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  • 1985-1989  (3,552)
  • 1915-1919
  • 1985  (3,552)
  • Polymer and Materials Science  (3,130)
  • Engineering General  (422)
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Years
  • 1985-1989  (3,552)
  • 1915-1919
Year
  • 101
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 1449-1478 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The infrared amide I band of collagens (rat and cod skin) and related compounds (polyproline, polyglycine, and polytripeptides) was studied. Assignment of amide I-band components for polyproline II and polytripeptides (Gly-Pro-Pro)n and (Gly-Pro-Gly)n in the solid state and water solution was made. Three amide I components observed in the polypeptide spectra were attributed to three different peptide CO groups in each triplet. On the basis of this assignment, the interpretation of the amide I multicomponent structure in collagen and isomorphous oligo- and polypeptides was attempted. The ordering of intra- and intermolecular hydrogen bonds involving peptide CO groups in collagen and related compounds was discussed.
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  • 102
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A combination of novel methods of macrostructural analysis and theoretical chemistry were applied to study the metalloenzyme carboxypeptidase A and its complexes with two inhibitors - glycyl-L-tyrosine and a protein inhibitor isolated from potatoes. The methods of macrostructural analysis applied to the study of the crystal structures of these molecules include structural superposition, distance matrix analysis, and linear distance plot analysis, and the approach is complemented by the examination of computed physicochemical properties, including electrostatic potential surfaces, bulk hydrophobicity, and complementarity of van der Waals surfaces. The structural analysis identified folding domains in carboxypeptidase A that relate to such domains in carboxypeptidase B and are involved in the conformational changes following complexation with the inhibitors. The nature of these conformational changes and their relation to the physicochemical properties suggest their role in determining recognition and reactivity characteristics of the enzyme. The analysis also revealed a distinction between conformational changes in the secondary and tertiary structure of the protein that provides insight into the structure-function relationship in carboxypeptidase. Notably, some inhibitor-induced changes in structure occur in regions in which the interacting molecules are not in contact, while some of the contact regions, such as the active site, incur only minor perturbation. The analysis reveals the interrelation between the enzyme-ligand interaction and the structural perturbation outside the active site, thus illuminating one aspect of the link between the structural organization of the protein and its function.
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  • 103
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 1845-1850 
    ISSN: 0006-3525
    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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  • 104
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 1853-1861 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(Pro-Nle-Gly) was found to have a CD spectrum characteristic of a random polypeptide and an x-ray powder pattern that does not reveal any regular secondary structure. In its electron micrograph, however, filaments and fibers were seen. This is a random polymer with supramolecular structure. It suggests that the supramolecular structure seen in electron micrographs of elastin preparations and related polypeptides does not necessarily imply an ordered structure at the molecular level.
    Additional Material: 6 Ill.
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  • 105
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Heat denaturation of native globular proteins is a cooperative process usually connected with the melting of the main part of their regular secondary structure. In this paper, a noncooperative temperature-induced melting of the regular secondary structure in the carbonic anhydrase B at pH 2.6 in heavy water is observed by ir spectroscopy. The molecules of carbonic anhydrase B in an acid medium, unlike the native ones, do not have a specific tertiary structure. Nevertheless, the β-structure content is about the same in both of these states. A temperature-induced noncooperative melting process takes place from 10 to 67°C with a decrease of the antiparallel β-form content by about one third. The remaining part of the β-form melts with a more intensive heat absorption, with a maximum at 87°C. The whole melting process is practically reversible. We assume that the observed noncooperative process displays a general property of a new type of structural state of the globular protein - the “molten globule state.”
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  • 106
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of sodium ion concentration on the binding isotherms and association and dissociation reaction rates for the interaction of the closely related intercalating dication, propidium, and the monocation, ethidium, with DNA have been determined by spectrophotometric binding and stopped-flow kinetics methods. The binding of propidium to DNA is best described by a neighbor-exclusion binding isotherm (two base pairs per binding site) with negative ligand cooperatively on binding. The cooperativity parameter is fairly independent of salt concentration, while the log of the observed equilibrium binding constant varies with -log [Na+], with a slope of two for the propidium-DNA interaction. These effects of the sodium ion on the equilibrium binding of propidium with DNA are similar to those previously described for the dication, quinacrine [Wilson, W.D. & Lopp, I.G. (1979) Biopolymers, 18, 3025-3041]. Ethidium behaves, as a function of salt, as a monocation binding to DNA with neighbor exclusion and without ligand cooperativity. Equations are derived for two limiting kinetics models for intercalation involving binding of the intercalator to a preequilibrium, open state of DNA (model I) or binding form a preequilibrium externally associated state of the intercalator with DNA (model II). Model II gives the best fit to all of the kinetic results if it is assumed that the initial external interaction of the intercalator with DNA is similar to the exchange of free and condensed simple counterions. Intercalation then occurs from this state following an opening transition of the base pairs of the double helix. This model predicts a larger effect of salt concentration on the association than on the dissociation reaction, and that is what is experimentally observed. The intercalation conformational change makes a significant contribution to the ionic effects for both the equilibrium binding and the kinetic constants. The dissociation results and the association reaction results under pseudo-first-order conditions could be fit with single exponential curves under the conditions of our experiments.
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  • 107
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    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 2024-2025 
    ISSN: 0006-3525
    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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  • 108
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    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 1705-1720 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A model has been developed for approximating the free energy of collagen fibril formation (ΔFf) and the equilibrium solubility of collagen under physiological conditions. The model utilizes an expression of Flory for rodlike polymers, with the modification that the “pure” anisotropic phase is defined as a collagen fibril containing about 0.3 g water/g collagen. The model also assumes that χ1, the polymer-solvent interaction term, is entirely due to hydrophobic effects. χ1 is estimated from hydrophobic bond energies of amino acid side chains, using the results of Némethy and Scheraga. The temperature dependence of χ1 is utilized to calculate equilibrium solubilities and ΔFf as a function of temperature.
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  • 109
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    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 1809-1822 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A unified representation of helical parameters (n,h) based on a polar mapping is proposed. Its application to the case of polysaccharides allows a straightforward comparison of all secondary structures displayed by this class of biopolymers in the solid state. Based on the concept that a disordered state of a polymer may be described by a succession of local helical parameters, the application of this unified representation has been extended to the simulation of chain behavior in solution.
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  • 110
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 1801-1808 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied the structure of solid films obtained by x-ray diffraction, from several basic polypeptides with a defined sequence. The alterating polypeptides poly(Ala-Lys), poly(Leu-Lys), poly(Val-Lys), and poly(Arg-Leu) all show a cross-β-structure in which layers of hydrophilic side chains alternate with layers containing hydrophobic side chains. The other polypeptides studied are not in the β-conformation and appear to be in the α-helical conformation. The helices obtained from poly(Lys-Ala-Ala) and poly(Lys-Ala-Ala-Lys) appear to be packed in an unusual fashion, which favors interaction between alanine side chains. Such behavior is not found in poly(Lys-Leu-Ala).
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  • 111
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    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 1823-1840 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermally induced coil-helix transition of poly(γ-benzyl-L-glutamate) (PBLG) and poly(γ-methyl-L-glutamate) (PMLG) in binary solvent mixtures was investigated by calorimetric and optical rotatory dispersion (ORD) measurements. Dichloroacetic acid was the common active solvent, and the inert solvent was one of the chlorinated hydrocarbons, such as chloroform, 1,3-dichloropropane, 1-chlorobutane, or 1-chlorooctane.The thermodynamic parameters characterizing the intramolecular polypeptide and polypeptide-solvent interactions were calculated using the Karasz and Gajnos theoretical model [(1973) J. Phys. Chem. 77, 1139-1145]. It was found that the enthalpy (ΔH1) and entropy (ΔS1) of helix stabilization in the absence of the active solvent depend on the inert solvent, but only in the case of PBLG. This is explained by the additional helix stabilization achieved by the stacking of the benzyl groups. The stacking is more pronounced in less polar chlorinated hydrocarbons with longer aliphatic chains. The results obtained indicate that the maximum helix stability is reached in chlorinated hydrocarbons with 12 C atoms. In the case PMLG, with an aliphatic ester side group, ΔH1 and ΔS1 are independent of the inert solvent.The ORD measurements were used to determine the maximum fraction of helicity attained at constant solvent composition and the transition temperature, Tc, at the point where fH = 0.5. It was found that, for the same solvent composition, Tc was higher than the temperature of the midpoint of the calorimetric peak. This is explained by the fact that the maximum fraction of helicity is less than unity. The finite transition width was taken into account by calculating the phase boundaries for different fractions of helicity using the value of σ estimated from the calorimetric and van't Hoff enthalpies in the usual manner.
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  • 112
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    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 1963-1979 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: At low temperature and low salt concentration, both imino proton and 31p-nmr spectra of DNA complexes with the intercalators ethidium and propidium are in the slow-exchange region. Increasing temperature and/or increasing salt concentration results in an increase in the site exchange rate. Ring-current effects from the intercalated phenanthridinium ring of ethidium and propidium cause upfield shifts of the imino protons of A · T and G · C base pairs, which are quite similar for the two intercalators. The limiting induced chemical shifts for propidium and ethidium at saturation of DNA binding sites are approximately 0.9 ppm for A · T and 1.1 ppm for G · C base pairs. The similarity of the shifts for ethidium and propidium, in both the slow- and fast-exchange regions over the entire titration of DNA, shows that a binding model for propidium with neighbor-exclusion binding and negative ligand cooperativity is correct. The fact that a unique chemical shift is obtained for imino protons at intercalated sites over the entire titration and that no unshifted imino proton peaks remain at saturation binding of ethidium and propidium supports a neighbor-exclusion binding model with intercalators bound at alternating sites rather than in clusters on the double helix. Addition of ethidium and propidium to DNA results in downfield shifts in 31P-nmr spectra. At saturation ratios of intercalator to DNA base pairs in the titration, a downfield shoulder (approximately -2.7 ppm) is apparent, which accounts for approximately 15% of the spectral area. The main peak is at -3.9 to -4.0 ppm relative to -4.35 in uncomplexed DNA. The simplest neighbor-binding model predicts a downfield peak with approximately 50% of the spectral area and an upfield peak, near the chemical shift for uncomplexed DNA, with 50% of the area. This is definitely not the case with these intercalators. The observed chemical shifts and areas for the DNA complexes can be explained by models, for example, that involve spreading the intercalation-induced unwinding of the double helix over several base pairs and/or a DNA sequence- and conformation-dependent heterogeneity in intercalation-induced chemical shifts and resulting exchange rates.
