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  • 1985-1989  (4,152)
  • 1987  (4,152)
  • Polymer and Materials Science  (3,144)
  • Biochemistry and Biotechnology  (560)
  • Engineering  (448)
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  • 1985-1989  (4,152)
Year
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987) 
    ISSN: 0887-3585
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 13-19 
    ISSN: 0887-3585
    Keywords: two-dimensional electrophoresis ; ethylnitrosourea ; somatic mutations ; structural variants ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The feasibility of detecting human somatic structural gene mutations by two dimensional electrophoresis has been investigated. A lymphoblastoid cell line was grown as a mass culture in the presence of ethylnitrosourea, after which cells were regrown as single cell clones. A total of 257 polypeptide spots were analyzed in gels derived from 186 clones. Four structural mutations were detected by visual analysis of the gels. Computer analysis of gels corresponding to the mutant clones was also undertaken. At a spot size threshold of 200 spots to be matched using a computer algorithm, all four mutant polypeptides were detected. These results indicate the usefulness of the two-dimensional approach for mutagenesis studies at the protein level.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 1-12 
    ISSN: 0887-3585
    Keywords: protein crystallography ; protein refinement ; empirical energy simulations ; error analysis ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The uncertainties in the refined parameters for a 1.5-Å X-ray structure of carbon-monoxy (FeII) myoglobin are estimated by combining energy minimization with least-squares refinement against the X-ray data. The energy minimization, done without reference to the X-ray data, provide perturbed structures which are used to restart conventional X-ray refinement. The resulting refined structures have the same, or better, R-factor and stereochemical parameters as the original X-ray structure, but deviate from it by 0.13 Å rms for the backbone atoms and 0.31 Å rms for the sidechain atoms. Atoms interacting with a disordered sidechain, Arg 45 CD3, are observed to have larger positional uncertainties. The uncertainty in the B-factors, within the isotropic harmonic motion approximation, is estimated to be 15%. The resulting X-ray structures are more consistent with the energy parameters used in simulations.
    Additional Material: 6 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 20-33 
    ISSN: 0887-3585
    Keywords: calmodulin ; peptide ; calmodulin-binding peptide ; peptide design ; hydrophobic moment ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A basic, amphiphilic α helix is a structural feature common to a variety of inhibitors of calmodulin and to the calmodulin-binding domains of myosin light chain kinases. To aid in recognizing this structural feature in sequences of peptides and proteins we have developed a computer algorithm which searches for sequences of appropriate length, hydrophobicity, helical hydrophobic moment, and charge to be considered as potential calmodulin-binding sequences. Such sequences occurred infrequently in proteins of known crystal structure. This algorithm was used to find the most likely site in the catalytic (γ) subunit of phosphorylase b kinase for interaction with calmodulin (the δ subunit). A peptide corresponding to this site (residues 341-361 of the γ subunit) was synthesized and found to bind calmodulin with approximately an 11 nM dissociation constant. A variant of this peptide in which an aspartic acid at position 7 in its sequence (347 of the γ subunit) was replaced with an asparagin was found to bind calmodulin with approximately a 3 nM dissociation constant.
    Additional Material: 8 Ill.
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  • 5
    ISSN: 0887-3585
    Keywords: proteolytic cleavage ; immunological cross-reaction ; amber fragment ; temperature-sensitive mutant ; stationary growth-phase ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Immunological cross-reaction was employed for identification of proteolytic fragments of E. coli RNA polymerase genered both in vitro and in vivo. Several species of partially denatured but assembled RNA polymerase were isolated, which were composed of fragments of the two large subunits, β and β′, and the two small and intact subunits, α and σ. Comparison of the rate and pathway of proteolytic cleavage in vitro of unassembled subunits, subassemblies, and intact enzymes indicated that the susceptibility of RNA polymerase subunits to proteolytic degradation was dependent on the assembly state.Using this method, degradation in vivo was found for some, but not all, of the amber fragments of β subunit in merodiploid cells carrying both wild-type and mutant rpoB genes. Although the RNA polymerase is a metabolically stable component in exponentially growing cells of E. coli, degradation of the full-sized subunits was found in two cases, i.e., several temperature-sensitive E. coli mutants with a defect in the assembly of RNA polymerase and the stationary-phase cells of a wild-type E. coli. The in vivo degradation of RNA polymerase was indicated to be initiated by alteration of the enzyme structure.
    Additional Material: 9 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 54-63 
    ISSN: 0887-3585
    Keywords: domain association ; protein folding ; viscosity dependence ; solvent effects ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The equilibria and kinetics of ureainduced unfolding and refolding of the α subunit of tryptophan synthase of E. coli have been examined for their dependences on viscosity, pH, and temperature in order to investigate the properties of one of the rate-limiting steps, domain association. A viscosity enhancer, 0.58 M sucrose, was found to slow unfolding and accelerate refolding. This apparently anomolous results was shown to be due to the stabilizting effect of sucrose on the folding reaction. After accounting for this stabilization effect by using linear free-energy plots, the unfolding and refolding kinetics were found to have a viscosity dependence. A decrease in pH was found to stabilize the domain association reaction by increasing the refolding rate and decreasing the unfolding rate. This effect was accounted for by protonation of a single residue with a pK value of 8.8 in the native state and 7.1 in the intermediate, in which the two domains are not yet associated. The activation energy of unfolding is 4.8 kcal/mol, close to the diffusion limit. The negative activation entropy of unfolding, -47 cal/deg-mol, which controls this reaction, may result from ordering of solvent about the newly exposed domain interface of the transition state. These results may provide information on the types of noncovalent interactions involved in domain association and improve the ability to interpret the folding of mutants with single amino-acid substitutions at the interface.
    Additional Material: 8 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 34-41 
    ISSN: 0887-3585
    Keywords: adrenergic receptors ; affinity chromatography ; electron microscopy ; oligomeric structure ; target size analysis ; HPLC digest mapping ; receptor evolution ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: We have characterized the structure of purified beta-adrenergic receptors by a combination of photoaffinity labeling, high performance liquid chromatography (HPLC)-tryptic mapping, CNBr fragmentation, target size analysis, and electron microscopy of purified receptor molecules. Guinea pig lung beta-adrenergic receptors purified by affinity chromatography, ion exchange chromatography, and HPLC size exclusion chromatography or photoaffinity labeled with [125]-iodocyanopindolol diazirine displayed mobilities on sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) that corresponded to Mr = 68,000. Purified, radioiodinated guinea pig lung beta-receptors were subjected to complete trypsin digestion and subsequent reverse-phase HPLC analysis, which revealed nine peptides. Active site labeling and tryptic digestion of partially purified hamster lung beta-receptors produced one peptide, whereas CNBr digestion of the same material produced two labeled fragments, yielding information about the location of the active site within the primary sequence. Purified guinea pig lung receptors were examined with transmission electron microscopy. Electron micrographs revealed slightly asymmetric, rod-shaped structures with an average length of 13 nm and width of 3.4 nm. Many receptors were arranged as apparent dimeric structures. These findings confirm data obtained from target size analysis of guinea pig lung beta-receptors in situ which suggest that receptors may exist as oligomeric arrays in the native membrane. Taken together, these data provide information about putative functional domains of the beta-adrenergic receptor and its quaternary structure.
    Additional Material: 8 Ill.
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  • 8
    ISSN: 0887-3585
    Keywords: intrahelical ion pairs ; frequency of ion pairs in exposed helices ; alpha-helix stabilization ; protein tertiary structure stabilization ; protein-folding pathway ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A survey of 47 globular proteins was made to determine the probability of occurrence of ion pairs separated by 1, 2, 3, … and 8 residues in the alpha helices. As a control, the probability of occurrence of like charged pairs was also determined. The survey showed that ion pairs of the type i, i±3 and i, i±4 are the most predominant. Such a preference was not observed for like charged pairs. The observed frequency of ion pairs is significantly greater than their expected frequency. The normalized frequencies of occurrence of the ion pairs were also found to increase generally with the helix length. These results indicate that the ion pairs may contribute to the stability of solvent-exposed alpha helices. Since the stabilization of protein secondary structure, these results may throw light on the mechanism of protein folding.
    Additional Material: 5 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987) 
    ISSN: 0887-3585
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 79-80 
    ISSN: 0887-3585
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 11
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 72-77 
    ISSN: 0887-3585
    Keywords: CO equilibrium constants ; des-(Arg 141α)HbA ; heme proteins ; high-affinity state ; kinetics ; ligand binding ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A few years ago we reported that histidine (HC3) 146β plays a major role in the pH-dependent propeties of the R-state of human hemoglobin, accounting for close to 50% of the R-state Bohr effect. We have extended these studies by examining the role of arginine 141α, another group known to affect the overall Bohr effect. We have compared the pH dependencies of the rate constants for the dissociation and combination of the fourth carbon monoxide molecule, I4 and I′4, respectively, for native hemoglobin A (HbA) and a control reconstututed HbA, and des-(Arg 141α) HbA, the hemoglobin molecule resulting from the enzymatic removal of the C-terminal arginine of the α-chain of human Hb. From these kinetic contants the pH dependence of L4, by about 80% between pH 6 and 8, where the aldkaline Bohr effect normally occurs, The sum of the effects of the removal of His 146β and of Arg 141α is grater than 100%. This suggests that at least one of these modifications altrs the contrubutions of other residues of this Bohr effect.
    Additional Material: 4 Ill.
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  • 12
    ISSN: 0887-3585
    Keywords: hybrid immunologlobulin ; compatible plasmids ; transfection ; mouse IgG1 ; mouse IgG2a ; dansyl ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: We have produced a series of hybrid IgG1-IgG2a mouse immunoglobulins with identical light chains (L) and variable regions to facilitate the identification of structural features associated with functional differnces between immunoglobulin isotypes. Hybrid heavy chain (H) constant region gene segments were generated by genetic recombination in Escherichia coli between plasmids carrying mouse γ1 and γ2a gene segments. Crossovers occured through out these segments although the frequency was highest in regions of high nucleotide sequence homology. Eleven variant immunoglobulins produced by transfected hybridoma cell lines are assembled into H2L2 tetramers and properly glycosylated. In addition, all 11 immunoglbulins have identical antigen combining sites specific for the fluorescent hapten ε-dansyll-L-lysine. Protein A binding was used as probe of the structural integrity of the Fc portion of the variant antibodies. Differeneces in protein A binding between IgG1 and IgG2a appear to be due to amino acid differances at postions 252 (Thr→Met) and 254 (Thr→Ser) of the heavy chain (EU numbering).
