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  • Chemistry  (12)
  • FLUID MECHANICS AND HEAT TRANSFER  (4)
  • Magnetism  (2)
  • 1
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der thermische Abbau von Poly-N-vinyl-carbazol (PVK) wurde mittels „flash“-Pyrolyse, kontrollierter Pyrolyse und dynamisch-thermogravimetrischer Analyse untersucht. Die Analyse der Abbauprodukte erfolgte über Gas-Flüssig-Chromatographie sowie Massenspektrometrie als Trennungs- und Identifizierungsverfahren. Das untersuchte PVK wurde durch radikalische Polymerisation in Benzol mit AIBN als Katalysator dargestellt.Aus den Versuchsergebnissen ergibt sich, daß PVK fast vollkommen über einen stufenweisen „unzipping“ Mechanismus in das Monomere zerfällt. Die Zusammensetzung der Pyrolysate ermöglicht eine Formulierung des Abbaumechanismus des Polymeren. Mit Hilfe des Verfahrens der multiplen Aufheizgeschwindigkeiten wurde die Kinetik des thermischen Abbaus untersucht. Die Bruttoaktivierungsenergie der Depolymerisation wurde zu 40 kcal/mol gemessen und für die Reaktionsordnung wurde ungefähŕ 1 gefunden.Es werden einige thermodynamische Betrachtungen aufgeführt, um den Wert der Aktivierungsenergie des gesamten Prozesses zu erklären. Es wird ein Mechanismus vorgeschlagen.
    Notes: The thermal degradation of poly-N-vinyl-carbazol (PVK) has been studied using flash pyrolysis, controlled pyrolysis and programmed thermogravimetry analysis techniques. The degradation products have been analyzed using gas-liquid chromatography and mass spectrometry as separation and characterization techniques. The examined PVK has been prepared by free radical polymerization in benzene using AIBN as catalyst.It is shown from experimental results that PVK breaks up almost completely into the monomer through a stepwise unzipping mechanism. The composition of the pyrolyzate allows to propose a mechanism for the polymer degradation. Thermal degradation rates have been analyzed using a multiple heating rates procedure. A value of 40 kcal/mol has been found for the overall activation energy of depolymerization and a value approximately equal to one for the order of reaction.Some thermodynamic considerations have been made in order to explain the value of the activation energy of the whole process. A mechanism is suggested.
    Additional Material: 7 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 25 (1987), S. 1099-1111 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric relaxation behavior of a nonaligned and an aligned liquid-crystalline (LC) polymer are reported for the ranges 10-3.5 to 105 Hz and 274-363 K. Multiple processes (δ and α) are observed that follow a Vogel equation for the temperature dependence related to the apparent glass transition temperature. The occurrence of these processes and the variation in their relaxation strengths as sample alignment is changed is interpreted in terms of a molecular theory for the dielectric behavior of a LC polymer that involves the director order parameter Sd, the mesophase order parameter S, the dipole moment components of the mesogenic head groups, and their associated relaxation functions.
    Additional Material: 8 Ill.
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  • 3
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: The study of the surface enhanced Raman spectroscopy (SERS) excitation profiles of 1,5-dimethylcytosine on metal colloids allows a more detailed determination of the behavior of the functional groups of this molecule in the adsorption process on the metal supports. Silver has shown its effectiveness and selectivity as a support for this technique from the point of view of its stability and capability to enhance the Raman signal coming from the adsorbate. The results are discussed in terms of the two well-known theories proposed up to now to explain the SERS phenomenon: electromagnetic and chemical (or charge transfer) models. © 1996 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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  • 4
    ISSN: 1075-4261
    Keywords: 9-aminoacridine ; fluorescence ; SERS ; dimerization ; excimer ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Fluorescence spectroscopy and surface-enhanced Raman spectroscopy (SERS) have been applied to study the aggregation and excimer emission of 9-aminoacridine (9AA) and 9-aminoacridine hydrochloride (9AA-HCl) in aqueous solution and on silver colloids. The effect of the drug concentration, pH, and chloride concentration on these processes has been investigated. The excimer emission of 9AA is connected to the dimerization of this drug in solution: the formation of 9AA dimers is greatly favored when the drug is under the amino form at neutral and acidic pH, while at alkaline pH the imino 9AA form tends to form large-sized aggregates which cannot be excited to render excimer emission. 9AA is adsorbed on the silver surface under two different forms: strongly and weakly attached 9AA, each one corresponding to the different drug tautomers: imino and amino. The interaction of 9AA with silver induces a charge transfer from the adsorbate to the metal leading to a remarkable fluorescence quenching, a basicity decrease of the adsorbed drug and a considerable weakening of the dimer-excimer emission. Furthermore, an attribution of the main Raman features appearing in the SERS spectra has been proposed, providing marker bands for the imino and amino 9AA tautomers, and a mechanism for the molecular dimerization is also suggested. © 1998 John Wiley & Sons, Inc. Biospectroscopy 4: 327-339, 1998