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  • 113
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C-nmr has been employed to probe the molecular conformation and crystal structure of (1 → 6)-β-D-glucan (pustulan) in the solution, gel, and solid states. CP/MAS 13C-nmr spectra recorded for partially crystalline solid pustulan display a resonance near 82 ppm that is absent in solution spectra. The intensity and peak width of this resonance were found to depend on relative crystallinity as determined by x-ray diffraction. CP/MAS spectra of aqueous pustulan gels also exhibit the 82-ppm resonance, suggesting that the gelation mechanism may involve microcrystalline junction zones. Since the 82-ppm resonance is absent in the CP/MAS spectrum of the (1 → 6)-β-linked dimer gentiobiose, we tentatively conclude the crystal structure of this dimer does not adequately model the yet undetermined structure of pustulan.
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  • 114
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    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 2357-2369 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The frequencies observed for adenine in the Raman spectra of adenosine monophosphate (AMP) and biopolymers such as poly(A), DNA, and RNA are compared with those calculated for a model compound, 9-methyladenine, in which the methyl group is taken as a unit mass concentrated on the carbon. The force field used is a Urey-Bradley field already tested on polycrystalline adenine and its analogs D-substituted on the nitrogens, on the carbon at position 8, and on both. Assignments for adenine residue Raman bands are proposed and discussed on the basis of observed and calculated D-shifts. These assignments are examined, in particular, for bands common to both adenine and guanine residues by analysis of their behavior for Raman hypochromism.
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  • 115
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    Biopolymers 24 (1985), S. 2403-2415 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new method for determining the length distribution of microtubule preparations, using quasi-elastic light scattering (QELS) is described. The experimental electric field autocorrelation functions are analyzed using a closed-form expression recently described by Hallett, Craig, and Nickel [(1985) Biopolymers 24, 947-960], which is incorporated into an exponential sampling procedure. The resulting length distributions are compared with those obtained for the same samples with electron microscopy (EM). If standard grid-preparation procedures were used, the EM results yielded shorter length distributions than QELS. When grids were prepared at lower microtubule number densities, less grid washing was required. In these cases, excellent agreement between the EM and QELS techniques were achieved.
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  • 116
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    Biopolymers 24 (1985), S. 2131-2143 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The free fractions of monovalent and divalent counterions were determined on salt-free solutions of pectins. The effects of charge density, distribution of the carboxyl groups, polymer concentration, and the nature of the counterion were investigated by determinating the calcium and sodium activity coefficients (with specific electrodes) and by measuring the transport parameters (by conductimetry). Poor agreement for calcium ions was found with the Manning theory. The strong binding of these ions to highly charged polymers, which is ascribed to a dimerization process was demonstrated in very dilute solutions.
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  • 117
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    Biopolymers 24 (1985), S. 2145-2164 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The translational and rotational diffusion coefficients have been calculated for a simple, segmentally flexible model: the hinged dumbbell (HD). In the HD, two spherical subunits are attached to an universal joint by means of frictionless connectors. In addition to the case in which hydrodynamic interactions are neglected (NI), we have also considered two more cases, including hydrodynamic interaction by means of the Kirkwood-Riseman approximate treatment (KR) and using accurate procedure based in the series expansions for the two-sphere diffusion tensor (SE). Expressions for the friction coefficients of the HD are given for the three cases, and the diffusion coefficients are evaluted inverting the 9 × 9 resistance matrix, for two HDs with different dimensions. The KR treatment, which includes a contribution from the finite volume of the subunits, is shown to be an excellent approximation to the more rigorous procedure. In the NI case for rotation, the various coefficients present different deviations with respect to the SE results. A rough estimate of the errors of the NI relaxation times indicates that they may be smaller than 15% for a HD with identical beads. However, the influence of hydrodynamic interaction should be more important for the rotational diffusivity of a small sphere attached to a larger one. The error of the NI result for the translational diffusion coefficient is of about 25% for the two HDs.
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  • 118
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    New York : Wiley-Blackwell
    Biopolymers 24 (1985) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 119
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    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 2195-2205 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five models of collagen molecular structure incorporating a variable h-spacing were evaluated by comparing theoretical densitometric scans of segment long spacing (SLS) banding patterns with experimental densitometric scans. The five models tested assumed a shift in the h-spacing of different residues: (1) proline only, (2) hydroxyproline only, (3) proline and hydroxyproline (in the same direction), (4) proline and hydroxyproline (in opposite directions), and (5) all residues shifted depending on their relative hydrophobicity. The best correlation coefficients were obtained when, in the theoretical models, the proline residues were expanded axially and/or the hydroxyproline residues were contracted. Using the hydrophobic model, the results showed that in general the more hydrophobic a residue is, the larger its h-spacing. Theorectical models with the α2-chain in the A position of the triple helix (α2,α1,α1) correlated best with the experimental data. In conclusion, these studies suggest that variation exists in the h-spacing of the amino acid residues proline and hydroxyproline in SLS prepared for electron microscopy and stained with phosphotungstic acid and uranyl acetate. Some of this variation may be due to drying and may not be present in hydrated molecules.
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  • 120
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    Biopolymers 24 (1985), S. 2177-2177 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 121
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    Biopolymers 24 (1985), S. 2181-2184 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 122
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(dA-dT) · poly(dA-dT) undergoes a reversible conformational transition in the presence of Co(NH3)63+ or spermidine in low salt (10 mM NaCl + 1 mM Na cacodylate). This transition is similar, as judged by changes in the CD spectrum, to the B-to-X transition of the polymer provoked by alcohol and Cs+ [Vorlickova et al. (1983) J. Mol. Biol. 166, 85-92; (1982) Nucleic Acids Res. 10, 6969-6979] and by meso-substituted porphyrin ligands [Carvlin et al. (1983) Nucleic Acids Res. 11, 6141-6154]. Under the salt conditions indicated, the CD transition begins with Co(NH3)63+ at about 70 μM and is complete by 150 μM; with spermidine, it begins at about 300 μM and is complete by 600 μM. Total intensity light scattering shows a marked increase at trivalent cation concentrations somewhat below those at which the CD transition begins. Quasielastic laser light scattering (QLS) measurement of the translational diffusion coefficient, DT, shows that, in the presence of Co(NH3)63+, the hydrodynamic radius, Rh, increases from 260 to 1450 Å over the concentration range of 25 to 200 μM. With spermidine, Rh is 550±50 Å up to 200 μM, then increases rapidly. Values of Rh in this range are generally found for toroidal or other compact condensed forms of DNA. Such forms - toroidal, spheroidal, and rodlike structures - are observed in electron micrographs of poly(dA-dT) · poly(dA-dT) when the trivalent cation concentration is in the transition range. Above that range, extensive aggregation of the polymer chains is seen. Taken together, these results suggest a sequenc of related secondary and tertiary structure changes as trivalent cations are added to a low-salt solution of poly(dA-dT) · poly(dA-dT). At very low Co(NH3)63+ or spermidine, condensation of the polymer takes place while it is still in the B-form. Further additions of trivalent cation provoke a transition from B- to X-form, finally resulting in extensively aggregated polymer. These results are different from those generally observed with native DNA, where condensation with polyamines or Co(NH3)63+ in aqueous solution is not accompanied by secondary structural change. They are also different from those we have seen with poly(dG-me5dC) · poly(dG-me5dC), where condensation and the B-Z transition occur at the same ionic conditions. These distinctions are another entry in the growing catalog of sequence-dependent structural effects that may be important in the regulation of the biological activity of DNA.
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  • 123
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The assignments of several 1H lines in the spectrum of the lac repressor DNA-binding domain (or “headpiece”) are documented. These new assignments complement those obtained in a previous study [E.R.P. Zuiderweg, R. Kaptein, and K. Wüthrich (1983) Eur. J. Biochem. 137, 279] and were made from pure absorption phase two-dimensional nuclear Overhauser enhancement (2D NOE) spectra and 1H 2D double-quantum spectra of this protein. Based on the complete set of resonance assignments, a large number of interresidue NOEs are identified; these are documented and their relation with distance constraints is discussed. The identification of these NOEs is a prerequiste for the determination of the spatial structure of this protein, for which no crystallographic data are available.
