreement with the experimental data.     

Global existence via Ginzburg-Landau formalism and pseudo-orbits of Ginzburg-Landau approximations

The so-called Ginzburg-Landau formalism applies for parabolic systems which are defined on cylindrical domains, which are, close to the threshold of instability, and for which the unstable Fourier modes belong to non-zero wave numbers. This formalism allows to describe an attracting set of solutions by a modulation equation, here the Ginzburg-Landau equation. If the coefficient in front of the cubic term of the formally derived Ginzburg-Landau equation has negative real part the method allows to show global existence in time in the original system of all solutions belonging to small initial conditions, inL . Another aim of this paper is to construct a pseudo-orbit of Ginzburg-Landau approximations which is close to a solution of the original system up tot=. We consider here as an example the socalled Kuramoto-Shivashinsky equation to explain the methods, but it applies also to a wide class of other problems, like e.g. hydrodynamical problems or reaction-diffusion equations, too.     

Unbiased Bayes estimates and improper priors

Given two random variables (X, Y) the condition of unbiasedness states that:E(X |Y=y)=y andE(Y |X=x)=x both almost surely (a.s.). If the prior onY is proper and has finite expectation or non-negative support, unbiasedness impliesX=Y a.s. This paper examines the implications of unbiasedness when the prior onY is improper. Since the improper case can be meaningfully analysed in a finitely additive framework, we revisit the whole issue of unbiasedness from this perspective. First we argue that a notion weaker than equality a.s., named coincidence, is more appropriate in a finitely additive setting. Next we discuss the meaning of unbiasedness from a Bayesian and fiducial perspective. We then show that unbiasedness and finite expectation ofY imply coincidence betweenX andY, while a weaker conclusion follows if the improper prior onY is only assumed to have positive support. We illustrate our approach throughout the paper by revisiting some examples discussed in the recent literature.This work was partially supported by C.N.R. grant N.80.02970.10 (G.C.) and by C.N.R. grant altri interventi (P.V.). A preliminary draft was written while the Authors were visiting the Department of Statistics at Carnegie Mellon University.The paper is the result of close cooperation between the two authors. However subsections 3.1 and 3.3 are mainly due to G.C. while subsection 3.2 and section 4 are mainly due to P.V.     

Structures and magnetic properties of tetranuclear nickel(II) complexes with unusual mu3-1,1,3 azido bridges

Pyrazolate-based dinucleating ligands with thioether-containing chelate arms have been used for the synthesis of a family of novel tetranuclear nickel(II) complexes [L2Ni4(N3)3(O2CR)](ClO4)2 that incorporate three azido bridges and one carboxylate (R = Me, Ph). Molecular structures have been elucidated by X-ray crystallography in four cases, revealing Ni4 cores with a unique topology in which two of the azido ligands adopt an unusual mu3-1,1,3 bridging mode. The compounds were further characterized by mass spectrometry, IR spectroscopy, and variable-temperature magnetic susceptibility measurements. Magnetic data analyses indicate a combination of significant intramolecular ferromagnetic and antiferromagnetic exchange interactions that give rise to an overall S(T) = 0 ground state. The sign and the magnitude of the individual couplings have been rationalized in the framework of the common magnetostructural correlations for end-to-end and end-on azido linkages, suggesting that these correlations also remain valid for the respective fragments of multiply bridging mu3-1,1,3 azido ligands.