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  • 1
    Electronic Resource
    Electronic Resource
    Effect of crosslinker on properties of copolymeric N-vinyl-2-pyrrolidone/methyl methacrylate hydrogels and organogels (1990)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 191 (1990), S. 331-343 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The γ-ray initiated copolymerisation of N-vinyl-2-pyrrolidone with methyl methacrylate in the presence of crosslinker has been effected to high conversion. At two fixed compositions of the principal monomers, the inclusion of different concentrations of the tetrafunctional crosslinkers ethylene dimethacrylate and a low molar mass poly(ethylene glycol) dimethacrylate produced crosslinked xerogels, which were subsequently swollen in water and 1,4-dioxane to yield hydrogels and organogels, respectively. These gels were characterised by determinations of sol fraction, equilibrium solvent content and uniaxial compression stress/strain measurements. Differences among the swelling and mechanical properties according to the nature and concentration of crosslinking agent and according to the nature of the swelling medium are noted and discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1990.021910207
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  • 2
    Electronic Resource
    Electronic Resource
    Observations on the swelling behaviour of copolymeric hydrogels containing N-vinyl-2-pyrrolidone (1990)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 191 (1990), S. 321-330 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer-water interaction parameters, sequence length distributions and contents of total, freezing and non-freezing water have been discussed for a family of hydrogels. The xerogel precursors contained N-vinyl-2-pyrrolidone (VP) with several co-monomers of different levels of hydrophobicity present in the xerogel over a wide range of composition. Common trends in the behaviour of these systems have been noted and rationalised. In particular the findings indicate that (i) in the poly-VP hydrogel ther are ca. 8-10 molecules of non-freezing water per VP unit and (ii) in the copolymeric hydrogels the maximum occurring in the variation of mole fraction of VP versus mole fraction of water is due substantially to the sharp increase in uptake of freezing (or bulk) water by copolymers rich in VP.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1990.021910206
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  • 3
    Electronic Resource
    Electronic Resource
    Copolymerization kinetics of 4-methoxystyrene with methyl methacrylate and 4-methoxystyrene with styrene: A test of the penultimate model (1990)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 28 (1990), S. 2097-2106 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The propagation kinetics for the copolymerization of 4-methoxystyrene with methyl methacrylate and 4-methoxystyrene with styrene have been investigated using a pulsed laser technique. The dependence of the copolymerization propagation rate constant on the monomer feed ratio shows a diviation from classic Mayo-Lewis model kinetics for 4-methoxystyrene with methyl methacrylate but not for 4-methoxystyrene with styrene. These results have been interpreted to indicate that a penultimate effect is apparent in the first monomer pair but not in the second. With r1r2 = 0.092 for the copolymerization of 4-methoxystyrene with methyl methacrylate and r1r2 = 0.95 for 4-methoxystyrene with styrene, it is suggested that a deviation of the product of the coplymerization reactivity ratios from unity may be an indication of the presence of a penultimate effect.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1990.080280807
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  • 4
    Electronic Resource
    Electronic Resource
    Polyacrylamide gels formed with Cr+3 ion and Cr(acetate)3: Thermodynamically and kinetically controlled crosslinking reactions (1992)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 1071-1075 
    Details
    ISSN: 0887-624X
    Keywords: polymer gels ; polyacrylamide ; metal ion crosslinking ; enhanced petroleum recovery ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gelation of buffered aqueous Cr+3/polyacrylamide (PAAm) solutions has been studied over the pH range 2-11. With Cr+3 supplied as Cr(NO3)3 and a 7.5% hydrolyzed PAAm the upper limit for gelation was about pH 7, but Cr(acetate)3/PAAm solutions gelled as high as pH 9. Evidence is presented that the formation of unreactive colloidal Cr(OH)3(H2O)3, rather than polymer crosslinking, is favored thermodynamically for Cr+3/PAAm solutions at pH 〉 7. The crosslinks formed in Cr(acetate)3/PAAm solutions at pH 7-9 are deduced to be kinetically controlled products. Independent evidence for the kinetic stability of Cr+3/PAAm gels above pH 7 has also been obtained. Other observations relevant to the mechanism of crosslinking of PAAm with Cr(acetate)3 are described.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1992.080300612
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  • 5
    Electronic Resource
    Electronic Resource
    Effect of crosslinking on the properties of poly(2-hydroxyethyl methacrylate) hydrogels (1991)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 189 (1991), S. 195-205 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 2-Hydroxyethyl-methacrylat wurde durch Initiierung mit γ-Strahlung in Masse mit zwei verschiedenen tetrafunktionellen Monomeren (Ethylenglycol-dimethacrylat und 1,2-Bis(acryloxymethyl)-tetramethyldisiloxan) und einem hexafunktionellen Monomeren (1,1,1-Trimethylolpropan-trimethacrylat) als Vernetzungsmittel copolymerisiert. Die erhaltenen Xerogele wurden anschließend mit Wasser bis zum Erreichen der Gleichgewichtsquellung behandelt. Um die drei Vernetzungsmittel vergleichen zu können, wurde unter Berücksichtigung von Molmasse und Funktionalität der Xerogele die theoretische Konzentration an Vernetzungsstellen zwischen 0,032 und 0,644 mol/l variiert. Die relative Hydrophobie der drei Vernetzungsmittel hat einen ausschlaggebenden Einfluß sowohl auf die Gleichgewichtsquellung als auch auf den Elastizitätsmodul der gequollenen Gele. Der Gehalt an nicht-einfrierbarem Wasser in mit 1,1,1-Trimethylol-propan-trimethacrylat vernetzten Gelen wurde anhand von DSC-Untersuchungen analysiert. Das Verhältnis von nicht-einfrierbarem zum Gesamtgehalt an Wasser in den Gelen nimmt mit steigender Vernetzungsdichte zu.