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  • 124
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    Biopolymers 24 (1985), S. 2301-2332 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Physical studies and conformational analysis of human glycophorin A suggest a revised model for its molecular organization, self-association, and interactions with the erythrocyte membrane. Intrinsic viscosity has been used to study, under more physiological conditions, the monomer-dimer equilibrium demonstrated previously by polyacrylamide-SDS gel electrophoresis. The results show that the equilibrium persists in the absence of detergent and support earlier indications that the dimer is probably the physiologically relevant form and that it is promoted by salt, inhibited by conventional denaturants, and abolished by carboxymethylation.Combined application of CD, fitted to the poly-(L-lysine) model spectra of Greenfield and Fasman, and conformational prediction, by the statistical method of Chou and Fasman and the stereochemical approach of Lim, suggests five helical sequences in glycophorin A: Arg-39 to Tyr-52 (A); Gln-63 to Glu-70 (B); Glu-72 to Leu-89 (C); Ile-95 to Lys-101 (D); and Leu-118 to Asn-125 (E). Sequence A occurs only at low pH and may be stabilized by favorable noncovalent interactions of O-linked tetrasaccharide side chains. The other four helices all occur in the dimeric form of glycophorin A at physiological pH and ionic strength. Sequence D is destroyed by trypsin, and is also lost on conversion to the monomeric form of the glycoprotein at low ionic strength. Sequence E is denatured by 6M guanidine hydrochloride/4M urea. Sequences B and C, which are separated by a single proline residue, are stable under all these conditions.Dimerization of the major, hydrophobic helical sequence, (C) may be promoted and directed by an adjacent short sequence of intermolecular parallel β-sheet (Leu-90 to Tyr-93). It is proposed that these two structures span the lipid bilayer in vivo, and that helices B and D lie, respectively, along the outer and inner surfaces of the membrane. Molecular organization in the N- and C-terminal regions of the molecule is discussed in terms of evidence from the present work and from other recent investigations.
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  • 125
    ISSN: 0009-286X
    Keywords: Essigsäure-Extraktion ; Extraktion mit chemischer Reaktion ; Lösungsmittel-Entwicklung ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 126
    ISSN: 0009-286X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Progress in liquid/liquid extraction. Liquid/liquid extraction continues to increase in importance. Classical areas of application, such as aromatic chemistry, hydrometallurgy, and reprocessing of spent nuclear fuels are being supplemented by new uses in biotechnology, in pharmaceutical production, and in water treatment. This upswing would be unthinkable without intensified R & D in chemistry and process engineering. Deeper knowledge of the physical chemistry of solvents permits purposeful choice of solvents for special separation tasks, advances in engineering elucidation of flow and mass transfer in proven and in newly designed extractors creates a basis for calculation or at least assessment criteria for the choice and operating behaviour of equipment. Yet much remains to be clarified. This article describes the current state of the art in the analysis of flow and mass transfer in countercurrent gravity feed columns with and without pulsation or agitator energy and in centrifugal extractors. A brief look at new designs demonstrates that scientific knowledge gave birth to the new ideas expressed therein.
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  • 127
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    Chemie Ingenieur Technik - CIT 57 (1985), S. 596-596 
    ISSN: 0009-286X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 128
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    Chemie Ingenieur Technik - CIT 57 (1985), S. 612-614 
    ISSN: 0009-286X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 129
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 130
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    Chemie Ingenieur Technik - CIT 57 (1985), S. 597-602 
    ISSN: 0009-286X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Investigation of damage to organic materials in chemical apparatus engineering. There are many different possible causes for the failure of structural elements or of linings and coatings made of organic materials under such load conditions as those found in chemical plant. Despite the general suitability of the engineering plastics used, design and manufacturing defects are often the cause of premature failure. Installation faults are also found on occasion. Other sources of damage include the chemical and physical effects of media on organic materials. These are due in part to the unsuitability of the material used, the effect of corrosive components in the media involved often being either not recognized or underestimated; on the other hand, the damage may also be caused by inherent stresses in the structural elements in conjunction with the physical or chemical effects of the media, resulting in stress cracking or stress corrosion cracking. Damage cases of this type are described on the basis of numerous examples, the causes ascertained through intensive investigation of the damage and suitable remedies described.
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  • 131
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Exergoeconomic evaluation of an air-fractionation plant. This article presents a method for minimization of capital investment and energy costs for process plants. To this end the operating parameters are divided into two groups, i. e. into those affecting only the operation of individual components or groups of components and those of importance for operation of the entire plant. Optimization can therefore be undertaken in two steps: (1) optimization of plant components or group of components with regard to the operating parameters of the first group, (2) optimization of the entire plant with regard to operating parameters of the second group. This approach is illustrated by investment cost/exergy loss diagrams.
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  • 132
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    Chemie Ingenieur Technik - CIT 57 (1985), S. 614-616 
    ISSN: 0009-286X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 133
    ISSN: 0009-286X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Selection of solvents in liquid-liquid extraction according to physico-chemical aspects. Selection of appropriate solvents for liquid-liquid extraction is frequently necessary in process design. High selectivity and capacity are important, but not the only considerations in choosing suitable solvents. In comparing the various solvents, their selectivity and capacity should be examined at infinite dilution of the solute in the solvent. The required limiting activity coefficients may be estimated if no experimental data are available. A preselection of solvents may be accomplished by considering the interactions of the molecules. There are certain parameters quantifying the ability of the components to interact. Therefore, a selection based merely on dielectric constants or solubility parameters is hardly conclusive.
    Additional Material: 7 Ill.
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  • 134
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    Die Makromolekulare Chemie 9 (1985), S. 233-238 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Surface grafting of low-molecular weight polyamines and poly(amino-amides) onto Dacron fabrics was performed by two different methods. The first one involves chlorosulfonation followed by a reaction with a polyamine such as triethylenetetramine, and finally with a vinyl-terminated poly(amino-amide). The latter involves the use of poly(1-acryloylbenzotriazole) in an intermediate step. The surfaces of the poly(amino-amide) - grafted materials showed a good heparin adsorbing capacity. Most of the adsorbed heparin was released only by elution with aqueous NaOH of pH 〉 10, thus confirming the strong interaction between polymer and heparin.
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  • 135
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    Die Makromolekulare Chemie 10 (1985), S. 25-42 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The derivation of simple kinetic equations will be briefly reviewed which are applicable not only to the predictions of the rate of emulsion copolymerization and copolymer composition, but also to the quantitative analyses of the chemical and physical rate processes involved in an emulsion copolymerization system and to the evaluation of their rate constants. The validity of these kinetic equations for predicting the rate of emulsion copolymerization and copolymer composition is demonstrated by comparing the theoretical predictions with the experimental data for the emulsion copolymerization of styrene and methyl methacrylate. The utility of these kinetic equations for evaluating the rate constants in an emulsion copolymerization system is also shown by using the experimental data for the emulsion copolymerization of vinyl acetate and methyl methacrylate.
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  • 136
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    Die Makromolekulare Chemie 10 (1985), S. 87-103 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The emulsion copolymerization kinetics of styrene-butyl acrylate was studied in a batch process. The effect of the initiator, emulsifier, chain transfer agent and monomer concentration on copolymerization rate and molecular weight distribution is discussed. Thermal and viscoelastic properties of copolymers were measured. It was found that the n-dodecylthiol introduced into the reactor with the monomers did not affect the copolymerization rate (no redox reaction with the initiator) but the molecular weight was strongly dependent upon its concentration. These two kinetic parameters increase with increasing the butyl acrylate concentration.
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  • 137
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    Die Makromolekulare Chemie 10 (1985), S. 149-158 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An experimental study of semi-continuous emulsion copolymerization of acrylonitrile (AN) and styrene (ST) was carried cut with an isothermal stirred vessel. Continuous addition of monomer emulsion (ME) was inserted between preliminary and finishing batch operations. A mathematical model to simulate the experimental results was also developed with a particular attention on the partition of hydrophilic AN between the aqueous and organic phases. The result of simulation was quite satisfactory even though the approximate rate expressions proposed by Szabo and Nauman (1) were employed.
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  • 138
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    Die Makromolekulare Chemie 10 (1985), S. 199-214 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Inverse emulsion copolymerization studies of acrylamide (Am) with methacrylic acid (MAA) are reported. Aqueous monomer emulsions in toluene were prepared with a blend of two surfactants (sorbitan sesquioleate - Cl8 - terminated acrylamide oligomers). Polymerization kinetics in presence of an oil soluble initiator (AIBN) were determined at 40°C as function of MAA content and aqueous phase pH : monomer reactivity ratios have been derived as rAm = 0.58 ± 0.02, rMAA = 4.40 ± 0.10 at pH 4 and rAm = 0.56 ± 0.005, rMAA = 0.15 ± 0.03 at pH 10. Particle size and stability of inverse monomer emulsions and final latexes were found to depend upon the aqueous phase pH, as well as the intrinsic viscosities of the copolymers; this suggests differences in polymerization mechanism versus the pH.
    Additional Material: 11 Ill.
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  • 139
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    Die Makromolekulare Chemie 10 (1985), S. 235-264 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Emulsion polymerization proceeds in a heterogeneous medium; in copolymerization, due to discrepancy in water solubility and interactions with the resulting copolymers, monomers are partitioned in a complex way between droplet, water and particle phases. As monomer swollen polymer particles are the main loci of polymerization, it is of great interest to know the monomer feed within the particle phase to understand the behaviour of this copolymerization whatever may be the process and the experimental conditions. Two approaches are examined in this lecture to investigate emulsion copolymer and colloid properties of the latexes. A first, simple one is based on experimental partition coefficients and a second one is based on more theoretical thermodynamic considerations (volume fractions, interaction χ parameters …). The latter gives a more general insight of emulsion processes and allows to investigate influence of many parameters like monomer-monomer, monomer-polymer, monomer-emulsifier interactions, interfacial tension, particle size, surface charge density… Computer programs are derived which give predictions in rather good agreement with experiments. The thermodynamic approach allows to study crosslinking effect as well as competition between polymerization rate and monomer diffusion rate if some control by diffusion does occur. Owing to these computer programs it becomes possible to correlate many experimental parameters. Most of experimental date are relative to styrene-acrylonitrile copolymerization.