    Additional Material: 8 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 111-117 
    ISSN: 0887-3585
    Keywords: crystallography ; antigen ; glycoprotein ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Neuraminidases from different subtypes of influenza virus are characterized by the absence of serlogical cross-reactivity and an amino acid sequence homology of approximately 50%. The three-dimensional structure of the neuraminidase antigen of subtype N9 from an avian influenza virus (A/tern/Australia/G70c/75) has been determined by X-ray crystallography and shown to be folded similarly to neuraminidase of subtype N2 isolated from a human influenza virus. This result demontrates that absence of immunological cross-reactivity is no measure of dissimilarity of polypeptide chain folding. Small differences in the way in which the subunits are organized around the molecular fourfold axis are observed. Insertions and deletions with respect to subtype N2 neuraminidase occur in four regions, only one of which is located within the major antigenic determinants around the enzyme active site.
    Additional Material: 4 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 90-110 
    ISSN: 0887-3585
    Keywords: compact units ; coefficient of compactness ; folding intermediates ; protein structural hierarchy ; primitive units ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The coefficient of compactness was recently introduced and used to locate domains in lysozyme and ribonuclease (Zehfus and Rose: Bio-chemistry 25:5759-5765, 1986). Nineteen additional proteins now have been analyzed by using this measure. Complete listings of compact units and plots showing their hierarchic organization are presented for all twenty-one proteins. Large compact units correspond well to protein domains; however, many smaller compact structures of equal or better compactness are also found. Since small compact units could represent subdomains or protein-folding intermediates, their structural composition is further examined.
    Additional Material: 2 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 118-129 
    ISSN: 0887-3585
    Keywords: homologous proteins ; hydropathy index ; chain flexibility ; α/β barrels ; tryptophan ; synthase aplha subunit ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The amino acid sequences of the α subunits of tryptophan synthase form ten different microorganisms were alingned by standard procedures. The α helics, β strands and turns of each sequence were predicted separately by two standard prediction algorithms and averaged at homologous sequence positions. Additional evidence for conserved secondary structure was derived form profiles of average hydropathy and chain flexibility values, leading to a joint prediction. There is good agreement between (1) predicted β strands, maximal hydropathy and minimal flexibility, and (2) predicted loops, great chain flexibility, and protein segments that accept insertions of various lengths in individual sequences. The α subunit is predicted to have eight repeated β-loop-α-loop motifs with an extra N-terminal α helix and an intercalated segment of highly conserved residues. This pattern suggests that the teritiary structure of the α subunit is an eightfold α/β barrel. The distribution of conserved amino acid residues and publilshed data on limited proteolysis, chemical modification, and mutagenesis are consistent with the α/β barrel structure. Both the active site of the α subunit and the combining site for the β2 subunit are at the end of the barrel formed by the carboxyl-termini of the β strands.
    Additional Material: 6 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 153-161 
    ISSN: 0887-3585
    Keywords: accessbility ; hydrophobic effect ; protein conformation ; Boltzmann statistics ; maximum likelihood ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Globular proteins fold into compact particles with interior amino acid residues shielded from the surounding aqueous environment. An early hypothesis holds that entropic hydophobic forces dirve this phenomenon. However, previous analyses based on a binary description of the accesible surfaces of amino acid residues in proteins did not support theis hypothesis. This report shows that a complete description of accessible surface areas is given by parametric distribution fuctions with three modes. The modes are formed by partitioning the available accessible surface area of the amino acids into three segments; the data for each segment are characterized by a mode-specific model. In the “repulsive” mode, probabilities of accessibility decrease exponentially with exposed surface area, as predicted by the hydrophobic hypothesis. A distinct “buried” mode is needed to account for an excess of residues at or near zero accessibility for most amino acids, consistent with the use of binary descriptions of accessibility. A third mode exists which is termed “near neutral” because it is described by a nearly uniform distribution of accessibility for the hydrophiliic amino acids. Empirical energies calculated for the repulsive mode correlate well with measured free energies of transfer of amino acids from water to organic solvents, while those from the buried mode correlate well with measured free energies of hydration of the side chains. Poor cross correlations between these energies give an explanation for the previous conflict in interpreting these data.
    Additional Material: 2 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 162-166 
    ISSN: 0887-3585
    Keywords: protein folding ; secondary structure prediction ; tertiary structure prediction ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: In recent years, the protein-folding problem has attracted the attention of molecular biologists. Efforts have focused on developing heuristic and energy-based algorithms to predict the three-dimensional structure of a protein from its amino acid sequence. We have applied a series of heuristic algorithms to the sequence of human growth hormone. A family of five structures which are generically right-handed fourfold α-helical bundles are found from an investigaion of ∼108 structures. A plausible receptor binding site is suggested. Independent crystallographic analysis confirms some aspects of these predictions. These methods only deal with the “core” structure, and conformations of many residues are not defined. Further work is required to identify a unique set of coordinates and to clarify the topological alternatives available to α-helical proteins.
    Additional Material: 3 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 130-152 
    ISSN: 0887-3585
    Keywords: amino acid hydophobicity scale ; QSAR ; amino acids ; peptide side chains ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The fragment method of calculation partition coefficients (P) has been extended to include the common amino acids (AAs). The results indicate that polar and charged side chains influence the hydrophobicity of atoms in the side chain in a predictable manner. Feild effects, as evidenced through polar proximity factors and bond factors, need to be considered for accurate estimation of transfer phenomena. The calculated log P and ΔG°′ values of the 20 AAs agree well with the observed values. Pro calculates to be more hydrophilic than the observed log P. Hydrophobicity scales for peptide side chain residues are compared and evaluated in terms of suitability. Calculated π values for nonpolar side chain residures agree well with the observed values; calculated values for uncharged polar side chain residues deviate by about 0.6 log units except for Gln and Cys; and polar side chain residues with charged side chains calculate as too hydorphilic. Reasons for the differences are explored. We also suggest that tightly bound water to polar moieties in amino acids and peptides may be transferred into the octanol phase during partitioning experiments. A quantitative methodology is persented which characterizes the thermodynamic partitioning of groups and individual atoms in amino acids and proteins.
    Additional Material: 7 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987) 
    ISSN: 0887-3585
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
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  • 20
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 177-187 
    ISSN: 0887-3585
    Keywords: evolution ; protein structure ; nucleotide binding domain ; gene sequence ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The intron/exon organization of the human gene for glycogen phosphorylase has been determined. The segments of the polypeptide chain that corresponds to the 19 exons of the gene are examined for relationships between the three-dimensional structure to the protein and gene structure. Only weak correlations are observed between domains of phosphorylase and exons. The nucleotide binding domains that are found in phosphorylase and other glycolytic enzymes are examined for relationships between exons of the genes and structures of the domains. When mapped to the three-dimensional structures, the intron/exon boundaries are shown to be widely distributed in this family of protein domains.
    Additional Material: 5 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 188-201 
    ISSN: 0887-3585
    Keywords: NMR ; NOE ; protein conformation ; structure data base ; structure fragments ; modelling ; distance matrices ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A method to build a three-dimensional protein model from nuclear magnetic resonance (NMR) data using fragments from a data base of crystallographically determined protein structures is presented. The interproton distances derived from the nuclear Overhauser effect (NOE) data are compared to the precalculated distances in the known protein structures. An efficient search algorithm is used, which arranges the distancs in matrices akin to a Cα diagonal distance plot, and compares the NOE distance matrices for short sequential zones of the protein to the data base matrices. After cluster analysis of the fragments found in this way, the structure is built by aligning fragments in overlapping zones. The sequentially long-range NOEs cannot be used in the initial fragments search but are vital to discriminate between several possible combinations of different groups of fragments. The method has been tested on one simulated NOE data set derived from a crystal structure and one experimental NMR data set. The method produces models that have good local structure, but may contain larger global errors. These models can be used as the starting point for further refinement, e.g., by restrained molecular dynamics or interactive graphics.
    Additional Material: 12 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 236-259 
    ISSN: 0887-3585
    Keywords: atomic probability distributions of proteins ; anisotropy and anharmonicity of motions in proteins ; multiple occupancy of atomic positions in proteins ; molecular dynamics simulation ; lysozyme ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Positional probability density functions (pdf) for the atomic fluctuations are determined from a molecular dynamics simulation for hen egg-white lysozyme. Most atoms are found to have motions that are highly anisotropic but only slightly anharmonic. The largest deviations from harmonic motion are in the direction of the largest rms fluctuations in the local principal axis frame. Backbone atoms tend to be more nearly harmonic than sidechain atoms. The atoms with the largest anharmonicities tend to have pdfs with multiple peaks, each of which is close to harmonic. Several model pdfs are evaluated on the basis of how well they fit probability densities from the dynamics simulations when parameterized in terms of the moments of the distribution. Gram-Charlier and Edgeworth perturbation expansions, which have been successful in describing the motions of small molecules in crystals, are shown to be inadequate for the distributions found in the dynamics of proteins. Multipeaked distribution functions are found to be more appropriate.
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  • 23
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 260-261 
    ISSN: 0887-3585
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Additional Material: 1 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987) 
    ISSN: 0887-3585
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 25
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 298-307 
    ISSN: 0887-3585
    Keywords: α-bungarotoxin ; neurotropism ; rhabdo-virus ; α-subunit ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Peptides corresponding to portions of loop 2 of snake venom curare-mimetic neurotoxins and to a structually similar region of rabies virus glycoprotein were synthesized. Interaction of these peptides with purified Torpedo electric organ acetylcholine receptor was tested by measuring their ability to block the binding of 125I-labeled α-bungarotoxin to the receptor. In addition, inhibition of α-bungarotoxin binding to a 32-residue synthetic peptide corresponding to positions 173-204 of the α-subunit was determined. Neurotoxin and glycoprotein peptides corresponding to toxin loop 2 inhibited labeled toxin binding to the receptor with IC50 values comparable to those of nicotine and the competitive antagonist d-tubocurarine and to the α-subunit peptides with apparent affinities between those of d-tubocurarine and α-cobratoxin. Substitution of neurotoxin residue Arg37, the proposed counterpart of the quatenary ammonium of acetylcholine, with a negatively charged Glu residue reduced the apparent affinity about 10-fold. Peptides containg the neutotoxin invarint residue Trp29 had 10- to 100-fold higher affinites than peptides lacking this residue. These results demonstrate that relatively short synthetic peptides retain some of binding ability of the native protein from which they are derived, indicating that such peptides are useful in the study of proetin interactions. The ability of the peptides to compete α-bungarotoxin binding to the receptor with apparent affinites comparable to those of other cholinergic ligands indicates that loop 2 of the neurotoxins and the strucually similar segment of the rabies virus glycoprotein act as recognition sites for the acetylcholine receptor. Invarient toxin residues Arg37 and Trp29 and their viral homologs play important, although not essential, roles in binding, possibly by interaction with complementary anionic and hydrophobic subsites on the acetylcholine receptor. The α-subunit peptide most likely contains all of the determinants for binding of the toxin and glycoprotein peptides present on the α-subunit, because these peptides bind to the 32-residue α-subunit peptides with the same or greater affinity as to the intact subunit.
