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  • Chemistry  (79)
  • Surface physics, nanoscale physics, low-dimensional systems
  • Wiley-Blackwell  (79)
  • 2000-2004  (5)
  • 1985-1989  (70)
  • 1970-1974  (4)
  • 1
    Electronic Resource
    Electronic Resource
    Reduktive Arylierung von Vinyl-trifluoromethansulfonaten durch Friedel-Crafts-Reaktion (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1255-1256 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reductive Arylation of Vinyl Trifluromethanesulfonates by Friedel-Crafts ReactionThe reaction of vinyl triflates 1 with benzene and toluene in the presence of aluminium trichloride gives alkyl-, alkenyl-, and 1,1-diarylalkanes 5, 6, 3, 9 depending on the structure of the substrate used. A mechanism for the reductive arylation is proposed.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200724
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  • 2
    Electronic Resource
    Electronic Resource
    Acetylene-norbornene copolymers (1989)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3937-3949 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metathesis ring opening polymerization has been used to copolymerize norbornene and 7,8-bis(trifluoromethyl)tricyclo[4,2,2,02,5]deca-3,7,9-triene. Subsequent thermal elimination of the precursor copolymers yielded acetylene-norbornene copolymers. The undoped copolymers were found to have electrical conductivity, spin concentration, and EPR linewidths which vary with composition. The location of the trans-C—H out-of-plane vibration, however, was invariant at 1010cm-1 indicating that conjugation length of n 〉 4 are present even at 40% acetylene content in the copolymer. The copolymers containing 79 mol % of acetylene units attained a doped conductivity of 0.02 S/cm with a dopant concentration of 6 mol % of I3- per sp2 carbon.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1989.080271206
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  • 3
    Electronic Resource
    Electronic Resource
    Configurational stereoselectivity in the nucleophilic substitution of poly(vinyl chloride) with sodium thiophenate: NMR study and Monte-Carlo simulation of the reaction (1986)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 24 (1986), S. 1753-1777 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nucleophilic substitution of the chlorine atoms of poly(vinyl chloride) with sodium thiophenate is assumed to obey an SN2 mechanism with inversion of configuration and a steric control according to which reactivities R of the triads follow the order Rmm 〉 Rmr ≫ Rrr. Such a reaction cannot be described by simple differential equations, but a Monte Carlo simulation, first generating a random Bernouillian chain and then simulating random attack of the chain by the reactant according to the triad reactivities, allows a good agreement with the experimental results of both the kinetics of a reaction carried out in cyclohexanone solution at 40°C and the evolution of the 13C and 1H NMR spectra of the tertiary carbon atoms, assuming the following parameters: Bernouillian probability for a meso placement in the initial chain: 0.431; relative reactivities of the mm, mr and rm, rr triads: 1, 0.5, and 0., respectively. The agreement is excellent until the reaction is about three-quarters complete; this shows a limiting level of about 60% substitution. Better agreement can be obtained up to the limit, if a secondary process of steric control by the substituant in a partially substituted mr triad is assumed. Other possibilities for that secondary process are discussed.
    Additional Material: 21 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1986.080240804
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  • 4
    Electronic Resource
    Electronic Resource
    Organochlorine pesticides by negative ion chemical ionization. Brain metabolites of lindane (1988)
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 16 (1988), S. 279-284 
    Details
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A gas chromatographic/mass spectrometric technique for the analysis of organochlorine compounds using negative ion chemical ionization is presented. Detection limits for some compounds (penta- and hexachlorobenzene and p,p′-DDE) are of the order of 60-120 fg injected, while others (lindane, aldrin, etc.) are in the low picogram range (1.0 pg for lindane). The extreme selectivity for chlorine-containing compounds enables the direct analysis of homogenates of biological samples without any extraction or purification step. Metabolic studies can thus be remarkably simplified. Results are presented on the application of this technique to the analysis of lindane metabolites found in rat brain after treatment with this pesticide.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bms.1200160154
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  • 5
    Electronic Resource
    Electronic Resource
    A comprehensive approach to the stereochemical and physical factors in nucleophilic substitution on PVC in the melt (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 38 (1989), S. 1685-1698 
    Details
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The nucleophilic substitution reactin of poly(vinyl chloride) (PVC) with sodium benzenethiolate (NaBT) has been studied in the melt with the aim of determining whether a conformational mechanism is applicable under conditions that would apply in the polymer processing. The evolution of unreacted syndio, hetero, and isotactic triads content, and of the apparent molecular weight has been followed by 13C-NMR and GPC, respectively. The kinetic behavior was defined by choosing appropriate mixing conditions of temperature, shear stress, load, and amount of plasticizer. In all cases the kinetic curves attain a plateau after a rather fast reaction period has elapsed. The conversion at the plateau, that is, the reaction efficiency, proved to depend linearly on the amount of nucleophile and is hardly influenced by the mixing conditions for a given stoichiometric composition. The mixing conditions have been found to affect markedly the kinetics but to be quite inoperative on the evolution of both the content of unreacted tactic triads and the apparent molecular weight with degree of conversion. The results are discussed by taking into consideration those previously obtained in solution.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1989.070380909