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  • 140
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    Die Makromolekulare Chemie 10 (1985), S. 297-303 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the characterisation of latices conductometry is the technique most commonly used. In this paper it is shown that a thorough characterisation of latices is possible based mainly on potentiometric titrations in aqueous and non-aqueous media and on spectrophotometry. Results obtained with these techniques in the study of acrylate latices prepared with nonylphenolpolyethyleneoxidesulphate as the emulsifier are presented. It is shown that this type of emulsifier is subjected to considerable hydrolysis during the emulsion polymerisation process.
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  • 141
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    Die Makromolekulare Chemie 10 (1985), S. 319-333 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the reaction of tertiary amines with vinylbenzyl chloride (VBC) copolymer latexes have been investigated. In this reaction, benzyl chloride groups on the latex particles are converted in high yield to quaternary ammonium groups. The course of the reaction is determined by amine reactivity rather than solubility. The kinetics are complicated by a severe retardation effect developing at conversions in excess of 30%. The limiting conversion appears to be associated with the maximum charge density that can be tolerated on a hydrophobic particle. A surface reaction model is invoked to explain the results.
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  • 142
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    Die Makromolekulare Chemie 10 (1985), S. 419-433 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polymer particles with an heterogeneous structure are synthesised in emulsion using the method of the continued addition of monomers in two successive stages. The last fraction contains a mixture with an excess of reactive monomer. The core structure is made with a copolymer of n-butylacrylate (BuA) and butylmethacrylate (BuMA), the shell structure with a terpolymer of BuA, BuMA and glycidylmethacrylate (MAG).The classical epoxy group titrations which have been carried out have allowed the appraisal of the particle's superficial reactivity which is weak (about 5 to 10%) and the total concentration of oxirane functions, which is about 90%. This means the initiator redox system and the general polymerisation conditions are favorable for the epoxy function preservation.A gas chromatography essay of sampling was used for the kinetic tracing studies of polymerisation which gives an interesting schematic representation of the particle microstructure. The radial display of glycidylmethacrylate (MAG) in the particle will be examined in detail.
    Additional Material: 8 Ill.
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  • 143
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    Die Makromolekulare Chemie 10 (1985), S. 69-86 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Batch emulsion copolymerizations of n-butyl acrylate (B) and styrene (S) have been carried out, using either potassium persulfate or “azocarboxy” as initiators and sodium dodecyl sulfate as emulsifier. Particle size vs conversion studies, within a broad range of initiator (0,37 to 3,3.10-3 mol. 1-1) and emulsifier (0,6 to 18.10-3 mol. 1-1) concentrations, 1/1 comonomer ratio and for two solid contents (20 and 50 %), have been investigated through dynamic light scattering and transmission electron microscopy methods. Molecular weight and surface characteristics of the emulsion copolymers were also estimated. From the results, it is suggested that, due to the water solubility of the n-butyl acrylate, the particle formation in this system follows a homogeneous nucleation mechanism where the limited flocculation step is strongly dependent upon the stabilizing properties of the latex.
    Additional Material: 9 Ill.
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  • 144
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    Die Makromolekulare Chemie 10 (1985), S. 105-128 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A dynamic computer model which can predict polymer and polymer particle properties such as molecular weight averages (MN and MW) and (long chain branching frequency) and particle size distribution for the emulsion copolymerization of styrene/butadiene has been developed. Heat balances about the latex reactor and cooling jacket with proportional/integral control are included. This model can be used to design, optimize and control emulsion copolymerization in well-mixed stirred tank reactors operated in batch, semi-batch and continuous modes for transient and steady-state operation.Details of modelling are described and then applications of the model are shown to illustrate the range of operational conditions of various production systems that can be investigated.
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  • 145
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    Die Makromolekulare Chemie 10 (1985), S. 129-148 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A semi-continuous emulsion copolymerization of acrylic monomers was investigated. Under the conditions used, the polymerization rate was equal to the rate of feeding of monomers and a steady state with a constant ratio of free monomers was reached. “Effective” reactivity ratios were calculated for several couples of monomers. Significant differences in the particle size distribution were found with monomers of different polarity. The extent of particle flocculation during the process was affected by the emulsifier distribution between the initial reactor charge and the monomer emulsion as well as by the electrolyte concentration. The tendency of particles to flocculate decreased with the increasing concentration of carboxylic groups on the particle surface. A different extent of acid hydrolysis of ester groups was observed by emulsion polymerization of various acrylic monomers.
    Additional Material: 18 Ill.
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  • 146
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    Die Makromolekulare Chemie 12 (1985), S. 239-249 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Behavior of the porphinato iron (heme) complexes embedded in phospholipid bilayer was described. Novel and finely modified heme derivatives were synthesized by expecting that compatibility of the heme with lipid bilayer and oxygen-binding ability of the heme are improved. The heme was oriented in parallel and molecularly dispersed to and in the bilayer, and reinforced the assemble bilayer structure. Oxygen-binding reaction was much influenced by fluidity of phase state of the environmental bilayer.
    Additional Material: 4 Ill.
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  • 147
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    Die Makromolekulare Chemie 12 (1985), S. 251-253 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 148
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    Die Makromolekulare Chemie 12 (1985), S. 255-263 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The magnetic properties of polymers containing nitroxyl, tetraphenylporphin (TPP)-Cu(II), -Ag(II), or -Co(II) in the side chains were studied by ESR and magnetic susceptibility(χM) measurements. The values of χM for the polymers containing nitroxyl, TPP-Cu(II), and -Co(II) were found to obey the Curie-Weiss law, and their magnetic moments showed the occurrence of a weak antiferromagnetic interaction between paramagnetic species. The value of χM for the polymer containing TPP-Ag(II) showed the presence of strongly interacting sites. This strong interaction possibly arises from a hyperexchange interaction through the C—O group situated among the Ag(II) ions. Polymers containing TPP-Co(II) adsorb oxygen below 180 K and the ratio of O2:Co(II) was found to be 1:1 at 77 K.
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  • 149
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    Die Makromolekulare Chemie 13 (1985), S. 13-32 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(N-acyl ethylenimine) of various molecular weights was synthesized by the cationic ring-opening polymerization of 2-H-2-oxazoline and 2-methyl-2-oxazoline. Acid hydrolysis afforded the linear poly(ethylenimine) which was used in the following grafting reactions. Vapor pressure osmometry, gel permeation chromatography and viscosity measurements were used to characterize the polymers synthesized. Potassium 2-(cytos-l-yl) propanoate and potassium 3-(cytos-l-yl) butanoate were synthesized in good yield from thenucleic acid base. These cytosyl pendant groups were grafted onto the poly(ethylenimine) using 4-chloro-1-(4-chlorobenzenesulfonyl) benzotriazole, 90% graft, and norborn-5-ene-2,3-carboximido diphenyl phosphate, 70% graft. Grafting of the t-butoxycarbonyl and n-butoxycarbonyl protected cytosyl pendant groups resulted in a 47% graft. Hypochromicity studies indicated an ordered structure at the local level. The secondary structure is a base-stacked conformation. Light scattering results gave insight into the tertiary structure of the macromolecule. The polymer exists in solution as stiff chains, rod-like in nature. Continuous mixing experiments were carried out with polyribonucleotides. The Job plots indicated increased level of ordered conformation with either an increase in the molecular weight or an increase of the base to base distance in the analog. Enhancement in the base-stacked conformation was higher in the polyinosinic acid complex than that of the polyguanylic acid complex.
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  • 150
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    Die Makromolekulare Chemie 13 (1985), S. 33-46 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three topics on molecular design of functional polymers having amino groups will be discussed. The first topic is on the synthesis of functional isoprene oligomers with one amino end group. The best condition for the synthesis is to seed a small amount of the amino-ended oligomer into a reaction system where isoprene was polymerized with lithium diisopropylamide as initiator. The highly active behavior of the amino-ended oligomer as chain transfer agent was ascribed to a “macromolecular effect”. The second topic is concerned with a study on the soluble poly(1,4-divinylbenzene) which was formed by polymerizing 1,4-divinylbenzene with lithium diisopropylamide in the presence of excess diisopropylamine in THF. Structural analyses with 400MHz1H NMR and 25 MHz13C NMR showed that there were 2 or 3 branchings per 100 monomeric units along the main chain. Population of the triad tacticities suggested the steric course of polymerization to proceed according to the Bernoulli statistics with respect to diad placements, m and r. Third topic is on a polyamine macromer which was prepared by allowing an ethylenediamine homologue, N,N′-diethylethylene-diamine (DEDA), to react with 1,4-divinylbenzene in the presence of lithium diisopropylamide as catalyst. Results on syntheses and properties of polystyrene-polyamine (SA) and poly(2-hydroxyethyl methacrylate)-polyamine (HA) graft copolymers will be presented with the emphasis on their biomedical behavior.
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  • 151
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    Die Makromolekulare Chemie 13 (1985), S. 137-155 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Water-soluble nonstoichiometric polyelectrolyte complexes (NPEC) are formed as a result of interaction of opposite charged polyelectrolytes used in nonequivalent ratios. One of the most important properties of NPEC is their ability to participate in intermacromolecular exchange and substitution reactions in aqueous solutions. The kinetics of exchange and substitution reactions has been studied by the method of luminescence quenching. It has been found that such reactions proceed by the contact mechanism and that addition of low molecular electrolytes to the reaction mixtures results in a dramatic increase in the rates of the reactions. The kinetics of the reactions is well described by the equation q = 1-exp(- kt∝) (here q is the degree of conversion and ∝ 〈 1), deduced under the assumption that exchange and substitution occur by the nucleation mechanism and the development of nuclei is inhibited in time. The studied reactions represent a new class of interpolymer reactions and they can be very important, in particular, for understanding the mechanism of functioning of biologically important macromolecules and for the interpretation of the physiological activity of polyelectrolytes.
