Classification of wines by means of multivariate data analysis using the SPME/CGC-chromatograms of volatile aroma compounds

The solid phase microextraction (SPME) is an effective solvent-free sample preparation technique for the capillary gas chromatographic (CGC) analysis of volatile aroma compounds of wines. Using discriminant analysis based upon only two terpene compounds, it was possible to analytically discern between the varieties Riesling, Muller-Thurgau and Silvaner grown in the same region. The discrimination of these varieties was unsuccessful for wines of different vintages (1988-1995). In order to obtain a highly significant classification, it was necessary to consider further aroma components described in wine literature. The differentiation between these wines by a similar high classification rate was obtained using a set of variables selected by mathematical methods. Wines prepared from known grape varieties were qualitatively recognized by factor- and cluster-analyses as well as the relative peak intensities of the terpene compounds in the SPME-CGC chromatograms. The composition of wine blends was quantitatively determined

Solid-phase molecular recognition of cytosine based on proton-transfer reaction. Part II. supramolecular architecture in the cocrystals of cytosine and its 5-Fluoroderivative with 5-Nitrouracil

<p>Abstract</p> <p>Background</p> <p>Cytosine is a biologically important compound owing to its natural occurrence as a component of nucleic acids. Cytosine plays a crucial role in DNA/RNA base pairing, through several hydrogen-bonding patterns, and controls the essential features of life as it is involved in genetic codon of 17 amino acids. The molecular recognition among cytosines, and the molecular heterosynthons of molecular salts fabricated through proton-transfer reactions, might be used to investigate the theoretical sites of cytosine-specific DNA-binding proteins and the design for molecular imprint.</p> <p>Results</p> <p>Reaction of cytosine (Cyt) and 5-fluorocytosine (5Fcyt) with 5-nitrouracil (Nit) in aqueous solution yielded two new products, which have been characterized by single-crystal X-ray diffraction. The products include a dihydrated molecular salt (CytNit) having both ionic and neutral hydrogen-bonded species, and a dihydrated cocrystal of neutral species (5FcytNit). In CytNit a protonated and an unprotonated cytosine form a triply hydrogen-bonded aggregate in a self-recognition ion-pair complex, and this dimer is then hydrogen bonded to one neutral and one anionic 5-nitrouracil molecule. In 5FcytNit the two neutral nucleobase derivatives are hydrogen bonded in pairs. In both structures conventional N-H^...O, O-H^...O, N-H^+...N and N-H^...N^-intermolecular interactions are most significant in the structural assembly.</p> <p>Conclusion</p> <p>The supramolecular structure of the molecular adducts formed by cytosine and 5-fluorocytosine with 5-nitrouracil, CytNit and 5FcytNit, respectively, have been investigated in detail. CytNit and 5FcytNit exhibit widely differing hydrogen-bonding patterns, though both possess layered structures. The crystal structures of CytNit (D<it>p</it>k_a= -0.7, molecular salt) and 5FcytNit (D<it>p</it>k_a= -2.0, cocrystal) confirm that, at the present level of knowledge about the nature of proton-transfer process, there is not a strict correlation between the D<it>p</it>k_avalues and the proton transfer, in that the acid/base <it>p</it>k_astrength is not a definite guide to predict the location of H atoms in the solid state. Eventually, the absence in 5FcytNit of hydrogen bonds involving fluorine is in agreement with findings that covalently bound fluorine hardly ever acts as acceptor for available Brønsted acidic sites in the presence of competing heteroatom acceptors.</p

The Forgotten Tradition. How the Logical Empiricists missed the Philosophical Significance of the work of Riemann, Christoffel and Ricci

Abstract. The paper attempts to show how the Logical Empiricists’ interpretation of the relation between geometry and reality emerges from a “collision” of mathematical traditions. Considering Riemann’s work as the initiator of a 19th century geometrical tradition, whose main protagonists were Helmholtz and Poincaré, the Logical Empiricists neglected the fact that Riemann’s revolutionary insight flourished rather in a non-geometrical tradition dominated by the works of Christoffel and Ricci-Curbastro roughly in the same years. I will argue that in the attempt to draw the line Riemann-Helmholtz-Poincaré-Einstein Logical Empiricists were led to argue that General Relativity raised mainly a problem of mathematical under-determination, i.e. the discovery that there are physical differences that cannot be expressed in the relevant mathematical structure of the theory. However, a historical reconstruction of the alternative line of development Riemann-Chritoffel-Ricci-Einstein shows on the contrary that the main philosophical issue raised by Einstein’s theory was rather that of mathematical over-determination, i.e. the recognition of the presence of redundant mathematical differences that do not have any correspondence in physical reality