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  • Polymer and Materials Science  (56)
  • SPACECRAFT PROPULSION AND POWER  (5)
  • 1995-1999  (29)
  • 1980-1984  (20)
  • 1975-1979  (11)
  • 1970-1974  (1)
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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1279-1285 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of β-pinene with styrene oxide (SO) and β-pinene with N-vinylpyrrolidone (VP) was investigated by using SnCl4 in dichloromethane diluent at low temperature. Monomer reactivity ratios were evaluated for both copolymers at -80°C; these are r1(SO) = 2.979 and r2(β-pinene) = 0.002 and r1(VP) = 0.096 and r2(β-pinene) = 0.294.
    Additional Material: 1 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 39 (1996), S. 435-444 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the Brownian dynamics simulation technique, we studied the fracture process of DNA chains subjected to transient extensional flow, letting the solution with DNA molecules pass through a very small orifice (radius = 0.0065 cm), thus experiencing extensional flow of the convergent (sink) type. The DNA molecules were modeled as FENE bead-spring chains with the springs obeying a modified Warner force law, as proposed by Reese and Zimm. The fracture yield was strongly dependent on flow rate and molecular weight, reaching, in our setup, a level of 100% at a flow rate of around 0.001 cm3/s for DNA with molecular weight 26 × 106 (T7 DNA). There was found to exist a critical flow rate (Qcrit) below which fracture did not occur, in accordance with what was observed in studies on polystyrene in transient extensional flow. We found that for DNA, the critical flow rate depended on the molecular weight as Qcrit ∼ M-14 when the hydrodynamic interaction effect (HI) was not included in the simulations. When HI was accounted for, the relation was found to be Qcrit ∼ M-1.1, close to the theoretical prediction for fracture of partly extended chains in transient extensional flow. © 1996 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
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  • 3
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 4
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The sequence of a cholecystokinin (CCK) related peptide was modified to obtain analogues, which intereact selectively either with CCK-B, or with δ-opioid receptors. Two kinds of peptides were designed, namely, the cyclic peptides of the H-Tyr-cyclo(D-Pen-Gly-Trp-L-/D-3-transmecaptoproline)-Asp-Phe-NH2 sequence (compounds 1a and 1b, respectively), and the linear peptides of the H-Tyr-D-Val-Gly-Trp-L/D-3-trans-methylmercaptoproline-Asp-Phe-NH2 sequence (compounds 2a and 2b, respectively). The only difference between the chemical structures of the linear analogues compared to the cyclic ones is that one covalent bond has been eliminated and a sulfur atom is replaced by a methyl group. Molecular modeling showed that, among low-energy conformers of cyclic compounds 1, there are three-dimensional structures compatible to the model for δ- receptor- bound conformer, suggested earlier[G. V. Nikiforovich. V. J. Hruby. O. Prakash, and C. A. Gehrig (1991) Biopolymers. vol. 31. pp. 941-955]. Results of binding assays fully supported the rationale for the design of compounds 1 and 2. The cyclic analogue 1a has Ki values of 4.5 and 〉 5000 n M at δ- and μ-opioid receptors, respectively; IC50 values of 3000 n M for both CCK-A and CCK-B receptors, whereas its linear counterpart 2a has ki values of 462 and 229 nM at δ- and μ-opioid receptors, respectively; and IC50 values of 1.6 and 〉 10.000 nM for CCK-A and CCK-B receptors, respectively. The results of this study demonstrate a possibility to redirect a peptide sequence that interacts with one type of receptors (CCK-B receptors) toward interaction with another type (δ-opioid receptors) belonging to a different physiological system. This redirection could be performed by changing the conformational properties of the peptide with very minimal changes in its chemical structure. © 1995 John Wiley & Sons, Inc.
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  • 5
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Four fractions of poly(vinyl chloride) (PVC) having appreciably different tacticity distributions were prepared by selective extractions on samples polymerised at temperatures between +60 and -50°C. They were degraded thermally at 180°C in the solid state to conversions in the range 0,2 to 0,5% and in solution at 200°C to conversions in the range 1,6 to 5%. The polyene sequence distribution was investigated by ultra violet/visible (UV/VIS) and resonance Raman spectroscopy. The results show that the type of polyene sequence distribution depends markedly on the tacticity distribution of the polymer. Cross-linking reactions occur more readily as the syndiotacticity increases. The results are discussed and interpreted with reference to previous work relating degradation processes and tacticity.