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  • 152
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    Die Makromolekulare Chemie 14 (1985), S. 1-1 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 153
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    Die Makromolekulare Chemie 14 (1985), S. 145-159 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Exciplex and excimer in polymers were investigated and compared with monomer and dimer model systems. Many condensation polymers(mostly polyesters) and a methacrylate polymer having excimer- or exciplex forming chromophores were prepared. Exciplex (or excimer) intensity, wavelength, and rise and decay of emission were discussed as functions of polymer structure, degree of polymerization, concentration, solvent, and temperature. Polymer effects on excimer and exciplex formation were always positive and it was not possible to explain them by local concentration effects. Specific intra- and interpolymer interactions and relaxation processes in polymers were also discussed.
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  • 154
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    Die Makromolekulare Chemie 14 (1985), S. 81-90 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bilayer membranes are formed spontaneously from single-chain, double-chain, and triple-chain amphiphiles which possess fluorocarbon tails. Their aggregation behavior is similar to those of the corresponding hydrocarbon amphiphiles. However, the bilayer characteristics are quite different between the two classes. Flurocarbon bilayers display limited miscibilities with hydrocarbon bilayers, and enhanced barrier capacities against permeation of ions and molecules. Membrane-bound fluorocarbon species show peculiar reactivities.
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  • 155
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    Die Makromolekulare Chemie 14 (1985), S. 119-130 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reverse electron transfer between photogenerated redox pair in bulk aqueous solutions can be efficiently suppressed by collecting the photoliberated electron to the positively charged surface of molecular assemblies such as micelles, bilayers and polymers. Zwitterionic viologen molecules serve as efficient electron carriers, which shuttle between the bulk phase and the surface of molecular assemblies. The molecular assemblies with aligned viologen units at the surface are particularly useful as molecular device for the electron enrichment and storage. Quantitative charge separation of the cage-escaped redox pair can be achieved by the use of the amphiphilic viologen molecular assemblies in combination with the zwitterionic viologen. The lifetime of charge-separated state can be extremely extended in these systems : ca 30 ms for the viologen bilayer and above 1 s for the polymer with pendant viologen. Amphiphilic viologen molecular assemblies also help to increase charge-separation of the photoinduced, intramolecular electron transfer in sensitizeracceptor linked system incorporated into the molecular assemblies. All of these phenomena are ascribed to cooperativity effects of aligned viologen units, which induce electron hopping a long the surface via successive electron exchange between viologen molecules.
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  • 156
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    Die Makromolekulare Chemie 186 (1985), S. 17-29 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This work deals with the modification reaction of dextran with ethyl and butyl chloroformate using tertiary amines as catalyst/acceptor systems and the DMF/LiCl system as solvent. The structure of the resulting polymers was determined by means of IR, 1H and 13C NMR spectroscopy as well as by chemical analyses. The reaction rate was found to increase in the following order: N,N′-dimethylaniline 〈 pyridine 〈 triethylamine. The presence of cyclic carbonates was observed when triethylamine was used as catalyst. A linear dependence of the reaction rate on polymer and pyridine concentrations and a more complex dependence on the n-alkyl chloroformate concentration were found. Reaction rate and yield decrease with increasing amount of LiCl in the solvent medium and increase with increasing chain length of the n-alkyl chloroformate. The activation energy was found to be 64 kJ/mol (15,3 kcal/mol). The equilibrium water content (EWC) values decreases progressively when either the content of carbonate groups or the side chain length increases. The hydrolysis in the heterogeneous phase showed that the time required for the polymer solubilization is dependent upon the nature of the carbonate groups, the temperature as well as the pH value of the medium. Dextranase was found to be inactive in the hydrolysis of water-insoluble modified dextrans. However, the hydrolysis takes place when water-soluble modified dextrans were used.
    Additional Material: 10 Ill.
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  • 157
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    Die Makromolekulare Chemie 186 (1985), S. 71-75 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The interaction of poly(1,1-dimethylpyrrolidinium-3,4-diylethylene chloride) [poly(diallyldimethylammonium chloride)] (1) with ferro- and ferricyanide anions was investigated by conductometric titration, viscometry, IR and Raman spectroscopy. It could be shown that the binding of ferro- and ferricyanide anions with 1 proceeds by means of an ionic mechanism and is accompanied by a spectral shift of the cyanide bands.
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  • 158
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    Die Makromolekulare Chemie 186 (1985), S. 123-129 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The potentiometric behaviour of poly(methacrylic acid) was examined in water/1,4-dioxane mixtures at 25°C. Conformational transitions were observed in about the same range of apparent ionization in the 1,4-dioxane concentration range 0 to 15 vol.-%. Transitions were not observed in the 1,4-dioxane concentration range 20 to 35% and the corresponding Henderson-Hasselbalch plots were found to be linear. Phase separations were observed to occur beyond 40 vol.-% 1,4-dioxane. The free energy of the conformational transition decreased very rapidly with the initial incorporation of 1,4-dioxane but slowly at higher concentrations. Van der Waals methyl-methyl interactions as the cause of the compact form has been inferred. The large increase in intrinsic viscosity observed for the unneutralized poly(methacrylic acid) in a relatively narrow range of composition of the 1,4-dioxane/water mixtures has been ascribed to a solvent induced conformational transition.
    Additional Material: 4 Ill.
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  • 159
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dissociation constants of partially ionized isotactic and atactic poly(2-dimethylaminoethyl methacrylate) in water/ethanol solutions were measured. The strong dependence of the apparent dissociation constant on the degree of ionization of the macromolecule is discussed using viscometric data and compared with the properties of low-molecular-weight model compounds. The values of the internal dissociation constants at various ionic strength in various water/ethanol solutions were obtained by extrapolation of the apparent dissociation constants to zero ionization degree of the macromolecule. The conformational structures of macromolecules in solution are discussed.
    Additional Material: 4 Ill.
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  • 160
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    Die Makromolekulare Chemie 186 (1985), S. 145-158 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mixtures of poly(ethylene oxide) and polyether sulfone have previously been shown to be miscible and undergo phase separation on heating, the minimum in the cloud point occurring at about 80°C and at 10:90 w/w PES:PEO composition. This paper describes an attempt to understand the thermodynamics of this system and to simulate the spinodal curves of the phase diagram using a modified form of the equation-of-state theory of Flory et al. Two methods were used to gain information about the interactional energy of the polymers. Heat of mixing measurements at 90°C on low molecular weight analogues were used to obtain a value of X12 of -40 J. cm-3. A modified form of the equations for the melting point depression of PEO in the blend was used to obtain values of X̄12 in the range of -35 to -50 J. cm-3 at 52°C, the melting point of PEO. In order to adjust the location of the simulated spinodal, using a value of X12 = -40 J. cm-3, it was necessary to assume an unfavourable non-combinatorial entropy contribution of Q12 = -0,048 J. cm-3 · K-1. If the spinodals were simulated assuming Q12 = 0 and hence X12 ≡ X̄12 then a value of X12 = -18 J · cm-3 must be used. This is not inconsistent with the melting point depression result considering the large uncertainties in this method and the fact that the results are obtained at a lower temperature. The simulated spinodals are not very molar mass dependent which corresponds to the similar findings of the cloud point. The shape of the spinodal is dominated by the value of the surface area to unit volume ratio S2/S1 through its effect on the interactional terms in the spinodal equation.
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  • 161
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    Die Makromolekulare Chemie 186 (1985), S. 191-201 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of crystallinity and radiation crosslinking on the water induced depression of the glass transition temperature in Nylon 4 [poly(2-pyrrolidone)] has been investigated by differential scanning calorimetry. Radiation crosslinking was effective in preventing exothermic events associated with crystallization during the measurement of the incremental change in heat capacity (ΔCp); a parameter necessary for the theoretical evaluation of the depressed glass transition temperature. ΔCp, when normalized to account for fractional crystallinity, was found to deviate substantially from a linear two phase relation. A simple three phase representation of morphology is proposed to account for this deviation, and assumptions have been made regarding the distribution of plasticizer, leading to good agreement between the theoretical and experimentally observed depressions of the glass transition temperature.
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  • 162
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    Die Makromolekulare Chemie 186 (1985), S. 273-281 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reactive microgels containing sulfo groups were prepared by copolymerization of N,N′-methylenediacrylamide (1) and 2-acrylamido-2-methylpropanesulfonic acid (2) in water. The composition of the microgels, their structure, density, molecular weight and viscosity in solution were examined depending on the composition of the monomer mixture and the reaction conditions.
    Additional Material: 1 Ill.
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  • 163
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High molecular weight poly(thio-1,1-dimethylethylene) [poly(isobutylene sulfide)] obtained by anionic polymerization of 2,2-dimethylthiirane (isobutylene sulfide) was degraded to a mixture of low molecular weight compounds when treated with a catalytic amount of methyl trifluoromethanesulfonate. The following degradation products were found: 2,2,5,5-tetramethyl-1,4-dithiane (3), 2,2,6,6-tetramethyl-1,4-dithiane (4), 2-isopropyl-4,4-dimethyl-1,3-dithiolane (2), and an equimolar mixture of 3,3,6,6-tetramethyl-1,2,5-trithiepane (5) and 2-methylpropene (isobutylene). The formation of dithiolane 2 is explained by a hydride transfer to a transient carbenium ion.
    Additional Material: 4 Ill.
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  • 164
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    Die Makromolekulare Chemie 186 (1985), S. 357-366 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dilute solution properties of poly(ethylene oxide)-polydimethylsiloxane-poly(ethylene oxide) (POE-PDMS-POE) triblock copolymers, of a POE-PDMS segmented block copolymer and of a grafted PDMS-g-(POE-co-POP) copolymer are investigated by means of viscosity, light scattering and small angle neutron scattering. The experiments indicate that the copolymers are molecularly dispersed or aggregated, depending on the properties of the solvents. A rather compact conformation is deduced from the viscosity measurements. Negative A2-values are observed in preferential solvents for one of the segments, a positiv A2-value in a common solvent for both segments forming the block copolymer.