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  • 6
    Electronic Resource
    Electronic Resource
    Instrument-independent database for collisionally activated dissociation in RF-only quadrupoles. The case of C2H3O+ and C3H7+ (1989)
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 3 (1989), S. 377-380 
    Details
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Dynamically correct (i.e., instrument-independent) branching ratios can be measured under single-collision conditions in tandem mass spectrometers incorporating RF-only quadrupole collision cells. The absolute branching ratios were measured as a function of the center-of-mass interaction energy ECM for the collisionally activated dissociation (CAD) of CH3CO+ (m/z43) from several source compounds (ethanol, oxirane), and CH3CO-X (where X = H, CH3, CH3CH2, CH3CO, CH3COCH2, and C6H5)). The energy dependences of the branching ratios for C2H3O+ from CH3CO-X source compounds are quite distinct from those observed for C2H3O+ from ethanol or ethylene oxide, or for the C3H+7 ions (also m/z 43) from n-pentane. Hence, one can use the CAD of m/z 43 to distinguish CH3CO-X compounds from other source compounds, including sources of C3H7+ ions. Therefore, the characteristic branching ratios of ionic substructures may provide for tandem mass spectrometry a „fingerprinting“ capability analogous to the use of group frequencies in infrared spectroscopy.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/rcm.1290031102
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  • 7
    Electronic Resource
    Electronic Resource
    Photolithography of polytetrafluoroethylene for adhesion (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 37 (1989), S. 2529-2536 
    Details
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Irradiation of polytetrafluoroethylene (PTFE) with Mg(Kα) X-rays is shown to protect the surface against the chemical etching steps used to prepare PTFE for adhesion. Preirradiated etched samples of PTFE have adhesion strengths to epoxies of less than 3% of that for nonirradiated etched samples. The major portion of this decrease in adhesion strength occurs for X-ray exposures of less than 10 min and failure in every case occurs in PTFE and not in the bonded transition region. XPS measurements (20 Å sampling depth) show little difference in F content between irradiated and nonirradiated samples, but thermal desorption shows increasing short chain fluorocarbon desorption with irradiation time. These results are consistent with previous studies showing that irradiation produces free radicals that lead to branching and/or crosslinking, and a surface rich in low molecular weight fluorocarbons. The crosslinked surface is resistant to deep (10,000 Å) chemical attack and rich in short chain fluorocarbons; both effects are expected to lead to weak adhesive bonding.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1989.070370906
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  • 8
    Electronic Resource
    Electronic Resource
    Single-column ion chromatography for the determination of chloride, sulfate, and nitrate in water (1989)
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 12 (1989), S. 568-569 
    Details
    ISSN: 0935-6304
    Keywords: HPLC-IC ; Inorganic anions ; Water analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jhrc.1240120822
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  • 9
    Electronic Resource
    Electronic Resource
    Synthesis of Silaproline, a New Proline Surrogate (2000)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 807-811 
    Details
    ISSN: 1434-193X
    Keywords: Proline analogues ; Asymmetric synthesis ; Schöllkopf's method ; Silicon ; Amino acids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The asymmetric synthesis of a new proline surrogate, incorporating the dimethylsilyl group at position 4 of proline using Schöllkopf's bis-lactim ether method, is described.
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  • 10
    Electronic Resource
    Electronic Resource
    Mechanisms of Cyclopalladation Reactions in Acetic Acid: Not So Simple One-Pot Processes (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 217-224 
    Details
    ISSN: 1434-1948
    Keywords: Reaction mechanisms ; Cyclopalladation ; Acetic acid ; Pd-C bond stability ; Polynuclear species ; Palladium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The processes operating during the synthetic cyclopalladation reactions of imines in acetic acid have been studied from a kinetico-mechanistic point of view. These reactions include a fast initial coordination to the palladium through the N-donor atom of the imine, followed by the proper C-H bond activation to produce the acetato bridged dimeric species. At this point, the lability of the bridging acetato groups, the hydrolysis of the C-Pd bonds, and/or the hydrolysis of C=N exo bonds contribute to the generation of dark red polynuclear compounds. The processes occurring after the C-H activation have been followed kinetically, both from palladium acetate plus imine, and the synthetically pure isolated acetato dimers as starting materials. The kinetic and activation parameters have been found identical within experimental error whatever the starting material was (k323 = 1.5 × 10-4 s-1; ΔH# = 51 kJ mol-1; ΔS# = -163 JK-1 mol-1 ΔV# = +19 cm3 mol-1 for the 4-ClC6H4-CH=N-CH2-C6H5 imine derivative 1a). Acidolysis of C-Pd bonds has been found to occur in these polynuclear species. When alternative monomeric Cbenzylic-Pd bond-containing complexes are possible follow ups of the reactions produce them as final dead-end complexes (k323 = 2.2 × 10-5 s-1; ΔH# = 61 kJ mol-1; ΔS# = JK-1 mol-1 ΔV# ≈ 0 cm3 cm-1 for the [2,4,6-(CH3)3]C6H2-CH=N-CH2-[2-(CH3]C6[H4] imine derivative 3d). The same study has been carried out with primary amines in order to check the validity of the data if C=N bond hydrolysis is taking place in the imine derivatives with exo C=N bonds. For complexes with similar type of metallacycles, the results agree reasonably well with the proposed mechanism [k323 = 1.2·10-4 s-1, ΔH# = 46 kJ·mol-1, ΔS# = -180 J·K-1mol-1, ΔV# = -16 cm3·mol-1 for the polynuclear formation of the C6H5-CH2-NH2 derivative 4e; k323 = 3.0·10-4 s-1, ΔH# = 55 kJ·mol-1, ΔS
    Additional Material: 1 Ill.
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