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  • 26
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 308-329 
    ISSN: 0887-3585
    Keywords: conformational dynamics ; normal mode analysis ; Young's modulus ; rigid structural elements ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The normal mode analysis of conformational fluctuation is carried out for a small globular protein, bovine pancreatic trypsin inhabitor. Results are analyzed mainly to reveal the mechanical construction of the protein molecule. We take dihedral angles, including peptide ω angles, as independent variables for the normal mode analysis. There are 306 such angles in this molecule. Motions in modes with frequencies lower than 120 cm-1 are showned to involve atoms in the whole protein molecule, and spatial change of displacement vectors is continues, i.e., those of atoms near in space are similar. To quantitate the observation of the continuity, a correlation function of direction vectors of atomic displacement is calculated. From this function we define a Quantity that is interpreted as the wave length of an equivalent elastic plane wave. From this Quantity we deduce eefective young's modulus for each mode. For the mode with the lowest frequency 4.4 cm-1, it terned out to be 0.8 × 109 dyn cm-2, the value two orders magnitude softer than, for instance, α-helices. Prompted by this observation, the four lowest frequency modes and also the harmonic motions in the thermal equilibrium are analyzed further mainly to detect relatively rigid structural elements in the molecule. From this analysis emerges a mechanical picture of the protein molecule that is made up of relatively rigid elements held together by very soft parts.
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  • 27
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    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 2 (1987), S. 330-339 
    ISSN: 0887-3585
    Keywords: van der Waals radii ; conformation ; amino acid residue ; dipeptide approximation ; molecular modeling ; systematic conformationl search ; N-alkyl amino acid ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Effective van der Waals radii were celebrated in such a way that molecular models built from standard bond lengths and bond angels reproduced the amino acid conformations observed by crystallography in proteins and peptides. The celebrations were based on the comparision of the Ramachandbran plots prepared from high-resolution X-ray data of protins and peptides with the allowed φ,ψ torsional angel space for the depeptide molecular models. The celebrated radii are useful as criteria with which to filter energetically improbable conformations in molecular modeling studies of proteins and peptides.
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  • 28
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 111-125 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have prepared a number of high molecular weight, soluble, symmetrical dialkyl substituted germanium homopolymers and germanium-silicon copolymers. In solution, the absorption of the homopolymers was ∼ 20 nm red shifted from the crossponding silicon derivatives. This was somewhat unexpected based on theoretical predictions and has been rationalized on the basis of conformational arguments. In the solid state, samples of poly(di-n-hexylgermane) and poly(di-n-octylgermane) are strongly thermochromic. The effect is attributed to the conformational locking of the backbone which is caused by the crystallization of the side groups. In this regard, the germanium derivatives behave similarly to the corresponding silicon polymers, and the convergence of the long wavelength absorptions for both types of polymers is consistent with theoretical predictions. The germanium-silicon copolymers are also strongly thermochromic, but the long wavelength absorption is somewhat blue shifted (8 nm) from the respective homopolymers. As expected, the new germanium homo and copolymers are quite sensitive to light and readily undergo chain scission to produce lower molecular weight materials.
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  • 29
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 181-189 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinyl acetate-vinyl alcohol copolymers were fractionated in order to obtain their degree of hydrolysis distributions. In the method employed for fractionation, the differences in molecular weight of copolymer did not affect the fractional separation. Degree of hydrolysis distributions was found to be broad, with a pronounced maximum at a low degree of hydrolysis. Viscosity measurements were performed both for the precipitated fractions and unfractionated polymer. The Huggins constant was found to increase with a decrease in the degree of hydrolysis of polyvinyl acetate. These results were interpreted in terms of a polymer molecular association. From values of Huggins constants, comparative information about copolymer “blockiness” is also established.
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  • 30
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 271-284 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolyesters containing ethylene terephthalate and p-oxybenzoate units in mole ratios of ca. 80:20, 70:30, 40:60, and 20:80, respectively, were examined by direct pyrolysis-mass spectrometry to obtain information about the thermal stabilities and the sequences distributions of the two types of units as a function of composition. Thermal stability as measured by rate of volatilization increased with increasing oxybenzoate content, as did the amount of char residue formed. The electron impact mass spectrum of the volatile fragments showed the formation of predominantly linear fragments with carboxyl and vinyl end groups. Dimer, trimer, and tetramer fragments containing either or both types of units could be identified and their relative amounts could be estimated from peak intensities. The results were consistent with those expected for random distributions of the two units, i.e., for statistical copolymers.
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  • 31
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 23-30 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly[styrene (ST)-tetrahydrofuran (THF)-2-methyl-2-oxazoline(MeOz)] triblock and graft copolymers were prepared by ionic polymerizations. Poly(ST-THF) graft copolymers were synthesized by coupling of ST-4-vinylpyridine (4VP) copolymer with a large excess of PTHF dication. The ion coupling of PST dianion with PTHF dication was accompanied by the side reaction (abstraction of α proton of oxonium ion). After tosylation of terminal hydroxyl groups of PTHF blocks, cationic copolymerizations of MeOz with poly(ST-THF) block and graft copolymers were carried out, and characteristics of produced copolymers were investigated in some detail.
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  • 32
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 77-86 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The acetylation of linalool with acetic anhydride was carried out in the presence of polystyrene-bound aminopyridines and triethylamine. The catalytic activity of the immobilized aminopyridines increased with decreasing percentage of ring substitution and with increasing spacer-chain length. The increased activity is attributed to an increase in the amount of aminopyridine units complexed with acetic anhydride. The acetylation could be successfully conducted by use of a mixture of the immobilized aminopyridines and polymer-supported benzyldiethylamine, which effectively trapped acetic acid formed in the reaction system.
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  • 33
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 127-136 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radicals formed in poly(methyl methacrylate) (PMMA) under vacuum by UV irradiation at room temperature were carefully examined from 77 K to 300 K by electron spin resonance (ESR). The conventional nine-line spectrum was observed with significant overall intensity changes in contrast to previous reports. The intensity decreases greatly as the temperature increases from 77 K to 100 K. The intensity of the ESR spectrum increases as the temperature increases gradually from 100 K to 260 K. The spectral changes were reversible at all temperatures. Three different models are considered to interpret the temperature dependence of the intensity of the ESR spectrum. The results indicate that the ESR spectrum depends on (1) the steady-state concentration of the propagating radical in the polymer, (2) the conformational distributions of the radicals, and (3) the environmental structures of the polymer matrix.
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  • 34
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 171-180 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Based on dynamic thermogravimetric analysis (TGA) of fluorinated aromatic polyamides, we found that substituting terephthaloyl units for isophthaloyl units usually increased the thermal stability of the polymers. In contrast, the first steps of thermal degradation of poly(5,5′-sulfonyl-2,2′-difluoro-diphenyl terephthalamide) (2,2′-DIF-PSDPT) and poly(5,5′-sulfonyl-2,2′-difluorodphenyl isophthalamide)(2,2′-DIF-PSDPI) followed almost the same curve. This was attributed to the relative flexibility of the —SO2— group, and also to the activating effect on the dehydrofluorination reaction, which was believed to be the first step of the degradation of the ortho-fluorinated aromatic polyamides, , resulting in the formation of benzoxazole groups, , on the polymer backbone. With fluorinated aromatic polyamides having ortho fluorine to the amide nitrogen, the electron releasing —CH2— group deactivated the nucleophilic substitution of the dehydrofluorination reaction and the electron withdrawing group —SO2— activated the reaction, so that the onset degradation temperatures of the fluorinated aromatic units R in followed the order:
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  • 35
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 231-239 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New bicyclic and tricyclic compounds have been synthesized by the Lewis acid-catalyzed condensation of epoxides with cyclic acid anhydrides or cyclic bislactones. These materials take part in the anionic addition polymerization of amine-functional polyamides with diepoxides, and modify the shrinkage that is characteristic of the reaction. It is possible to control the extent of shrinkage by choosing an appropriate comonomer and by adjusting the concentration of this material in the reaction mixture.
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  • 36
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 653-667 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three types of wholly aromatic block copolymers were synthesized using the phosphorylation reactions of Yamazaki and Higashi. Each copolymer contained blocks of rigid and flexible units. The first copolymer, PBA/PABH-T, contains blocks of poly(p-benzamide) and the polyterephthalamide of p-aminobenzhydrazide. The second copolymer, PBA/MPD-I, contains blocks of poly(p-benzamide) and poly(p-phenylene isophthalamide), whereas the third, PPD T/MPD-I, contains blocks of poly(p-phenylene terephthalamide) and poly(m-phenylene isophthalamide). Three synthetic routes were used for the preparation of the block copolymers. In the two-step polycondensation (A), monomers of the flexible block are added to the rigid prepolymer. The multistep method (B) differs in that the rigid prepolymer is carboxy-terminated prior to addition of the monomers of the flexible block. Carboxy-terminated prepolymer of the rigid block is reacted with amine-terminated prepolymer of the flexible block in the two-pot condensation (C). The presence of a considerable amount of the flexible homopolymer is indicated by viscosity, extraction, and NMR studies, particularly when methods A and C were used. The flexible homopolymer can be extracted by using a nonsolvent for the rigid blocks. Extraction of the rigid homopolymer (which may also be presumed to be produced) entails a more elaborate procedure. In principle, one can use these methods to obtain pure block copolymer for study of mixtures with the rigid and flexible homopolymers. Phase studies of some of these systems will be reported in a following paper.
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  • 37
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 711-717 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some regularities of radical alternating copolymerization of maleic anhydride with allyl chloroacetate are studied. The formation of donor-acceptor complexes between comonomers with complexing constant Kc = 0.052 L/mol is found using 1H NMR spectroscopy. The kinetic parameters for this copolymerization reaction are found and the quantitative contribution of monomer complexes to chain-growth radical reactions is calculated. It is shown that either a “free-monomer” mechanism (dilute solutions) or a “mixed” mechanism (concentrated solutions) prevails for chain growth during radical copolymerization depending on total monomer concentration. It is found that inhibition of degradative chain transfer in the course of the reaction studied takes place owing to the presence of α-chlorine atom in the allyl chloracetate molecule and formation of charge transfer complex.