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  • 165
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    Die Makromolekulare Chemie 186 (1985), S. 407-422 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The free radical crosslinking copolymerization of styrene with a bi-unsaturated comonomer (divinylbenzene, ethylene dimethacrylate), present in small proportions, yields three-dimensional polymer networks. The gelation time tc is generally longer than expected if all double bonds originating from the bi-unsaturated monomer (including the pendent double bonds) were isoreactive. This delay in gelation has been attributed to the formation of intramolecular cyclizations, or to the lower reactivity of the pendent double bonds with respect to growing radicals. This paper, devoted to an investigation of the network forming reaction after gelation, presents some additional evidences in favor of the latter assumption, resulting from the variation of the fraction of extractable polymer, of the swelling degree and of the modulus of the swollen networks as a function of the overall degree of conversion. Furthermore, a direct proof of the role of the pendent double bonds is given by the “two-step” crosslinking experiments carried out.
    Additional Material: 6 Ill.
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  • 166
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Branched polysaccharides of cellulose having β-glycosidically linked D-glucose branches were synthesized by condensation of 3,4,6-tri-O-acetyl-(1,2-O-ethylorthoacetyl)-α-D-glucopyranose with activated cellulose acetates (DS ≈ 2) in boiling chlorobenzene in the presence of a catalytic amount of 2,6-dimethylpyridinium perchlorate. The branched polysaccharides were converted into water-soluble polysaccharides by saponification and then tested for their antitumor activity. Synthetic, branched polysaccharides with 30% or more branching were found to be completely soluble in water. The structure of branched polysaccharides was determined by methylation analysis, and it was found that branching occurred preferentially at the Cxyh6 positions by β-glucosidic linkages. The antitumor activity for Sarcoma 180 transplanted to mice was high for polysaccharides with a high DP. Cellulose did not react with acetyl glucose orthoester even after activation.
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  • 167
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    Die Makromolekulare Chemie 186 (1985), S. 473-481 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymers from styrene and a mixture of p- and m-chloromethylstyrene were reacted with sodium cyclopentadienide in THF and precipitated in methanol at temperatures lower than -20°C to obtain soluble cyclopentadienylated polymers. Due to extensive gelation, the content of cyclopentadienyl groups could not be increased to more than 4 mol-% except with extremely low molecular weight polymers. An improved method, in which the copolymer was cyclopentadienylated in the presence of metallic sodium, gave soluble polymers with up to 29 mol-% cyclopentadienyl groups. Pendant cyclopentadienyl groups undergo Diels-Alder/retro-Diels-Alder addition to give thermoreversible cross-linked polymers. The amount of gel fraction of a 4 mol-% cyclopentadienylated polymer as a function of the heating time was examined in the temperature range of 40-80°C. The DSC curve of a 29 mol-% cyclopentadienylated polymer showed an exothermic peak due to the Diels-Alder reaction and an endothermic peak starting around 390°C, a temperature higher than that found for the degradation of polystyrene.
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  • 168
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    Die Makromolekulare Chemie 186 (1985), S. 513-525 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple method for calculating the moments of the radius of gyration of polymers is developed. It can be applied to any molecule which does or does not possess close circuits in its structure. In the Rouse theory of viscoelastic behaviour, various functions such as the zero-shear-rate viscosity, η0, and the steady-state recoverable compliance, Je0, are directly related to the moments of the radius of gyration and hence the results obtained may prove useful for interpreting rheological data.
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  • 169
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    Die Makromolekulare Chemie 186 (1985), S. 573-582 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The degradation of poly(oxycarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene) [poly-(bisphenol-A carbonate)] in cyclohexanone is shown to be efficiently catalyzed by organic salts and metal carbonates. The catalysis is of homogeneous type. More precisely, only the associated fraction of the dissolved salt is active. The apparent activation energy of the degradation ranges between 113 and 130 kJ · mol-1 (27 and 31 kcal · mol-1), being similar to energies usually observed for hydrolysis or alcoholysis of esters. A reaction mechanism based on the ketoenolic equilibirum in cyclohexanone is proposed to explain the fast degradation observed. The influence of the nature of ions is also assessed: the reactivity increases with decreasing cation diameter, whereas the nature of the anion is of no matter.
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  • 170
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    Die Makromolekulare Chemie 186 (1985), S. 633-640 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Probabilities of configurations conducive to the intramolecular back-biting abstraction of a hydrogen atom have been evaluated for growing unperturbed poly(vinyl acetate) chains. A realistic rotational isomeric state model was used for the chain statistics. Probabilities are found to be smaller than those seen in an earlier treatment of the polyethylene chain. The smaller probabilities of poly(vinyl acetate) contribute to the virtual absence of short branches. The present study therefore provides support for the validity of the Roedel mechanism for the formation of short branches in the free radical initiated polymerization of ethylene.
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  • 171
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology of cast and annealed films from poly[bis(trifluoroethoxy)phosphazene] \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm \{ PBFP,\rlap{--} [(CF}_{\rm 3} {\rm CH}_{\rm 2} {\rm O)}_{\rm 2} {\rm P = N\rlap{--} ]}_{\rm n} {\rm \} } $\end{document} has been studied by electron, scanning electron and optical microscopy. Several polymorphic forms and one mesophase (hexatic) have been established. From THF solution, PBFP has a chain folded morphology (α-orthorhombic) which transforms into a chain extended 2D hexagonal mesophase at T(1). It remains in this state until final melting occurs at Tm = 245°C approximately. Upon cooling the melt, it quickly reverts to the hexagonal mesophase again, but then passes into a chain extended (3D) γ-orthorhombic modification. This material is much more stable thermodynamically than the α-form, which is friable or brittle. PBFP cannot be quenched to a glassy form from the molten state, but it can be disordered as assessed by its reduced T(1) enthalpy and less well defined morphology assessed by electron microscopy. Another crystal modification (β-monoclinic) has been found in solution cast low molecular weight PBFP films.
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  • 172
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    Die Makromolekulare Chemie 186 (1985), S. 707-714 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The chemical dehydrochlorination of poly(vinyl chloride) was studied in solution in N,N-dimethylformamide. By comparison with solutions in tetrahydrofuran, examined previously, the reaction was found to occur at a significantly enhanced rate for the four systems studied, a mass polymer of 55% syndiotacticity and a low temperature polymer of 63% syndiotacticity, dehydrochlorinated with potassium hydroxide or with potassium tert-butoxide. Furthermore, at dehydrochlorination levels up to about 60%, markedly longer polyene sequences are formed, the more so in the case of potassium tert-butoxide., where they reach values of at least 65, as assessed by Raman spectroscopy. For levels of 80%, and greater, there is a significant decrease in the sequence lengths, the result of cross-linking, which is facilitated by the substantial loss of the \documentclass{article}\pagestyle{empty}\begin{document}$\rlap{--} ({\rm CHCl \hbox{---} CH}_{\rm 2} \rlap{--} )_n$\end{document} sequences that sterically protect the long polyenes in the les heavily dehydrochlorinated materials. Limited results are also presented for chemically dehydrochlorinated PVC prepared by the urea clathrate method; the insolubility of this polymer probably leads to degradation on the surface of the particles only.
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  • 173
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    Die Makromolekulare Chemie 186 (1985), S. 695-705 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The chemical dehydrochlorination of poly(vinyl chloride) was studied in solution in tetrahydrofuran. Two materials, a mass polymer of 55% syndiotacticity and a low temperature polymer of 63% syndiotacticity, were dehydrochlorinated with potassium hydroxide and with potassium tert-butoxide. The dehydrochlorination products were characterised by their chlorine contents and by UV/visible, IR and Raman spectroscopy, as a function of reaction time. The course of the reaction was found to be substantially independent of tacticity and the dehydrochlorinating reagent. Initially, the reaction follows a similar path to that occurring during photo- and thermal degradation, but as the dehydrochlorination continues, longer conjugated polyenes are formed than by these two latter processes. Sequences of 60 double bonds occur at the dehydrochlorination levels of about 55% that are attained after reaction times of 24 h. These sequences are sterically protected from cross-linking reactions by the presence of longish sequences of unreacted —CHCl—CH2— units.
    Additional Material: 6 Ill.
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  • 174
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From the break-down in the viscosity and from the increase of the intensity of the scattered light, associated with the entrance into the two-phase region, the pressure dependence of the demixing temperature of solutions of PVC 37 000, PVC 75 000 and PVC 100 000 in phenetole and PVC 75 000 in o-xylene was measured up to 1 000 bar. (The numbers in the codes of the PVC specimens are their approximate molecular weights.) The application of pressure increases the demixing temperatures of PVC in both solvents by about 1 K/100 bar. For a qualitative forecast of the pressure effects, the solubility parameter theory in combination with the corresponding states principle, and an empirical correlation to the relative distance of the critical demixing temperature to the melting point of the pure solvent were used. The results of both concepts are in accord with the experimental findings.
