Siloxane-Based Nanobuilding Blocks by Reaction Between Silanediol and Trifunctional Silicon Alkoxides

The preparation of nanostructured organic-inorganic materials by assembling of nanobuilding blocks allows controlling the extent of phase interaction, which in its turn governs structure-properties relationships. We present here the synthesis of siloxane-based nanobuilding blocks prepared by reacting diphenylsilanediol with vinyltriethoxysilane and triethoxysilane. The reaction products were obtained by non-hydrolytic condensation between silanediol and ethoxide groups in inert atmosphere, in the presence of pyridine, triethylamine or butyl lithium. Different synthetic conditions were examined by means of ATR-FTIR and NMR spectroscopies, showing the formation of siloxane bonds. In the case of triethoxysilane the reaction carried out in the presence of pyridine leads to Si–H bond preservation in the final product. Air stable products with improved Si–O–Si hydrolytic stability can be obtained by removal of the base after the reaction completion. The condensation products can be described as a mixture of siloxane rings involving difunctional and trifunctional silicon units.     

Gas-phase ion/molecule reactions between dimethoxyphosphonium ions and aromatic hydrocarbons

Ion/molecule reactions between O=P(OCH(3))(2)(+) phosphonium ions and six aromatic hydrocarbons (benzene, toluene, 1,2,4-trimethylbenzene, naphthalene, acenaphthylene and fluorene) were performed in a quadrupole ion trap mass spectrometer. The O=P(OCH(3))(2)(+) phosphonium ions, formed by electron impact from neutral trimethyl phosphite, were found to react with aromatic hydrocarbons (ArHs) to give (i) an adduct [ArH, O=P(OCH(3))(2)](+) and (ii) for ArHs which have an ionization energy below or equal to 8.14 eV, a radical cation ArH(+ *) by charge transfer reaction. Collision-induced dissociation experiments, which produce fragment ions other than the O=P(OCH(3))(2)(+) ions, indicate that the adduct ions are covalent species. Isotope-labeled ArHs were used to elucidate fragmentation mechanisms. The charge transfer reactions were investigated using density functional theory at the B3LYP/6-311 + G(3df,2p)//B3LYP/6-31G(d,p) level of theory. The potential energy surface obtained from B3LYP/6-31G(d,p) calculations for the reaction between O=P(OCH(3))(2)(+) and benzene is described.     

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Pressure broadening study at low temperature: application to methane

We studied the R(0) line profile in the CH4 v4 band from room temperature to 188 K with N2 as a perturber, to 100 K with O2 as perturber, and from room temperature to 15 K using He as a perturber. The N2 and O2 measurements were performed over a total pressure range of 15-110 mbar, and for the He measurements the maximum sample pressure at 15 K was 1.10 mbar. Broadening parameters were determined, taking into account the confinement narrowing (Dicke effect), and narrowing parameters, deduced from the soft or hard collision model, are compared with the dynamic friction coefficient calculated values. We also obtained preliminary values for the temperature dependence of the N2, O2 and He line broadening parameters for this transition.     

Nucleon-nucleon interaction and some reactions with3He,3H

Experimental measurements and theoretical calculations are discussed for theA = 3 nuclei. With the sum rule formalism, the need for a better bound state is investigated. Some reactions on³He and³H like electron scattering, photodisintegration,-capture involve transitions to the continuum but with the work developed by Merkuriev, Gignoux and Laverne (1976) some progress is possible. The same realisticNN interactions used for calculating the bound state wave function of the three nucleon system are incorporated in the scattering equations based on the Faddeev approach.Presented at the symposium Mesons and Light Nuclei, Bechyn, Czechoslovakia, May 27–June 1, 1985.     

Coloring of universal graphs

LetG be a graph andr a cardinal number. Extending the theorem of J. Folkman we show that if eitherr or clG are finite then there existsH with clH = clG andH (G) _r ¹ . Answering a question of A. Hajnal we show that countably universal graphU ₃ satisfiesU ₃ (U₃) _r ¹ for every finiter.     

Surface characterization of three marine bacterial strains by Fourier transform IR, X-ray photoelectron spectroscopy, and time-of-flight secondary-ion mass spectrometry, correlation with adhesion on stainless steel surfaces

Adhesion of bacterial strains on solid substrates is likely related to the properties of the outer shell of the micro-organisms. Aiming at a better understanding and control of the biofilm formation in seawater, the surface chemical composition of three marine bacterial strains was investigated by combining Fourier transform IR spectroscopy, X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary-ion mass spectrometry (ToF-SIMS). The D41 strain surface showed evidence of proteins, as deduced from the NH2 and NCO XPS and ToF-SIMS fingerprints; this strain was found to adhere to stainless steel, glass, or Teflon surfaces in a much higher quantity (2 orders of magnitude) than the two other ones, DA and D01. The latter are either enriched in COOH or sulfates, and this makes them more hydrophilic and less adherent to all substrates. Correlations with physicochemical properties and adhesion seem to demonstrate the role of the external layer composition, in particular the role of proteins more than that of hydrophobicity, on their adhesion abilities.     

The synthesis of imidazole-2-thione nucleosides

Ribosylation of the trimethylsilyl derivative ( 1b ) of imidazole-2-thione ( 1a ) using either stannic chloride or silver perchlorate as catalyst resulted in the formation of the acylated derivatives of 1-(β-D-ribofuranosyl)imidazole-2-thione ( 3c ) and 1,3-di-(β-D-ribofuranosyl)imidazole-2-thione ( 4c ) with the latter predominating ( 4c:3c , ca. 2:1 ). The diribosylated nucleoside 4c was shown to be the N,N-disubstituted product rather than the N,S-disubstituted product by ¹H nmr and ¹³C nmr spectroscopy. Employment of the iodine-catalyzed fusion procedure reversed the aforementioned product ratios and provided the monoriboside 3c in excellent yield. When the trimethylsilyl derivative ( 5b ) of 2-methylthioimidazole ( 5a ) was reacted with 2,3,5-tri-O-benzoyl-D-ribofuranosyl bromide ( 2d ) in acetonitrile, the major product was 1,3-di-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-imidazole-2-thione ( 4b ). The formation of 4b in this reaction is thought to arise via the Hilbert-Johnson mechanism.