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  • 38
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 433-436 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 39
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 451-465 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A group of block copolymers containing diacetylenes as chain extenders in their hard segments was prepared, based on urethanes, esters, ureas, and amides as hard segments and polybutadienes, polyethers, polyesters, and polysiloxanes as soft segments. Almost all block copolymers were photoreactive, but there was a wide range of sensitivities. The photoreactivity of the copolymers was found to depend on the reactivity of the monomer unit, on the width of the diacetylene stacks in the hard segments, and on the degree of phase separation in the solid films.To explore the range of monomer reactivities we prepared 15 crystalline monomers. Urethanes were in general the most reactive, and this was attributed in part to the specific effect of hydrogen bonding which brings about a shortening of the C1 to C4 distance between diacetylenes tend to reduce the photoreactivity.The behavior of identical diacetylene units in the monomer crystal, in the homopolymer, and in the block copolymer is discussed in this paper.
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  • 40
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 551-563 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three copolyimides containing crosslinkable alkyne groups either in the main chain backbone or as endgroups, have been synthesized and characterized in regard to their structure, molecular weight, solubility, film-forming properties, crystallinity, crosslinking behavior, and thermal stability. A good correlation between the structure of the polymers and their properties has been established.
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  • 41
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 581-593 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The H-abstraction by ĊH3 and ĊD3 radicals from PMMA molecules is investigated at 77 and 120 K. The film samples are prepared from the mixture of normal and deuterated PMMA. The reaction is of the first order with respect to radical concentration. Its rate is retarded in time as compared to the exponential law. An analysis of the molecular product ratio for the reaction allows the primary isotopic effect to be estimated. The initial reaction rate depends nonmonotonously on the proportion of the deuterated polymer in the matrix. Namely, there exists a range of isotopic compositions, with the reaction rate increasing with the portion of a deuteropolymer in the mixture. At 77 K the reaction rate of ĊD3 is lower than that of ĊH3 in PMMA of a mixed isotopic composition. This results from the proximity of ĊD3 with unreactive parental macromolecules, which reduces the local H concentrations around ĊD3 as compared to the mean concentration. At 120 K the radical decay rates do not differ. This fact cannot be explained by unfrozen mobilities of radicals at high temperatures or by their migration from parental macromolecules. The phenomenon is interpreted in terms of thermal fluctuations involving a great area around a radical and ensuring its migration within this area. The electron spin echo method is used to estimate the distance between a radical and its parental macromolecule, a ≥ 9.6 Å. This is the lower limit of the reaction accessibility.
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  • 42
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 637-652 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of di-n-butyl itaconate (DBI) intiated with AIBN was kinetically investigated in benezene. The polymerization rate (Rp) was expressed by: Rp = k[AIBN]0.5[DBI]1.7. The polymerization showed a considerably low overall activation energy of 15.3 kcal/mol. The initiator efficiency of AIBN in this system decreased with increasing DBI concentration, ranging from 0.34 to 0.55°C, which is ascribable to viscosity effect due to the monomer. From an ESR study, the polymerization system was found to involve two kinds of persistent radicals, namely, primary propagating (III) and propagating (I) radicals. The relative concentration of III to I increased with decreasing monomer concentration. Azo-nitrile initiators such as AVN and ACN similarly produced two persistent radicals, while MAIB, DBPO, and PBO yielded only propagating radical I as persistent. The MAIB-initiated polymerization of DBI was also performed in benzene. Similar kinetic features were observed, that is, a higher dependence of Rp on the DBI concentration and a low overall activation energy (14.4 kcal/mol). The following rate equation was obtained at 50°C:Rp = k[MAIB]0.5[DBI]1.6. The initiator efficiency of MAIB decreased with increasing DBI concentration, ranging from 0.32 to 0.53 at 50°C. The concentration of propagating radical I was determined by ESR at 50 and 61°C, from which kp and kt were estimated. The kp value increased with increasing monomer concentration, while the kt one decreased with the DBI concentration. These values are much lower compared with those of MMA.
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  • 43
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 685-702 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Modified polyimide films containing cobalt have been prepared by the addition of cobalt(II) chloride to a solution containing one of the diamines 4,4′-oxydianiline (ODA) or 4,4′-diaminodiphenylsulfide (DDS) and one of the dianhydrides 3.3′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) or 4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride (BDSDA) and characterized by thermal methods, UV-visible spectra, room-temperature direct-current electrical resistivity measurements, and X-ray photoelectron and Auger electron spectroscopy. A principal goal of this work was to establish if there was coordination of the potential donor atoms of the polymide to cobalt. UV-visible spectra of the modified polyamic acid solutions and polyimide films and a titration study of a model system do not show any appreciable coordination with either the polyamic acid or the polyimide; rather, the cobalt(II) appears to be coordinated to the solvent, N,N-dimethylacetamide (DMAc), as [Co(DMAc)4]2+, until the temperature is raised above 200°C. X-ray photoelectron spectra of films cured only to 200°C also do not show significant shifts in the binding energies of the potential donor atoms from those binding energies of the undoped polymers, confirming little direct coordination of the cobalt to atoms of the polyimide. Heating the films to 300°C in a forced-air oven causes the formation of a cobalt oxide layer on the air side of the polymer. Direct-current electrical resistivity measurements on this surface show a 104-106 reduction in resistivity due to this layer.
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  • 44
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 743-743 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 45
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 215-221 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The laser Raman phonon spectroscopic technique has been used to study the photopolymerization reaction of 1,4 bis[β-pyridyl(2)vinyl] benzene (P2VB). Raman and infrared spectroscopy have been used to study the intramolecular vibrations of the reactant and the product and to characterize them. Absence of any large Stokes' shift between absorption and emission bands of the monomer crystal shows that exciton-phonon coupling is weak, and the reaction is not likely to be phonon mediated. Phonon spectroscopy shows that the reaction proceeds by a heterogeneous mechanism. Sharp phonon bands of the product, however, suggests that the photopoly P2VB lattice is highly ordered.
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  • 46
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 285-297 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electronic paramagnetic resonance (EPR) and conductivity of pristine and iodine-doped PPMQ were studied. The pristine polymer EPR signal exhibited a Lorentzian line shape. Unpaired spin density measurements indicated that the spin concentrations of the undoped polymer lie in the range of one spin per 150-190 repeat units at room temperature. The peak-to-peak width doubled, the line shape became asymmetric and the spin concentration in the polymer increased slightly after doping with iodine. EPR saturation experiments show that the spin lattice relaxation time T1 is sensitive to trace impurity. Considerable reduction of T1 after doping with iodine shows strong coupling between the spin system and N-iodonium nucleus. Conductivity increases up to 5 orders of magnitude by iodine doping; at room temperature, the best value found was 0.017 S/cm. The activation energy for conductance after doping is about half that of pristine polymer.
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  • 47
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 327-335 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alternating copolymers of β-methylstyrene and maleic anhydride were prepared by free-radical-initiated polymerization in bulk and in toluene as a solvent. The reactivity ratios k1c/k12 and k2c/k21 were calculated from the change of copolymerization rate with a monomer feed at a constant total monomer concentration according to the generalized model of Shirota and coworkers. From the equation Rp = Rp(f) + Rp(CT) were calculated Rp(f) and Rp(CT), and it was found that in toluene the copolymerization proceeds predominantly by the addition of CT-complex monomers. Termination occurs predominantly by homotermination of β-methyl-styrene macro free radicals, kt22, but the cross termination kt21 is also operative.
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  • 48
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 343-351 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of vinyl chloride in the presence of systems containing a transition metal compound/Lewis base and an organoaluminum compound of a different length of carbon chain have been carried out. The influence of the structure and the concentrations of particular components on the polymerization yield and molecular weight of the products has been determined. The polymerization of vinyl chloride proceeds according to the free radical mechanism, and the effectiveness of such types of initiators decreases with an increase in the length of the substituent chain in the organoaluminum chain. When using ethyl derivatives, the maximum degree of vinyl chloride conversion is about 75%, and for polystyryl or polyisoprenylaluminum of an average polymerization degree of 50-100, the conversion did not exceed 0.5%. The maximum polymerization degree of vinyl chloride in block copolymers containing polyisoprenyl or polystyryl units was 90-300.
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  • 49
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 437-441 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 50
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1553-1562 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of organometallic cocatalysts on the polymerization of disubstituted acetylenes were investigated. Diphenylacetylene did not polymerize with TaCl5 alone, while it produced a polymer quantitatively in the presence of appropriate cocatalysts (Me4Sn, Et3SiH, etc.). The poly(diphenylacetylene) formed was an insoluble yellow solid. 1-Phenyl-1-alkynes (1-Phenyl-1-butyne and -1-octyne) polymerized with TaCl5 and NbCl5 alone to yield polymers whose weight-average molecular weights (Mw's) were ca. 5 × 105. Use of cocatalysts (nBu4Sn etc.) to the polymerization of these monomers accelerated the reaction, and increased the polymer molecular weights up to ca. 1.5 × 106. The poly(1-phenyl-1-alkynes) were soluble white solids. Internal octynes (2-, 3-, and 4-octynes) gave mixtures of a polymer and cyclotrimers with TaCl5 alone. In contrast, cyclotrimers formed virtually selectively by addition of cocatalysts. Thus, various effects of organometallic cocatalysts were observed depending on the kind of monomer.
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  • 51
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1619-1631 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The total absorption spectrum of the UV absorber sodium 2-(2′-hydroxy-5′-methylphenyl) benzotriazole sulfonate (TINS) has been resolved into contributions by two ground-state forms in acetonitrile-water solvent mixtures and hydrogen bonding polymer and protein substrates. These two ground-state species can be assigned to (i) a planar intramolecularly hydrogen bonded form which can undergo the efficient nonradiative energy dissipation process of excited-state intramolecular proton transfer (ESIPT), and (ii) a fluorescent nonplanar species in which ESIPT is effectively prevented. The mole fractions of each contributing conformer in the polymeric substrates have been estimated. In all the polymer systems studied, a significant proportion of the TINS molecules exist in the nonplanar form and thus may not contribute to photostabilization of the substrate. The proportion of nonplanar molecules varied from 11 to 86% in synthetic polymers and 20 to 41% in protein substrates.
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  • 52
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1653-1662 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: MS and GPC analyses are used to identify the cyclic oligomers formed in the polycondensation reactions of aromatic dithiols and dibromoalkanes leading to aromatic-aliphatic polysulfides. A correlation exists between the two sets of data obtained by these techniques. Mass spectra of the cyclic oligomers formed in the polymerization reactions are reported.