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  • 175
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Investigations with ca. 100 organic liquids in a temperature range from -20°C to 90°C result in a survey of the solubility behaviour of PVC. The experimental results were compared with the predictions of the solubility parameter theory: Accepting δ = 9,75 (cal/cm3)1/2 as the solubility parameter for PVC, all solvents (except ketones in which PVC is soluble independent of their solubility parameters) are located within the range of δPVC ± 0,75. Only three of the 100 liquids examined turned out to be (endothermal) theta-solvents, namely the aromatic solvents o-xylene, phenetole and dimethyl phthalate. The theta-temperatures in o-xylene and phenetole were determined viscometrically by means of the temperature dependence of the Mark-Houwink exponent to be 84 and 88°C, respectively. Viscosity measurements were also performed in the temperature range of 25 to 60°C with solutions of PVC 75 000 in 10 thermodynamically good solvents used for rheological investigations. In all cases the intrinsic viscosities decrease slightly with increasing temperature, i.e., all solutions are weakly exothermal. The binary cluster integral, β, was determined (taking the monomeric unit as the statistical segment) and the polar contribution, βe, was calculated from Yamakawa's theory. The correlations between the non-polar part of (βn = β - βe) and the solubility parameter of the solvent, found by Utracki, were tested and found to be valid for the present systems, too.
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  • 176
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    Die Makromolekulare Chemie 186 (1985), S. 831-836 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three methods were used for the determination of transfer constants to the metallic complex in the telomerization reaction with redox catalysis. The first one consists in the determination of DPn as a function of the mole ratio of telogen to monomer at the beginning of the reaction. The second one is based on the variation of the conversion degree of telogen to monomer. The last one requires the knowledge of the cumulated DPn and the conversion degree of monomer samples during the reaction. The proposed laws were checked following the methyl acrylate telomerisation with CCl4 as a telogen and CuCl2 as a catalyst at 120°C. The transfer constant to CuCl2 was found to be about 600 according to the three methods.
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  • 177
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    Die Makromolekulare Chemie 186 (1985), S. 837-846 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conductivity behaviour of a partially neutralized methoxycarbonylcellulose (carboxymethylcellulose, CMC) solution was investigated at different frequencies using a home made conductance bridge. The equivalent conductance of CMC solutions has very poor dependence on frequency contrary to the behaviour of simple ionic compounds. The effect of concentration on the polyelectrolyte behaviour was investigated conductometrically and it was observed that the polymer concentration has little effect on polymer charge fraction and polymer counterion fraction. Sodium ion-binding on the polymer molecule was also investigated.
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  • 178
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    Die Makromolekulare Chemie 186 (1985), S. 881-892 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The isothermal crystallization of isotactic polypropene samples cooled from the melt is studied. Particular emphasis is given to the morphology which develops depending on the melting and crystallizing conditions. Thus, the evolution of birefringence for samples crystallized between -20°C and +150°C is explained in terms of a quadritic arrangement of lamellae. The evolution of the relative amounts of radial and tangential lamellae is followed by differential thermal analysis, small angle light scattering and optical polarization microscopy.
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  • 179
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(p-hydroxycinnamic acid) was synthesized by thionyl chloride activated polycondensation of p-hydroxycinnamic acid at ambient temperatures and by polycondensation of its various monomeric esters at elevated temperatures. The thionyl chloride activated polycondensation proceeds as a 2-stage process, yielding reduced viscosities of up to 102 mL/g. 360 MHz proton NMR spectra indicate an all-trans structure and the absence of side reactions. The polymer with a melting temperature of 313°C can be pressed into films.
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  • 180
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(oxythiocarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene) (1) was obtained from 4,4′-isopropylidenediphenol (Bisphenol A) and thiophosgene under phase transfer conditions, using quaternary ammonium and phosphonium salts and crown ethers as catalysts. The polymer was identified by IR and 1H NMR spectroscopy, and the molecular weights were estimated from inherent viscosity measurements. The influence of catalysts, solvent and thiophosgene addition was studied in order to find the best conditions. It was found that tetrabutylammonium bromide, dichloromethane and the addition of thiophosgene at once gives the highest yields and inherent viscosities. Other catalysts and solvents were less efficient or unefficient for this reaction.
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  • 181
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    Die Makromolekulare Chemie 186 (1985), S. 923-931 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dialkyldiallylammonium salts 1a-c were prepared by quaternization of diallylamine with alkyl bromides and their polymerizability as oriented molecular assemblies in aqueous solution is discussed. Thin films of those ammonium salts on the glass wall were incubated by adding a phosphate buffer solution to yield giant spherical vesicles with diameters ranging from 10 to 100 μm. When large amounts of the ammonium salt were applied, it was necessary to add more than 5 mol-% of cholesterol in order to stabilize the resulting giant vesicles. By ultrasonication of the film-aqueous solution system, much smaller vesicles with diameters ranging from 0,03 to 0,2 μm were obtained. The stabilizing effect of cholesterol addition to the system of the small vesicles is similar to that observed for the giant vesicles. Under an inert atmosphere, the vesicles in aqueous solution were polymerized by ultraviolet irradiation. From the results of TEM and NMR spectroscopy, it was concluded that the molecules were polymerized in the vesicles without changing the profile of molecular assembly during an irradiation of 6 h. However, when the ammonium salts were dissolved homogeneously in degassed benzene, the ultraviolet irradiation polymerization did not proceed beyond a conversion of 5% under the same conditions.
    Additional Material: 8 Ill.
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  • 182
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    Die Makromolekulare Chemie 186 (1985), S. 865-879 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The extent of reaction of functional groups (pA), the extent of conversion of monomer molecules (qM), the true relative polymer yield (yp), the constitutional repeating unit-based apparent relative polymer yield (yPU), and the monomer-based apparent relative polymer yield (yPM) are defined and their interrelationships given. The use of yPU instead of yp overestimates the true yield, except in the limit of high degrees of polymerization. Use of yPM, on the other hand, always underestimates the true yield, especially at infinite degrees of polymerization. The correct expression for the calculation of the mass fraction of i-mers in reactants with a Schulz-Flory “most probable” distribution is given and shown to become identical with the usual approximation in the limit of vanishingly small mass of the leaving molecule.
    Additional Material: 2 Ill.
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  • 183
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    Die Makromolekulare Chemie 186 (1985), S. 847-864 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equations are derived for the time dependence of the extent of functional group reaction, pA, for catalyzed and uncatalyzed, irreversible, stoichiometric polycondensations of the AB and AA/BB type following pseudo-second-order and third-order chemical kinetics, resp., based on amount-of-substance concentrations. The resulting functions 1/(1 - pA) - f(t) for pseudo-second-order polycondensations and 1/(1 - pA)2 - f(t) for third-order polycondensations are predicted to be non-linear for low extents of reaction and practically linear for higher ones which agree with previous, hitherto unexplained experimental observations. The slope of the linear part does not give the true rate constant, contrary to traditional assumptions. The extent of non-linearity at small conversions and the deviation of the apparent rate constant from the true one depends on the initial amount of A groups, the molar mass of the leaving molecules, and the initial mass of the reaction mixture, if the molar concentrations are based on masses (“molalities”). The density of the leaving molecules enters, in addition, if the molar concentrations are volume related (“molarities”). The equations predict, for a given system, that the range of the non-linear region increases with decreasing rate constants, i.e., with decreasing temperature, in accordance with experimental observations.
    Additional Material: 6 Ill.
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  • 184
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    Die Makromolekulare Chemie 186 (1985), S. 907-913 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction between the MgTiCl6·4CH3COOC2H5 complex and alkylaluminium compounds was studied. The solid samples, recovered after increasing reaction times, were analysed. Elemental analyses, X-ray diffraction patterns, and IR spectra clearly indicated the formation of activated, high-surface MgCl2. Polymerizations of ethylene were carried out employing, as the solid component of the catalyst system, both MgTiCl6·4CH3COOC2H5 and the recovered samples. The lower induction time in the latter case was related to the extent of MgCl2 formation and its degree of activation.
    Additional Material: 4 Ill.
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  • 185
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Quantitative determinations by 13C NMR performed with insoluble polyurethanes allow to study the kinetics of the polymerization in bulk between hydroxytelechelic polybutadiene G 1000 and 4,4′-methylene diphenylisocyanate (MDI). Comparisons have been made with (G 1000 + MDI) polymerization and (monoalcohol or G 1000 + phenyl isocyanate) model reactions in toluene. With [NCO]/[OH] = 1 and T ≤ 60°C, in solution as well as in bulk, conversions are not complete. Because of the presence of gels, part of the reactive functions have been found to be trapped. For kinetic tests, only the first stage of the polymerization (conversion 〈 70%) may be taken into account. In bulk, the two alcohol functions are equally reactive, whereas in toluene, the hydroxylated 1,4 ends of the polybutadiene chains are more reactive. As evidenced for model reactions in the foregoing paper of this series, the kinetics fit better with the 3rd order than with the 2nd order equation. Nevertheless, at higher temperatures, the 2nd order may be used. The autocatalysis phenomenon found effective for model reactions is negligible in polymerization. All kinetic constants and activation parameters calculated must be considered to be apparent ones only.
    Additional Material: 13 Ill.
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  • 186
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A styrene-isoprene-styrene block copolymer was selected for the preparation of new asymmetric membranes which have blood compatibility properties after chemical modification by addition of gazeous N-chlorosulfonyl isocyanate to the double bonds of the polyisoprene sequences. The membranes were examined with a scanning electron microscope. The permeability of the membrane was studied as a function of time, pressure and viscosity.
    Additional Material: 9 Ill.
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  • 187
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    Die Makromolekulare Chemie 186 (1985), S. 597-608 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three cases of equilibrium copolymerization are re-treated theoretically. The expression of the molecular weight distribution of the copolymer is a two-dimensional distribution function with two random variables m and n, where m and n are the numbers of two different monomeric units, respectively. The molecular parameters of the copolymer, such as the number- and weight-average molecular weights, number-average degree of polymerization, copolymer composition and equilibrium conversions of comonomers, are derived. The relation between the parametric variables in the formulae and the equilibrium copolymerization conditions are determined from two binary cubic equations.
    Additional Material: 2 Ill.