    Additional Material: 6 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 3 (1997), S. 449-455 
    ISSN: 1075-4261
    Keywords: surface-enhanced Raman spectroscopy ; γ-aminobutyric acid ; Raman spectra ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: The surface-enhanced Raman spectroscopy (SERS) of γ-aminobutyric acid (GABA) adsorbed on silver colloids in H2O and D2O were recorded and analyzed. When the concentration is greater than 10-3 M, the adsorbed species is the anionic form of the amino acid that interacts with the surface through both functional groups. According to the vibrational interpretation of the spectra, it is assumed that at concentrations in the order of or less than 10-3 M, GABA undergoes chemical transformations, which increase upon dilution, and spectra are recorded that are the result of the competitive adsorption between the amino acid in its anionic form and the products resulting from the chemical transformations. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 449-455, 1997
    Additional Material: 5 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 65 (1997), S. 277-285 
    ISSN: 0020-7608
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We briefly describe a nonclassical nonlinear thermodynamic theory with statistical foundations. This statistical approach is based on a generalization to arbitrary nonequilibrium conditions of the Gibbs ensemble algorithm, the so-called nonequilibrium statistical operator method, which can be considered to be encompassed within the scope of Jaynes' predictive statistical physics. This emerging formalism is used to provide a study of the technoindustrial process of thermal stereolithography (or infrared-laser-induced rapid prototyping). The experimental results are interpreted and the technical requirements fundamental for the success of the process are pointed out.   © 1997 John Wiley & Sons, Inc. Int J Quant Chem 65: 277-285, 1997
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 21 (1990), S. 679-682 
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectra of 1.5-dimethylcytosine (DMC) as the solid and in aqueous solution are reported. A tentative assignment of Raman bands is made. Surface-enhanced Raman spectra obtained on silver and on copper colloids show appreciable differences from the normal unenhanced Raman spectra. The geometry of DMC-metal interactions is discussed.
    Additional Material: 6 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 23 (1992), S. 61-66 
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: SERS spectra of cytosine, 1-methylcytosine, 5-methylcytosine and 1,5-dimethylcytosine on silver and on copper colloids are reported. A study of the influence of pH on the normal Raman spectra of these compounds was made in order to understand better the behaviour of these molecules on metal surfaces. The results obtained indicate remarkable changes in the type of adsorbate - metal interactions depending on the metal used as the SERS support. These interactions are also influenced by the presence of methyl groups in the cytosine molecule.
    Additional Material: 9 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 22 (1991), S. 819-824 
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Surface-enhanced Raman spectra of cytidine and cytidine 5′-monophosphate adsorbed on copper and silver colloids were investigated. As an aid to the interpretation with regard to the metal-adsorbate binding sites, the normal Raman spectra of the complexes of these substances with the metal ions were also obtained. The adsorption of the cytosine moiety in these substances occurs preferentially through the carbonyl bond, the pyrimidine ring adopting a non-planar orientation on the surface. However, in the complexes involving the metal ions the N-3 position is found to be the site through which the base interacts with these metals. The ribofuranose ring does not seem to participate significantly in the interaction of these substances with copper and silver in either the colloidal or ionic states.
    Additional Material: 6 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 26 (1995), S. 149-154 
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: SERS spectra of cytosine, 1-methylcytosine, 5-methylcytosine and 1,5-dimethylcytosine on a gold colloid are reported. A tentative assignment of Raman bands is made by comparison with the normal Raman spectra in aqueous solution. This analysis reveals a preferred non-planar orientation of cytosine and 1-methylcytosine and a more planar orientation of 5-methylcytosine and 1,5-dimethylcytosine with respect to the metal surface, the C=O group being determinant in the interaction. A comparative study using the result obtained previously using silver and copper colloids as supports shows important differences in the electrodynamic behaviour of these molecules which depend on the presence of the methyl substituents and the nature of the metal on which they adsorb.
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