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  • 53
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1709-1712 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 54
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1697-1708 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal degradation of vinylidene chloride/methyl acrylate/phenylacetylene (VDC/MA/PA) terpolymers containing a constant 9 wt % methyl acrylate and small but varying amounts of phenylacetylene has been examined in the solid phase and in bibenzyl solution. Thermally promoted degradative dehydrochlorination, largely uncomplicated by methyl chloride formation, readily occurs at temperatures approaching 200°C. Incorporation of phenylacetylene into the polymer structure greatly facilitates degradative dehydrochlorination. Indeed, the presence of phenylacetylene induces the formation of polyene segments during the polymerization so that all the terpolymers, even at very low phenylacetylene loading, are tan in color. The decreased stability of polymers containing internal unsaturation arises from an increased rate of initiation for the degradation reaction. The propagation rate is largely unaffected by the level of unsaturation initially present in the polymer. Thus random double bonds have been identified as the principal defect sites responsible for the facile degradation of Saran copolymers. Species which promote the degradation of Saran polymers probably do so by facilitating the introduction of double bonds into the structure. The ratio of hydrogen chloride to stilbene formed for degradation of the terpolymers in bibenzyl solution is ca. 35:1. This is strongly reminiscent of PVDC degradation and suggests that for degradation of either the homopolymer or Saran copolymers the chain-carrying allylic radical pair does not dissociate to any appreciable extent as dehydrochlorination occurs.
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  • 55
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1717-1728 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bulk polymerization and copolymerization of N-(1,1′-dimethyl-3-oxobutyl) acrylamide oxime have been studied. Polymerization of diacetone acrylamide oxime was carried out with different initiating systems. The rate of polymerization of diacetone acrylamide oxime with azoisobutyronitrile as the initiating system was much higher than with peroxides. However, in the case of perester initiating systems (t-butyl perbenzoate and t-butyl per ethyl-2-hexanoate), cobalt salt promoted the polymerization rate markedly. Diacetone acrylamide oxime readily formed copolymers with a variety of comonomers (crosslinking agents and reactive diluents). Gel permeation chromatography has shown a higher reactivity of diacetone acrylamide oxime with trimethylol propane trimethacrylate as crosslinking agent and N-vinyl-pyrrolidone as reactive diluent. Therefore, the dynamic mechanical analyses presented an increase in Tg with trimethylolpropane trimethacrylate and N-vinyl-pyrrolidone as comonomers. The terpolymer formed with diacetone acrylamide oxime, trinethylolpropane trimethacrylate, and N-vinyl-pyrrolidone exhibited interesting mechanical properties and high temperature behavior.
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  • 56
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1681-1695 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal degradation of vinylidene chloride/phenylacetylene copolymers containing small but varying amounts of phenylacetylene has been examined in both the solid phase and in bibenzyl solution. Incorporation of phenylacetylene into the poly(vinylidene chloride) structure greatly facilitates degradative dehydrochlorination. Indeed, the presence of phenylacetylene promotes the formation of polyene segments during the polymerization process so that all the copolymers, even at very low phenylacetylene loading, are tan in color. The decreased stability of polymers containing interal unsaturation arises from an increased rate of initiation for degradative dehydrochlorination. The propagation rate is largely unaffected by the level of unsaturation initially present in the polymer. The ratio of hydrogen chloride to stilbene formed for degradation of these copolymers in bibenzyl solution is approximately 35:1. This suggests that the chlorine atom of the initially-formed radical pair preferentially abstracts an adjacent hydrogen atom rather than interacting with solvent, i.e., the chain-carrying radical pair does not dissociate appreciably as the unzipping dehydrochlorination occurs. Thus random double bonds introduced in a variety of ways may be identified as principal defect sites responsible for the initiation of the degradative dehydrochlorination of poly(vinylidene chloride). Species which promote the degradation of poly(vinylidene chloride) probably do so by facilitating the introduction of random double bonds into the structure.
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  • 57
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1745-1753 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solid polymer electrolytes with different stoichiometries were prepared from molten poly(ethylene oxide) (PEO) containing various amounts of potassium thiocyanate (KSCN). X-ray diffraction and conductivity measurements revealed that both morphology and conductivity were dependent on their stoichiometries, and that the highest conductivity at ambient temperature corresponded to 3.98 × 10-6 S cm-1 for the amorphous complex with the composition of X = 0.15 (X = [KSCN]/[EOunit]). The temperature dependence of the conductivity showed a WLF-type behavior for the amorphous complex, whereas it showed an Arrhenius-type behavior for a crystalline complex with the composition of X = 0.2. It was also found that the ionic mobility at 60°C of the amorphous complex was approximately 2.25 times greater than that of the crystalline complex. Furthermore, results of the infrared reflection spectroscopy measurements suggested that the mobility of potassium ion (K+) was correlated to the degree of the interaction between K+ and ether oxygens.
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  • 58
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1755-1767 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The grafting of methyl methacrylate (MMA) onto polybutadiene (PB) latexes prepared by seeded emulsion polymerization at 50°C was investigated as a function of: (a) initiator concentration used in the secondary polymerization, (b) monomer-to-polymer ratio, (c) the specific surface area of the seed latex, and (d) the degree of conversion. The thin layer chromatography/flame ionization detection (TLC/FID) technique was used to determine the proportion of graft copolymer in the core/shell latex, It was found that grafting PMMA onto PB depended upon the concentration of initiator, decreasing as the concentration was increased. The amount of grafting increased with increasing specific surface area of the seed latex, while the molecular weight of the acetone-soluble graft copolymer decreased. The amount of graft copolymer was found to decrease concurrently with increasing monomer-to-polymer ratio and degree of conversion. These results suggest a hydrogen abstraction mechanism in the formation of graft PB-PMMA through a chain transfer process.
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  • 59
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1825-1846 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal degradation behavior of polyacrylamide and poly(acrylamide-co-acrylate) was studied by differential scanning calorimetry, thermogravimetric analysis, gas chromatography/mass spectrometry, and carbon-13 solid state nuclear magnetic resonance. The degradation products over the temperature range of 115-450°C were characterized. Mechanisms are proposed for the degradation processes involved.
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  • 60
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1887-1907 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The NMR spectra and UV absorptions of polynucleotide analogs with a poly(ethylenimine) (PEI) backbone containing adenine, cytosine, and hypoxanthine pendants have been examined. As has been shown in single-stranded polynucleotides, these polymers also exhibited base stacking behavior in aqueous solution as well as in 2,2,2-trifluoroethanol. Such stacking resulted in significant UV hypochromicities and observed differences in the NMR spectra compared to the corresponding model compounds. From continuous variation mixing experiments, well-defined base pairing interactions were observed between complementary graft polymers in aqueous solutions. Enhanced UV hypochromicity due to such interactions was also observed.
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  • 61
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1967-1978 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dimethyl phosphonomethylheptamethylcyclotetrasiloxane (II) and 1, 3-bis(dimethyl phosphonomethyl)tetramethyldisiloxane (III) have been prepared by Arbuzov reaction of trimethyl phosphite with bromomethylheptamethylcyclotetrasiloxane (I) and 1, 3-bis(bromomethyl)tetramethyldisiloxane, respectively. Dimethyl phosphonomethylmethylsiloxane dimethylsiloxane copolymers have been prepared by acid-catalyzed ring-opening polymerization of II with hexamethyldisiloxane (MM) as an end-capping reagent and by reaction of II with III as an end-capping reagent. Dimethylsiloxane polymers with dimethyl phosphonomethyldimethylsiloxy end groups have been prepared by acid-catalyzed polymerization of octamethylcyclotetrasiloxane (D4) and III. Under these conditions hydrolysis of the dimethyl phosphonate ester groups was a problem. On the other hand Arbuzov reaction of trimethyl phosphite with bromomethylmethylsiloxane dimethylsiloxane copolymer gave a dimethyl phosphonomethylmethylsiloxane dimethylsiloxane copolymer with uniform properties. These polymers have been characterized by 1H-, 13C-, 29Si-, and 31P-NMR spectroscopy. Their molecular weight distributions have been determined by gel permeation chromatography (GPC) and their thermal stability measured by TGA.
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  • 62
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1979-1988 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cationic ring-opening polymerization of trioxane and 1,3-dioxolane was found to be initiated by CO+CIO4- groups on a carbon black surface, which were introduced by the reaction of COCI groups with AgCIO4. The activation energy of the ring-opening polymerization of trioxane was estimated to be 15.5 kcal/mol. In the polymerization system, poly(oxymethylene) and poly(1,3-dioxolane) formed were effectively grafted onto carbon black depending upon the propagation of these polymers from the carbon black surface; for instance, the grafting ratio of poly(oxymethylene) onto carbon black increased with an increase in conversion and went up to about 180%. Although the grafted chain of poly(oxymethylene) was subject to stepwise thermal depolymerization from the chain ends, the thermal stability of poly(oxymethylene)-grafted carbon black was improved by acetylation of hemiformal end groups. The molecular weight of ungrafted poly(oxymethylene) formed in the polymerization was determined to be 1.8-2.0 × 104. Furthermore, the copolymerization of trioxane with 1,3-dioxolane, styrene, and other comonomers initiated by CO+CIO4- groups and the thermal stability of these acetal copolymer-grafted carbon black were investigated.
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  • 63
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1463-1474 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel poly-Schiff bases (PSB's) that contain trans-1,2-bis(9-carbazolyl)cyclobutane(DCZB) units were synthesized by the direct polycondensation of trans-1,2-bis(3-formyl-9-carbazolyl)cyclobutane with aromatic diamines in n-amyl alcohol at 160°C. Complexation of these PSB's and of poly(vinyl DCZB) (PVDCZB) with iodine produced cation-radical salts which resulted form the transfer of an electron from DCZB moieties to iodine. All the undoped polymers were insulators having electrical conductivity of the order of 10-10-10-12 S cm-1 depending on the structure of polymers. By doping with iodine, the electrical conductivity increased by several orders of magnitude and reached a value of 10-3 S cm-1 in the case of PVDCZB and 10-5-10-6 S cm-1 in the case of PSB's. The electrical conductivity of doped PSB's increased with decreasing diamine length. PVDCZB having the same iodine content per carbazole unit as poly(9-vinyl-carbazole) (PVK) has a greater electrical conductivity than PVK.
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  • 64
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1523-1543 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparation of new model polymers of polynucleotides with poly(vinylamine-vinylalcohol) [P(Vam-Val)] backbones and different kinds of nucleic acid base derivatives as grafted pendants is described. At first, the grafting of (-) and (±)-2-(thymin-1-yl)propionic acid [(-) and (±)TPA] onto linear P(Vam-Val) at the amino group via an amide bond was carried out in a mixed solvent of ethanol-dimethylformamide by selective N-acylation of the active ester of N-hydroxy-5-norbornene-2,3-dicarboximide (HONB) or N-hydroxysuccinimide (HOSu). This procedure gave the corresponding hydroxyl polymers P[Vam(-)T-Val] and P[Vam(±)T-Val]. In addition, direct, low temperature esterification was used to graft (-), (±)TPA, and (±)-2-(uracil-1-yl)propionic acid, [(±)UPA], onto the hydroxyl polymer at the hydroxyl group via an ester bond. This process gave the corresponding copoly(Vam-Val) with different or the same kinds of nucleic acid base derivatives. P[Vam(-)-Ve(-)T], P[Vam(±)T-Ve(±)T], P[Vam(-)T-Ve(±)U], and P[Vam(±)T-Ve(±)U] are representative examples. The related monomer and segmental model compounds were also prepared by this method; 3-aminopentane, 3-pentanol, 3-amino-1-propanol, and threo-2-amino-4-pentanol were employed in the syntheses. The segment models were separated and purified using HPLC techniques.