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  • 188
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    Die Makromolekulare Chemie 186 (1985), S. 665-669 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using the spin probe method, the rotational mobility of two probes in poly(oxytetramethylene) (POT) in the region of rapid and slow rotation was investigated. Based on the relaxation diagram the obtained ESR results are compared and discussed in connection with other literature data. It was found that the behaviour of the probes corresponds to the α + β relaxation in the range of high frequencies. Differences in mobility of the probes as well as anisotropy effects of rotations are also discussed.
    Additional Material: 1 Ill.
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  • 189
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that the kinetic laws established for polymerization reactions can be applied for telomerization reactions provided the number-average degrees of polymerization DPn are greater than ten. For DPn 〉 10 it is necessary to calculate the molecular distributions. Values of DPn obtained with the method of Mayo and the molecular distribution method are compared and an experimental application is given by the radical-initiated telomerization of glycidyl methacrylate (2,3-epoxypropyl methacrylate) with bromotrichloromethane.
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  • 190
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    Die Makromolekulare Chemie 186 (1985), S. 1477-1494 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymers of the title monomer have been made using 24 different metathesis catalysts, based on Nb, Mo, W, Re, Ru, Os and Ir compounds. Their structure, determined by 13C NMR spectroscopy, varies from all-cis (ReCl5) to all-trans (RuCl3, OsCl3) and from fully biased (head-tail) to unbiased. The bias stems partly from an inability to from head-head dyads containing cis double bonds and partly from the dipolar interaction between the propagating metal-carbene complex and the monomer in forming the [2 + 2] transition state. Arguments are presented to show that the formation of biased polymers proceeds largely through a metal carbene species in which the last-added monomeric unit has its methyl group adjacent to the metal centre (PH). In high-cis polymers the sequences of three double bonds are such as to indicate that a kinetic distinction must be made between species in which the previous double bond formed was cis or trans (PHc or PHt), consistent with the observation that high-cis polymers of related monomers have a blocky cis/trans distribution.
    Additional Material: 3 Ill.
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  • 191
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    Die Makromolekulare Chemie 186 (1985), S. 1425-1434 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Grafting of acrylic acid onto a pre-activated polypropylene film was investigated, varying the concentrations of monomer and Fe2+ -ions, the polymerization time and temperature. Experiments were planned according to a scheme of a latin square, and statistical analyses were performed for the optimization of the grafting variables. The concentration of ferrous ions was found to be the most significant variable for the graft level. At low concentration, ferrous ions act as activator of grafting but no grafting takes place at relatively high concentrations. The distribution of grafted poly(acrylic acid) within a PP film was examined by microphotometry of the coloured slides of the film. The grafted layer of PP reaches the center only at about 30% of grafted poly(acrylic acid) and up to 70% the distribution of grafted poly(acrylic acid) is still non-uniform with a decreasing amount of the polyacid from the surface to the center. The film samples containing 30% of grafted poly(acrylic acid) already show conductivity in alkaline media and are interesting ion conducting materials.
    Additional Material: 3 Ill.
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  • 192
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For the determination of transfer constants CT to the telogen in telomerization reactions started with free radicals we used three methods. The first one is the method of Mayo, the second one is based on the variation of the conversion degree of telogen to monomer and the last method requires the knowledge of the cumulated number-average degree of polymerization DPn and monomer conversion αM of the samples during the reaction. Verifications of the proposed laws are made for methacrylic acid telomerization with CCl3Br and methyl methacrylate telomerization with benzenethiol as a telogen and 2,2′-azoisobutyronitrile as the initiator at 70°C. The transfer constant to CCl3Br is ca. 0,03 and that to C6H5SH ca. 1,5.
    Additional Material: 3 Ill.
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  • 193
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two principal methods are described for the determination of the cumulative number-average and weight-average degrees of polymerization in polymerization and telomerization reactions. The first method for the calculation of both quantities uses the ratio of monomer concentration and concentration of radicals created. In the second the instantaneous number-average degrees of polymerization of short intervals of monomer conversion are added up. A comparison of the two methods is given and an application is studied for redox telomerization of ethyl acrylate with carbon tetrachloride.
    Additional Material: 1 Ill.
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  • 194
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    Die Makromolekulare Chemie 186 (1985), S. 1495-1504 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: One of the multipulse sequences in FT 13C NMR, the DEPT pulse sequence, was used to decrease the complexity and to improve the information content of 13C NMR spectra of macromolecules such as milled wood lignins (MWL) extracted from hardwoods (Birch and Aspen MWL). This sequence gives the possibility to edit subspectra selectively for CH, CH2 and CH3 carbons, and benefits from a large intensity enhancement for the carbon atom signals, due to polarization transfer. Thus, it is possible to discriminate precisely between quaternary and tertiary aromatic carbon atoms and to show unambiguously the presence of p-hydroxybenzoate structures in Aspen MWL and their absence in Birch MWL. In addition, the DEPT sequence has made possible the observation of signals which, with classical experiments, are overlapped by others signals, either partially, like the C-γ signal of syringaresinol units or completely like the C-α signal in cinnamaldehyde units. Preliminary results indicate that quantitative data might be obtained from the edited spectra.
    Additional Material: 3 Ill.
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  • 195
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    Die Makromolekulare Chemie 186 (1985), S. 1513-1518 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cobalt(II) complexes of poly(ethyleneimine)s 1 in aqueous solution are able to form with oxygen a μ-peroxo adduct as is evidenced from stoichiometry and spectral properties. The oxygen adduct of Co/1 is characterized by its higher rate constant and activation entropy of the oxygen dissociation step, in comparison with those of the low-molecular-weight analogue Co/tetraethylenepentamine (2). This is related with the smaller affinity of Co/1 to oxygen and the reversibility in oxygen-binding. The dissociation of the oxygen molecule coordinated to and bridged with Co/1 is facilitated by a distortion of its μ-peroxo structure due to electrostatic repulsion of polycationic 1.
    Additional Material: 6 Ill.
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  • 196
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The radical copolymerization of 1-acryloyl- and 1-methacryloyl-3-methylpyrazole (1a and 1b) with acrylic acid or methacrylic acid in solution was studied. Copolymers containing carboxyl as well as 3-methyl-1-pyrazolylcarbonyl groups as side chains were prepared via the reaction of 3(5)-methylpyrazole with activated poly(acrylic acid)s of various molecular weights. The hydrolysis data suggest that the release rates of the biocide 3(5)-methylpyrazole from the investigated copolymers vary significantly depending on the content of carboxyl groups and their change during the hydrolysis.
    Additional Material: 1 Ill.
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  • 197
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    Die Makromolekulare Chemie 186 (1985), S. 1613-1623 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The homogeneous system resulting from the reaction between tetrabenzylzirconium and triethylaluminium is an active catalyst for the polymerization of styrene, and p-methyl-, α-methyl and p-chlorostyrenes. The molecular weights and the structures of the resulting polymers are highly dependent on the nature of the monomer and on the reaction medium. In toluene, styrene and p-methylstyrene give essentially linear unsaturated dimers, whereas p-chlorostyrene leads to a polymer with a high molecular weight. In methylene dichloride higher oligomers and a polymer are obtained simultaneously from all the monomers. The comparative behaviour of the styrene derivatives was examined in copolymerization experiments under various experimental conditions. The ratios of monomer incorporation were compared with those reported in the literature for related systems. The results show that, according to the monomer and the reacting medium, the same catalytic system is able to induce polymerizations of the “coordinated anionic”, radical and cationic type.
    Additional Material: 6 Ill.
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  • 198
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    Die Makromolekulare Chemie 186 (1985), S. 1643-1655 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pore structure of various water-swollen fibers of cotton and regenerated cellulose was investigated by means of fiber penetration studies with saccharides and dextrans. From the data the volumes of the pores were obtained and average pore diameters and surface areas calculated assuming a slit pore geometry. There are difficulties in interpreting the results with respect to pore-size distribution. It is shown that the surface areas are suitable parameters of the fiber structure for describing equilibrium dye adsorption of direct dyes in cellulose fibers. From this a simple dying method results for characterizing the pore structure of cellulose materials.
    Additional Material: 5 Ill.
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  • 199
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The infrared spectra of five linear low density polyethylenes, containing methyl, ethyl, butyl, isobutyl and hexyl branches, respectively, were measured. Particular interest attaches to the region 800-1200 cm-1 where the spectra, although weak, show significant differences. The findings of an earlier study on the methyl rocking mode, in the vicinity of 900 cm-1, are confirmed and extended. In particular, no band was detected for the ethyl branched polymer and it must be an order of magnitude weaker than for methyl, butyl and hexyl branches. Conversely, it is displaced in frequency and is markedly stronger for isobutyl branches. The methyl wagging mode band is at about 1 150 cm-1 with the methyl branched polymer. It is relatively broad and probably consists of two overlapping components, specific for methyl branches in crystalline and amorphous regions. This mode is not of detectable intensity for ethyl, butyl and hexyl branches but, as with the rocking mode, it is anomalously strong for isobutyl branches.
    Additional Material: 1 Ill.
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  • 200
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    Die Makromolekulare Chemie 186 (1985), S. 1679-1683 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Relaxation processes in the soft segment phase of a block copoly(ether-ester) elastomer were investigated using the spin probe method. Rotational mobility of the two probes, differing in sizes, were analysed and the results were interpreted based on the relaxation diagram. It was found that the change in mobility of the probes, as detected by the change in ESR line shape, in the slow rotation region corresponds to the β-relaxation, whereas that in the rapid rotation region corresponds to the α + β-relaxation. The analysis of probe mobilities, including the way they rotate, indicates the necessity of inclusion of rotational anisotropy in the interpretation of the behaviour of probes of different size.
    Additional Material: 1 Ill.
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