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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 137-150 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Supports consisting of a thin layer (2-10%) of polystyrene (PS) grafted onto a poly(tetrafluoroethylene) (PTFE) core are an interesting alternative to controlled pore glass (CPG) carriers in oligonucleotide synthesis. The beads are mechanically stable, do not show significant swelling, and allow effective removal of substrates by short washing steps with organic solvents. PTFE-PS as an organic polymer has generally more hydrophobic properties than inorganic polymer supports and, therefore, is well compatible with organic solvents such as anhydrous MeCN. We found PTFE with a content of 2-3% PS graft to be a very good support for the synthesis of oligonucleotides of extended length. In comparison, PTFE with 5-10% grafted PS is especially useful for large-scale syntheses. Functionalization procedures minimized in the extent of side reactions are described as well as examples for the use of the supports in syntheses of oligonucleotides both on large scale and of extended chain length.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0006-3525
    Keywords: fractal measures ; high-performance capillary electrophoresis ; ion-exchange high-performance liquid chromatography ; high-performance liquid chromatography ; oligodeoxyribonucleotides ; oligoribonucleotides ; oligonucleotides ; polymerization processes ; chemical synthesis ; dynamics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper we put forward improved mathematical methods for detecting synthesis parameters in connection with analyzing crude products of chemically synthesized oligonucleotides. The crude products experimentally sampled are separated by high-performance capillary electrophoresis and ion-exchange high-performance liquid chromatography. The measured separation profiles of experimental syntheses can be expressed as target and nontarget yields; they are characterized by a few parameters. These parameters account for nonlinear synthesis equations that are solvable by employing iteration procedures. We provide here a theoretical as well as computational analysis based upon specific models for stepwise chain growth.Under nonconstant (nonuniform) conditions we use here an exponential form of growth, with different expressions for calculating the fractal dimension of the biochemical process under study. Step lengths of parameter variations in an interval of finite length have to be adjusted properly to find convergent solutions in a mathematical, regularly four-dimensional parameter space. It is conceivable to have most, if not all, of the calculating and plotting carefully done by a computer.This analysis represents the experimental situation up to 65-mer target oligonucleotides analyzed so far. We thus obtain the dynamics of the polymerization process limited in number by fractal models. The advantage, calculating these new methods as compared to qualitatively judged experimental methods, lies in the satisfactory evaluation of crude products, also of large amounts, of syntheses of these biopolymers. © 1998 John Wiley & Sons, Inc. Biopoly 45: 361-379, 1998
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of tert-butyl hydroperoxide by photochemically induced reactions in DMSOAbbreviations used: DMSO, dimethyl sulfoxide; DMSO-d6, completely deuterium labelled dimethyl sulfoxide; cw-ESR, continuous-wave Electron Spin Resonance; u. v., ultra violet; DMPO, 5, 5-dimethyl-I-pyrroline N-oxide; TMPO, 3, 3, 5, 5-tetramethyl-l-pyrroline N-oxide. and water was investigated by cw-e.s.r. spectroscopy. The products tert-butylperoxyl, methyl and sulfur-centered free radicals were identified. The tert-butoxyl free radical is involved in the primary process as shown by time-resolved e.s.r. technique. On the basis of directly identified radical species, a mechanism for the photochemically induced reactions of tert-butyl hydroperoxide in DMSO is proposed. At concentrations below 0.8 mol · l-1 the radical formation from tert-butyl hydroperoxide proceeds by cleavage of the O—O bond rather than by hydrogen abstraction.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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