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2231-2240 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complexes formed between palladium (II) and a polymeric ligand derived from L-asparagine, poly(N-methacryloyl-L-asparagine) (PNMAsn) have been investigated by electronic absorption and circular dichroism. N-isobutyroyl-L-asparagine (NIBAsn) was also synthesized and studied with the purpose of comparison with its polymeric analog. NIBAsn gives two complexes: at low pH, an optically active complex between one carboxylate and one secondary amide nitrogen (so-called 1N complex), and at higher pH, a 2N complex involving the primary and secondary amide group. This complex is also optically active. PNMAsn gives at low pH a 1N complex similar to that of NIBAsn, but at higher pH the 2N complex is formed between two carboxylate groups and two secondary amide groups of two different side chains of the polymer. At very high pH this 2N complex is hydrolyzed, i.e., the carboxylate-palladium bonds are replaced by hydroxyle-palladium bonds, and the complex becomes optically inactive.
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2261-2268 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(ethylene glycol methyl ether)-b-poly(ethylenimine hydrochloride) was characterized using potentiometric and viscosimetric titration methods. The average chemical compositions of the polyamine hydrochloride salts estimated by the acid-base titration,1H-NMR, and elemental analysis were compared. The apparent dissociation constant, pK, and the inherent viscosity of the polyamine hydrochloride were found to be highly dependent on the degree of neutralization. Very strong coulombic interactions among the charged sites were observed at low pH's for this polymer.
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2185-2193 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-phenylated aromatic polyureas were synthesized by the polyaddition of dianilino compounds to aromatic diisocyanates in sym-tetrachloroethane at around 100°C. Factors that influence the reaction, such as monomer concentration, reaction solvent, catalyst, temperature, and time, were studied to optimize the conditions for the preparation of high molecular weight polymers. Compared with the analogous unsubstituted aromatic polyureas, the N-phenylated polyureas were almost amorphous and soluble in a variety of solvents and had low glass transition temperatures. Some of the polymers could be cast into transparent flexible films from chloroform solutions.
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2323-2326 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2335-2341 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(p-benzoquinono)diimidazoles have been synthesized under mild conditions (100 or 150°C) by one-stage polycondensation in N,N-dimethylacetamide (DMAc) or in polyphosphoric acid of 2,3,5,6-tetraamino-p-benzoquinone (TABQ) with terephthalaldehyde and isophthalaldehyde. The model compound 2,6-diphenyl-1,5-dihydro-1′,4′-benzoquinono[2′,3′-d:5′,6′-d′]diimidazole was also prepared by condensation of TABQ with benzaldehyde in DMAc at 100°C. The prepared polymers were completely insoluble in organic solvents but slightly soluble (0.5%) in strong acids with viscosities (ηinh) in the range of 0.17-0.38 dL/g (c = 0.2% in formic acid). Their thermal stability was studied by TG analysis.
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1737-1744 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The products in inductively coupled plasma excited in organosilicic compounds were studied on chemical structures by spectroscopic methods. Plasma-polymerized tetramethylsilane (PA) contains not only Si—CH3 groups but also Si—H groups on IR and 29Si-NMR analyses. 13C-NMR spectrum of PA reveals that the crosslinked structure of PA is mainly constructed of Ch2 and CH groups. Plasma-polymerized octamethyleyclotetrasiloxane (PD4) is composed of Si—CH3 and Si—O groups. 13C- and 29Si-NMR spectra of PD4 point out the highly preservation of the structural units similar to the monomer. These data of PD4 suggest that PD4 is formed from the ring-opening polymerization by cleavages of Si—O bonds. 13C-NMR spectrum of poly[methyltrimethoxysilane] (PT) indicates the existence of CH3—O groups, meanwhile its 29Si-NMR analysis concludes that PT is chiefly composed of the structural units similar to the monomer. The surface analyses by XPS of PA, PD4 and PT suggest that these organosilicic plasma polymers resemble their starting materials.
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1769-1779 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of N-vinylcarbazole (NVC) in the presence of transition metal salts such as WCI6, MoCI5, TaCl5 and NbCl5 under different reaction conditions was studied. In general, aromatic solvents were found to be superior to aliphatic solvents in the polymerization of NVC, i. e., both conversion and molecular weight were higher in aromatic solvents. It was observed that the polymerization reaction proceeds rapidly and almost quantitatively, even at low monomer concentration (〈 5 × 10-2M) and at low catalyst to monomer mole ratio (10-5) in aromatic solvents. The copolymerization of NVC with acenaphthylene (ACN) was also investigated in solution at room temperature. The resulting homo- and copolymer were characterized by IR, NMR, x-ray diffraction, and elemental analysis. Thermal and photophysical properties are also reported. From the spectral data, the polymerization solvent was found to have a strong influence upon the polymer stereoregularity.
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1793-1801 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of two novel polyamide ligands 3 and 4, containing 2,17-diaza[3.3](6,6′)-2,2′-bipyridinophane or 6,6′-bis(2-picolylaminomethyl)-2,2′-bipyridine units as part of the polymer backbone, respectively, and of the appropriate diamide model compounds 1c and 2c is described. 1H-NMR and IR spectral data support the ligand structures; furthermore, 1H-VTNMR analysis on macrocyclic diamide 1c indicates a restricted rotation of the amide bonds at ambient temperature and suggests for this molecule a fixed syn conformation in solution, with a “face to face” arrangement of the dipyridinyl moieties. Model compound 2c and polyamide 4 form stable 1:1 complexes with transition metals Co(II), Ni(II), and Cu(II). Conversely, macrocyclic model 1c and polyamide 3 exhibit the unique property to specifically complex Cu(II), even in the presence of sizeable amounts of Co(II) and Ni(II). The IR spectral changes related to the ligands upon complexation are briefly discussed.
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 1811-1823 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymers which have different sized crown ethers as alkali cation binding sites and photodimerizable cinnamoyl units were prepared by the cationic copolymerization of corresponding monomers. The crown-cation complexation ratio (1:1 or 2:1) was investigated by measuring quantum yields φ of the photodimerization of the crown-connected cinnamoyl units in the presence of alkali metal chlorides and also by measuring the shift of λmax of alkali metal picrates in THF on addition of the crown polymers. A significant 1:2 complex formation of alkali cations with two different sized crown ether units in the side chain of the polymers was confirmed. The alkali metal cation binding ability and selectivity of the polymers, which were studied by a method of picrate salts extraction, were markedly different from those expected from the combination of polymers of same ring-size crown ether units. When irradiated with ultraviolet (UV) light, the cinnamic acid ester groups of the polymers caused dimerization even in dilute solutions. The cation binding ability of the polymers was largely enhanced by the photodimerization of the cinnamoyl moieties with suitable template cations.
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  • 74
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2543-2559 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Urethane reactions of phenyl isocyanate alcohol systems with toluene as solvent and various aprotic polar solvents (including tertiary amines) as additives were carried out at constant temperature of 10-40°C. Analysis of the variation of the second order rate constants of these systems and those available in the literature indicates that formation of the hydrogen bonding complexes (alcohol with phenyl isocyanate and with aprotic solvent) and electron donor number (DN) of the aprotic solvent are the two factors allowing satisfactory explanation of the catalysis and inhibition effects of the wide range of aprotic solvents (including amines, amides, etc.). Based on these considerations, an ion-pair mechanism and the resulting kinetic equation for the urethane reaction are proposed. Verification on the kinetic equation with experimental results for the systems of phenyl isocyanate with alcohol in toluene (for the self catalysis of the alcohol), with dimethyl formamide and dimethyl sulfoxide in toluene (for the catalysis of the aprotic solvents), and with triethylamine in toluene (for the catalysis of the tertiary amines) shows satisfactory. In the mechanism, the aprotic solvent is considered to solvate the complex of phenyl isocyanate/alcohol at the active hydrogen to form an ion-pair which can undergo the urethane reaction more easily.
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  • 75
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2569-2576 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An aromatic, diether-linked phthalonitrile resin, prepared from 4,4′-bis(3,4-dicyanophenoxy)biphenyl, can be converted into an environmentally stable, highly conductive material by thermal means. The conductivity of the pyrolyzed polymer can be varied and controlled as a function of both the pyrolytic temperature and annealing time. This allows the generation of a range of electrical behavior from an insulator to semiconductor and approaching metallic regions.
    Additional Material: 5 Ill.
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  • 76
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of molecular weight on thermal transitions and on their thermodynamic parameters is discussed for a random thermotropic liquid crystalline copolyether based on the reaction of a 1:1 molar mixture of 1,5-dibromopentane and 1,7-dibromoheptane with 4,4′-dihydroxy-α-methylstilbene. Optimum phase transfer catalyzed polyetherification reaction conditions were established for the synthesis of polymers containing bromoalkane chain ends only over a wide variety of molecular weights. All these copolyethers present a crystalline and an enantiotropic nematic mesophase over the entire range of molecular weights studied. Both the thermal transitions and their thermodynamic parameters are strongly molecular weight-dependent up to Mn = 10,000-12,000, after which they remain constant. The enthalpies and entropies of isotropization of the copolyethers are higher than those of melting. This is in contrast to the same thermodynamic parameters of the corresponding homopolyethers. The enthalpies and entropies of isotropization of both homopolymers and copolymers present similar values, suggesting that copolymerization does decrease the degree of order in the crystalline phase but does not significantly change the alignment degree of the mesogenic units in the nematic mesophase.
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  • 77
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2021-2024 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 78
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2699-2709 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization behavior of N-(p-aminobenzoyl)caprolactam was studied. It was found that polymerization could proceed by either elimination of caprolactam or by ring opening. Polymers prepared at temperatures above 200°C showed a greater tendency for ring opening to produce alternating aromatic/aliphatic copolymers than did polymers prepared at lower temperatures. Block copolymers of poly(p-benzamide) and nylon 6 were prepared by a two-stage hydrolytic polymerization process or by anionic polymerization at temperatures 〉 200°C. Polymer microstructures were determined using 13C-NMR spectroscopy by comparison with homopolymers and model alternating copolymers. The alternating copolymer prepared by condensation of N-(p-aminobenzoyl)-6-caproic acid showed a melting transition at 300-305°C in the DSC and a Tg in subsequent heating cycles of 116-119°C. Copolymers made with the two-stage process were rich in p-benzamide sequences and showed no Tg or Tm below 400°C. Copolymer made with NaH was rich in nylon 6 units, showed a Tm of 175-180°C and a Tg of 80-81°C, and was homogeneous in both the melt and solid.