    Additional Material: 6 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 183 (1982), S. 2399-2413 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A spectroscopic and conductimetric study of the cationic polymerization of 2-vinylfuran (1) and 2-methyl-5-venylfuran (2) showed the existence of an important side reaction originating from a hydride-ion shift from an unsaturated polymer molecule to an active species. The resulting allylic carbocation, in equilibrium with a doubly unsaturated polymer molecule, can react further and the repetition of the mechanism on progressively more conjugated species leads to the formation of a series of highly charge-delocalized carbenium ions absorbing throughout the visible region of the spectrum (and giving high electrical conductivity) and of neutral polyconjugated polymer molecules. Since the hydride-ion abstraction occurs from the tertiary carbon atom of the vinylic chain, vinylidene polymers of monomers such as 2-isopropenylfuran (3) and 2-isopropenyl-5-methylfuran (4) are not susceptible to it. Indeed, their cationic polymerization proceeds without colour formation and conductivity increase.
    Additional Material: 7 Ill.
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  • 7
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A spectroscopic (UV, IR, 1H NMR) study of the cationic polymerisation of 2-vinylfuran (1a) and 2-isopropenylfuran (2a) showed the existence of an important alkylation reaction at C5 which competes with normal propagation. The extent of this competition depends on the monomer used and the polymerisation temperature. A comparison of the spectra of standard polymers (prepared by radical or stereospecific polymerisation) with those of polymers obtained by cationic initiation allowed to assess the extent of alkylation and its regiospecificity at C5 2-Methyl-5-vinylfuran (1b) and 2-methyl-5-isopropenylfuran (2b) were found to undergo cationic polymerisation without any interference from alkylation reactions. Reactions between these four monomers and 2-methylfuran in the presence of typical acidic catalysts gave very high yields of alkylated products and no polymerisation, thus confirming the importance of this electrophilic reaction and its possible application to synthetic uses.
    Additional Material: 15 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1277-1284 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The products resulting from the reaction of PVC with sodium benzenethiolate were degraded to 0,3% at 180°C in the solid state and at 160°C in solution in trichlorobenzene. The polyene distribution of the polymers after degradation was studied by both UV-visible and resonance Raman spectroscopies, as a function of the degree of substitution. The results show that there are two types of behaviour: that of the PVC sample prior to the substitution reaction together with the samples modified up to a definite degree of substitution which depends on the starting isotactic content, and that of samples with higher degrees of substitution. The former group exhibits not only a steady improvement in thermal stability but also a preferential formation of polyenes of 7 - 9 double bonds whose concentration decreases with increasing degree of substitution. Conversely, for the second group of samples the thermal stability decreases with the degree of substitution and no specific absorption bands are observed. On the basis of earlier work on the selective substitution of the isotactic GTTG and heterotactic TTTG triads during the first stage of the reaction, the present results show that the bands at 393, 416, and 437 nm are related to specific polyenes which result from initiation by the above quoted conformations in PVC, a conclusion for which confirmatory evidence was obtained by resonance Raman spectroscopic examination of the samples. There is, therefore, clear evidence for the occurrence of two distinct degradation mechanisms, one involving initiation by the unstable triad conformations and the other via random initiation at stable and normal structures. To this may be added the initiation by defect structures, which have been extensively documented in the literature.
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  • 9
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Anionic polymerization of p-triphenylgermylstyrene (1a) and p-tributylgermylstyrene (1b) were investigated under high vacuum conditions (≈10-6 mbar). Both 1a and 1b were readily polymerized with sodium naphthalide, potassium naphthalide, or α-methylstyrylsodium oligomers to form “living polymers”. The addition of α-methylstyrene to these living systems gave the triblock copolymer, poly(α-methylstyrene-b-p-triphenylgermylstyrene-b-α-methylstyrene). Both monomers were also polymerized radically with AIBN as initiator. Some physical properties of the resulting polymers were examined.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 29 (1984), S. 1735-1741 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Three PVC samples having different tacticities, as well as the products resulting from their reaction with sodium thiophenate, which was previously found to occur selectively by some definite isotactic conformations, were degraded at 180°C in solid state up to 0.3%. In agreement with prior works, the stability of the substituted polymers was shown to be higher as the substitution extent increased up to a definite value, which depends on the overall isotactic content of the starting materials. On the other hand, the found changes in polyene distribution for the degraded samples with the substitution extent, as followed by UV-visible spectroscopy, demonstrate that the specific bands at 393, 416, and 437 nm, which are known to be characteristic for the most unstable PVCs, arise from the lability of some chlorine atoms located at GTTG′ (or TTTG) conformations, as prior results suggested. On the basis of the so-obtained correlation between the content of some isotactic triads (especially the GTTG′) and both the thermal instability and the formation of the above-indicated specific polyenes, new advances in the degradation mechanism are proposed.
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