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  • 79
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2747-2753 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fluorine-containing polyarylates having inherent viscosities of 0.2-0.8 dL/g were prepared from tetrafluoroisophthaloyl chloride and various bisphenols by low temperature solution polycondensation in chloroform with triethylamine or by two-phase polycondensation in a dichloromethane-water or nitrobenzene-water system with benzyltriethylammonium chloride as the phase transfer catalyst. These polyarylates were amorphous and were readily soluble in various solvents, including chloroform and N-methyl-2-pyrrolidone. The glass transition temperature of the polymer derived from 2,2-bis(4-hydroxyphenyl) propane was 150°C. These polyarylates started to lose weight around 350°C in an air or nitrogen atmosphere.
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  • 80
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2791-2798 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To investigate the polymerization systems driven by aromatization energy, 4-allylidene-2,6-dimethyl-2,5-cyclohexadien-1-one (Ia), 5,7-dimethyl-1-vinylspiro[2,5]octa-4,7-dien-6-one (Ib), 4,7-dimethyl-1-vinylspiro[2,5]octa-4,7-dien-6-one [Ic], 2-vinyl-2′-methylspiro[cyclopropane-1,4′-(1′-naphthalenone)] (Id), and 2-phenyl-2′-methylspiro[cyclopropane-1,4′-(1′-naphthalenone)] (Ie) were prepared and polymerized with sodium cyanide in N,N-dimethylformamide. Monomer Ia was highly polymerizable even at -65°C. Monomers Ib-Ie also polymerized well, giving powdery polymers that were soluble in common solvents. All the polymerizations took place through the aromatization of the cyclohexadienone ring, suggesting that the aromatization energy is the driving force for the polymerization of these monomers.
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  • 81
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2827-2838 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: p-Vinylphenyl glycidyl ether (VPGE), a styrene derivative with an epoxy pendant, was polymerized by various cationic initiators, and its selective vinyl polymerization was investigated at low temperatures below -15°C. BF3OEt2 (a metal halide) and CF3SO3H (a strong protonic acid) polymerized both vinyl and epoxy groups of VPGE, and produced cross-linked insoluble polymers. The HI/I2 initiating system and iodine, in contrast, polymerized its vinyl group in polar solvents (CH2Cl2 and nitroethane) highly selectively in the temperature range of -15 to -40°C to give soluble polymers with a polystyrene backbone and epoxy pendants; however, under these conditions, 10-15% of the epoxy groups of the polymers were consumed during the polymerization by the reaction with the growing species. The polymerization by HI/I2 in CH2CI2 involved a long-lived propagating species, as indicated by a progressive increase in the molecular weight (M̄n) of the polymers with monomer conversion and their fairly narrow molecular weight distributions (M̄w/M̄n ∼ 1.6). The differences between the polymerizations of VPGE and p-isopropenylphenyl glycidyl ether, an α-methylstyrene-type counterpart of VPGE, were also discussed with an emphasis on the effects of the α-methyl group in the latter monomer.
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  • 82
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2195-2206 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of interfacial polycondensation of bisphenol A with isophthaloyl chloride and terephthaloyl chloride in dichloromethane with triethylbenzylammonium chloride (TEBAC) as the catalyst was investigated via measurements of bisphenolate concentration by UV. The reaction was found to be second order with respect to bisphenolate. The dependence of the rate constant on stirring speed, amount of TEBAC, and reaction temperature was studied. The rate constant was increased with an increase of stirring speed, quantity of TEBAC added, as well as the reaction temperature. The activation energy was found to be 7.7 kcal/mol at a stirring speed of 700 rpm in the presence of 0.160 of TEBAC. The role of TEBAC was found to be interesting. It did not alter the equilibrium (the partition coefficient remained the same in the presence of TEBAC), but it did enhance the transfer rate of bisphenolate.
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  • 83
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2165-2173 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymerization of an isocyanide giving an insoluble homopolymer with another isocyanide giving a soluble homopolymer in ethanol solution using 0.5-1% of a nickel (II) catalyst in many cases gives a soluble copolymer containing pendant groups arising from both isocyanides. Thus, methyl isocyanide, which gives an insoluble homopolymer, gives chloroform-soluble copolymers incorporating 39-44% of pendant methyl groups when copolymerized with equimolar amounts of tert-butyl isocyanide or several aryl isocyanides. Similarly, cyclohexyl isocyanide, which also gives an insoluble homopolymer, gives chloroform-soluble copolymers incorporating 43-59% of pendant cyclohexyl groups when copolymerized with equimolar amounts of several aryl isocyanides. The compositions, chloroform solubilities, and polystyrene equivalent molecular weights are given for 33 different copolymers obtained by copolymerizations of various equimolar binary mixtures of the monomers CH3NC, (CH3)3CNC, cyclo-C6H11NC, C2H5NC, CH3CH=CHNC,(CH3)2C=CHNC, 2,4,6-(CH3)3C6H2CH=CHNC, C6H5CH(CH3)NC, CH2=CHNC, (CH3)3CCH=CHNC, C6H5NC, 2- and 4-CH3C6H4NC and 2-, 3-, 4-CH3OC6H4NC using the nickel (II) catalyst system.
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  • 84
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2175-2183 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Previous work by a number of researchers has noted the presence of anhydride during the imidization step of polyimide polymer processing from diester-diacids and diamines. This has been often, and incorrectly, dismissed as being due to the reversion of the intermediate amide-acid. Comparison of the relative rates of reactions among model compounds demonstrates the intermediacy of anhydride in the imidization reaction. When creation of the anhydride is blocked, the production of amide-acid is greatly slowed. Infrared and NMR observations of mixtures of monomers confirm the production of anhydride as a necessary intermediate in the imidization reaction occuring during the production of polyimide polymers from diester diacids.
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  • 85
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2221-2230 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymers of ethyl acrylate (EA) with lithium acrylate (LiA) with relatively low contents of LiA units (up to 30%) were synthesized by alkaline hydrolysis of poly(EA). 13C-NMR spectra of these copolymers registered in a mixture of deuterated benzene with deuterated methanol (85:15 v/v) presented configurational splittings of the ester methylene, methylene main chain, and ester carbonyl group signals. Assignments of these splittings were made and Bernoulli statistics with a meso probability of 0.48 could fit both poly(EA) and poly(EA-co-LiA). Only the C=O signal of the copolymer was sensitive to sequence distribution and indicated that the LiA units have a tendency to be isolated on the chain. Two-dimensional HETCOR pulse sequence helped to assign the main chain proton spectrum.
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  • 86
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2479-2491 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cure of pyromellitic dianhydride-oxydianiline polyamic acid is compared with that of a model compound, diphenylcarbamido-dicarboxy-benzene, both having been synthesized in 1-methyl-2-pyrrolidinone (NMP). Laser interferometry and thermogravimetric analysis showed that, analog to the diamic acid model compound, the polyamic acid forms complexes with NMP (repeat unit/NMP: 1/4 and 1/2). Thermal stability of these complexes was found to be similar to the ones of the diamic acid model compound as revealed by comparison of decomplexation temperature-heating rate curves. Activation energies of the decomplexation processes for the diamic acid are given. Anhydride formation, a reaction found in the cure of the model compound to compete with imidization, takes place also during the polyamic acid cure at fairly low temperatures. The molecular weight drop due to chain scission resulting from anhydride formation was followed by viscometry.
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  • 87
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The asymmetric reduction of prochiral aromatic ketones with modified reagents prepared from sodium borohydride and carboxylic acids in the presence of both chiral polymers and relating low molecular weight compounds having (+)-5,6-exo-dihydroxybornyl derivatives was carried out. The enantioface differentiation took place effectively by raising the reaction temperature, and the highest enantiomeric excess was achieved at 10°C (24.3%) in the presence of the chiral polymers. A higher optical yield (87.8%) can be obtained in the asymmetric reduction by using the low molecular weight (+)-5,6-exo-diol compounds. The effect of the reaction temperature, solvents, and the advantages of the chiral polymer-bound reagents were also discussed.
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  • 88
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2561-2568 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of 1,3,6-trioxacyclooctane initiated by trityl salts with various counterions in CH2Cl2 was investigated. The reaction mixtures and the isolated polymers were analyzed by GPC (double detection - IR and UV at 254 nm),1H-, and13C-NMR spectroscopy. In the early stage of polymerization only oligomers (mainly cyclic) were formed. With longer reaction times, linear polymers (yield 86-94%, M = 70,000-80,000) were obtained. The concentration of each individual oligomer passed through a maximum and decreased, reaching its equilibrium concentration. The time interval necessary to reach the maximum concentration increased with n. The total concentration of the oligomers was 0.2 mol L-1 regardless of the initiator used. Conditions for polymerization with virtually no termination were found. Addition of p-methoxystyrene to the “living” polyacetals resulted in block copolymers. GPC,1H- and 13C-NMR and acidolytic degradation were used to prove the formation of AB block copolymers. The reactive alkoxycarbenium growing species are responsible for the formation of block polyacetal-polymethoxystyrene copolymer.
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  • 89
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2605-2627 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a series of vinylbenzyl ether macromonomers of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-VBE) with number average molecular weights between 1,000 and 27,000 and narrow molecular weight distribution is presented. The reactivity ratio r1 was determined for the comonomer pairs methyl methacrylate (MMA) and butyl methacrylate (BMA), respectively (M1), and PPO-VBE (M2) over the entire range of molecular weights of the macromonomer. r1 was determined by the single experiment intergrated equation. Since both the monomer and macromonomer present an induction period, it has been shown that the determination of r1 from one single point experiment is not correct. Accurate r1 values can be obtained from one single copolymerization experiment only when the comonomer conversions are determined at several different reaction times. The macromonomer reactivity (1/r1) increases with its molecular weight up to about 5,000-7,000. Above these values its reactivity decreases. An attempt to explain this behavior based on the kinetic excluded free volume effect is presented.
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  • 90
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2643-2664 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rapid defluorination of fluoropolymer surfaces by their exposure to a hydrogen plasma excited by an inductively coupled RF field has been studied using ESCA. The results are interpreted in terms of a reaction/depth profile; the reaction is not uniform with depth leading to the formation of an approximately 20 Å thick boundary layer of defluorinated material.
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  • 91
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2711-2716 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several new copolymers have been synthesized. Initial polycondensation of mixtures of aryl and arylalkyl carboxylic acids containing aromatic hydroxyl and amine substituents led to random copolyamides. Thermal cyclization of these prepolymers (inherent viscosities of about 0.2 dL/g) gave copolybenzoxazoles with inherent viscosities of about 1.4 dL/g. Thermal stability as measured by TGA was similar for the 1:1 copolymers and the homopolymers containing hydrocinnamic units; i.e., catastrophic decomposition occurred at 450°C. Copolymers with lower ratios of the hydrocinnamic units displayed greatly improved thermal stability while maintaining good molecular weight.
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  • 92
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cationic polymerization of 2-vinyloxyethyl glycidyl ether (VEGE), a vinyl ether with an epoxy group, was conducted with various initiators in CH2Cl2 in the temperature range from +15 to -78°C, and the possibility of its selective vinyl polymerization was investigated. BF3OEt2 polymerized both vinyl and epoxy groups of VEGE to yield polymers partially insoluble in organic solvents. HI/I2, iodine, and CF3SO3H gave soluble, low-molecular-weight oligomers with epoxy pendants. 1H-NMR structural analysis of the oligomeric products showed that the epoxy/vinyl ratio of the pendants decreases in the order: 100% epoxy ∼ CF3SO3H 〉 HI/I2 ∼ I2 ≫ BF3OEt2. Although HI/I2 or iodine mainly polymerized the vinyl group, the reaction of the vinyl ether-type growing end with an epoxy group of VEGE took place during the polymerization, so that the monomer conversion leveled off at about 40%.
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  • 93
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2631-2642 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using fluorescence spectroscopy and gel content measurement, the photolysis of simple polyurethanes based on methylene 4,4′-diphenyldiisocyanate (MDI) is shown to depend on both the flexibility and crystallinity of the polymer. Polyurethane films based on MDI and 1,12-dodecanediol (MDI-12) can be either annealed or quenched to yield a semicrystalline (as measured by DSC and X-ray diffraction) or amorphous film, respectively. In the case of the quenched (amorphous) film, photolysis yields an ortho photo-Fries product whereas the annealed (semicrystalline) film does not. Similarly, for a given photolysis time the annealed film generates a lower extent of crosslinked gel. In addition, photolysis of amorphous polyurethane films derived from MDI and ethylene oxide oligomers shows that for relatively inflexible polymers with only three ethylene oxide segments, little or no ortho photo-Fries rearrangement products are generated upon photolysis. In contrast, photolysis of more flexible polyurethane films with approximately 13 ethylene oxide linkages yields the ortho photo-Fries product. Apparently, for aromatic diisocyanate based polyurethanes, the extent and mechanism of degradation is directly dependent on the crystallinity and main-chain flexibility of the polymer.
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  • 94
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    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 3413-3422 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Previous studies of the photodegradation of bisphenol A polycarbonate (BPA PC) indicate that both alkyl side chain and ring oxidation play significant roles. In order to determine the relative importance of these two pathways in the photoyellowing that accompanies photodegradation, side chain free polycarbonates based on 3,3′-dihydroxydiphenyl ether were synthesized and tested. Both accelerated weathering experiments using a QUV test apparatus and outdoor weathering indicated that these polymers photoyellowed faster than BPA PC. This suggests that ring oxidation is an important source of photoyellowing of aromatic polycarbonates.
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  • 95
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermotropic liquid crystalline (LC) polyethers and copolyethers have been synthesized from 4,4′-dihydroxy-α-methylstilbene (HMS) and α,ω-dichlorooligo(oxyethylene)s having between 2 and 5 as well as 8.7 oxyethylene units. Copolyethers were prepared from a 1:1 mol/mol ratio of two dissimilar spacers. These polymers have been prepared by a phase transfer catalyzed (PTC) polyetherification of bisphenols with these electrophiles by utilizing 50 mol% tetrabutylammonium hydrogen sulfate per phenol group. Kinetic experiments with either 5 or 50 mol% catalyst vs phenol groups in the polyetherification of 4,4%-isopropylidenediphenol with 2-chloroethyl ether have shown that a change in catalyst primarily affects the rate of reaction, with 50 mol % being faster. The prepared polyethers and copolyethers are soluble in common organic solvents. Both polyethers and copolyethers are crystalline. Polymers prepared to contain tetraoxyethylene spacers exhibit monotropic LC behavior. Copolymers prepared to contain tri- and tetraoxyethylene spacers (1 : 1 mol/mol) [PE34] were the only polymers exhibiting enantiotropic LC behavior. Longer spacers tend to destabilize the phase transitions, as suggested by the dependence of thermal transition temperatures upon the differential scanning calorimeter rate. All prepared polymers act as podants in solution, measured by picrate extraction experiments. Solid state complexes have been prepared from the polymer with a pentaoxyethylene spacer [PE5] and PE34 with LiCF3SO3. PE5 can dissolve LiCF3SO3 in the range of 0.21-2.2 mol salt/mol polymer (m.r.u.) [S/P] without the observation of free salt. PE5 complexes of/or below S/P of 0.43, upon annealing at room temperature, exhibited the two melting transitons observed in the polymer alone. PE5 complexes of/or above S/P of 0.77 only exhibited a Tg. The Tg of PE5 complexes were found to change nonlinearly with S/P, while Tm1 changed linearly. Tm2 was independent of S/P. Only one complex with PE34 gave two transitions (Tm2,Ti) in dynamic DSC experiments. Other PE34 complexes followed a behavior similar to PE5 complexes.
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2847-2870 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A systematic study has been made on the functions of external Lewis base (Be, methyl-p-toluate, MPT) and internal Lewis base (Bi, ethyl benzoate, EB) for the CW-catalyst system MgCI2/EB/PC/AlEt3/TiCl4-AlEt3/MPT (PC, p-cresol). Bi is a nonstereoselective modifier. It increases the active site concentrations and rate constants of propagation, kp, of both the isospecific and nonspecific sites, and thus the productivities of the stereoregular and irregular polypropylenes by five- to tenfold. It seems that Bi complexes with the MgCl2 support to lower the electronegativity of the surface Mg atoms. It also acts to lower the rate constant of chain transfer to aluminum alkyl, kAtr, by two- to fourfold. The action of Be is highly stereospecific. The isotacticity index of polypropylene is ≫ 95% in the presence of Be but ≪ 68% without it. Addition of Be decreases nonspecific [Ti*]a by about (11 ± 2)-fold; there is only about a twofold reduction of the isospecific [Ti*]i. It decreases kp,a about three times but has no effect on kp,i, so that the latter is (21 ± 4) times the former. Be decreases kAtr,i for transfer with aluminum alkyl much more than it does to kAtr,a; but it does not affect the rates of chain transfer with monomer and by β-hydride elimination or the rate of catalyst deactivation. The number of active sites without Be is [Ti*]i = 15% and [Ti*]a = 55% for a total of 70%. In the presence of Be they are both about 6%. Optimum performance in propylene polymerizations requires both Bi and Be in the case of the CW-catalyst.
    Additional Material: 14 Ill.
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  • 97
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2925-2929 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 98
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2941-2952 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(L-trans-3-ethylproline), L-PT3EP, and poly(D-trans-3-ethylproline), D-PT3EP, were prepared by ring opening polymerization of the corresponding N-carboxyanhydrides (NCA) using triethylamine as an initiator. Using circular dichroism spectroscopy, it was shown that the incorporation of an ethyl group at the 3 position of the pyrrolidine ring caused a noticeable change in the conformational behavior of the polymer in solution. The ethyl group limited to some extent rotation of the polymer chain around the C——CO bond and prevented the mutarotation between the two forms found in poly-L-proline polymers.
    Additional Material: 8 Ill.
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  • 99
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    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2963-2985 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Asymmetric linear and cross-linked imidazole-containing polymers were prepared from 1-[2(S)-methylbutyl]-4-vinylimidazole and 1-[2(S)-methylbutyl]-5-vinylimidazole. The esterolytic reactions of these linear and cross-linked asymmetric polymers with the enantiomeric substrates (R)- and (S)-4-(3-methylpentadecanoyl)-3-nitrobenzoic acid, (R)- and (S)-S-3Me15, were studied by measuring the pseudo-first order kinetics of the solvolysis of these enantiomeric substrates in the presence of these asymmetric polymers. The linear homopolymers and copolymers of 1-[2(S)-methylbutyl]-4- and 5-vinylimidazole showed hydrophobic and electrostatic effects in the solvolysis of the enantiomeric substrates with these linear asymmetric polymers. Cross-links were introduced into these asymmetric polymers to increase the rigidity and reduce the number of conformations available to the polymer. The reduced conformational mobility was expected to enhance any enantioselectivity in the solvolysis of the enantiomeric substrates with these polymers. Using these cross-linked polymers, hydrophobic interactions were observed in the solvolysis of a series of substrates with increasing alkyl chain length. Also, on changing the polarity of the solvent, a bell-shaped rate profile was observed in the solvolysis of the long chain substrate S-3Me15. This effect was attributed to a combination of the coiling of the cross-linked polymer chains and hydrophobic interactions with the substrate on changing solvent polarity. Even with the increased rigidity of these cross-linked polymers, no significant enantioselectivity in the solvolysis of the enantiomeric substrates was observed. So, neither the linear nor the cross-linked asymmetric polyvinylimidazoles showed enantioselectivity in the solvolysis of these enantiomeric substrates. In this case, the hydrophobic interactions and the reduced conformational mobility through crosslinking were not strong enough to bring about enantioselectivity in the solvolysis of these enantiomeric substrates.
    Additional Material: 3 Ill.
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  • 100
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    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 3015-3024 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ion conductivity of poly(ethylene oxide) (PEO)-based polyurethane networks containing alkali metal salts has been investigated. Consequently, it has been revealed that the conductivity is dependent on the following parameters: lattice energy of the alkali metal salt, concentration of alkali metal salt, and the cross-linking density of the network polymer (which is a function both of the amount of cross-linking agent and the molecular weight of PEO). Under optimal conditions, the conductivity at ambient temperature corresponded to 2.51 × 10-5 Scm-1, which is greater than that of a typical alkali metal-PEO system by a factor of about 102 to 103. Moreover, from the standpoint of the application to electrochromic displays (ECD), tensile bond strength between the polymer electrolytes and tungsten trioxide (WO3), which is the most promising electrochromic material, has been evaluated. The bonding strength of the bond of WO3 with the present electrolyte has been found to be much larger than that of the alkali metal-PEO system.
    Additional Material: 8 Ill.
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