    Notes: By means of γ-irradiation 2-hydroxyethyl methacrylate has been copolymerized in bulk with two different tetrafunctional monomers, ethylene glycol dimethacrylate and 1,3-bis(acryloxymethyl) tetramethyl disiloxane and with a hexafunctional monomer, 1,1,1-trimethylolpropane trimethacrylate. The resultant xerogels were subsequently swollen to equilibrium in water. In order to allow a comparison among the three crosslinkers, their molar masses and funtionalities were taken into account, the theoretical crosslink concentrations being varied from 0.032 to 0.644 mol dm-3. The relative hydrophobicity of the three crosslinkers was found to have a significant effect on both the equilibrium swelling and elastic modulus of the swollen gels. Non-freezing water in several gels crosslinked with 1,1,1-trimethylolpropane trimethacrylate was analysed by differential scanning calorimetry (DSC). The proportion of non-freezing water in the gel relative to the overall water content was found to increase with increasing crosslink density.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1991.051890118
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  • 6
    Electronic Resource
    Electronic Resource
    Solution conformation of a cyclic neurokinin antagonist: A nmr and molecular dynamics study (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1165-1173 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solution structure of a hexapeptide, cyclo(Gln-Trp-Phe-Gly-Leu-Met), which is a selective NK-2 antagonist, has been studied by a combination of two-dimensional nmr and molecular dynamics (MD) techniques. The simulation based on nmr and MD data resulted in the convergence to a family of structures. Free molecular dynamics for 50 ps in the presence of DMSO solvent molecules shows that the structure is energetically stable. One intramolecular hydrogen bond between the amide proton of Gin and the carbonyl oxygen of Gly was revealed. This result is consistent with the results from the measurement of the temperature coefficient of the amide protons. The extent of intermolecular hydrogen bonding between the amide protons of the peptide and DMSO was also revealed by the free MD simulation. The resulting structure of the cyclic peptide contains a variation type I′ β-turn in the Gly-Leu-Met-Gln segment. Comparison of the structure of this peptide with that of other NK-2 antagonist cyclic hexapeptides was made, and the activity of cyclic antagonists appears to be inversely related to the conformational rigidity of the cyclic peptides. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360340906
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  • 7
    Electronic Resource
    Electronic Resource
    Ab initio molecular orbital calculations on the transition state for the addition of a methyl radical to vinyl monomers (1994)
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 3 (1994), S. 905-913 
    Details
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ab initio molecular orbital calculations have been performed on the transition state for the addition of methyl radical to twelve vinyl monomers using the SV 3-21G basis set. A linear relationship has been found between the calculated energies of activation and previously calculated energies of reaction. This supports the assumption of an Evans-Polanyi type rule in previous work which attempted to correlate reactivity with calculated energies of reaction. The activation energies obtained for methyl addition to butadiene and styrene were calculated to be negative. This is caused by errors introduced by a number of sources, viz. basis set superposition error, spin contamination and zero point energy. These errors are discussed. Previous authors have reported reasonable agreement between calculated activation energies at SV3-21G and experimental values for methyl addition to ethylene, this work suggests that this agreement was coincidental and results from the fortuitous cancellation of errors. The nature of the transition state for these radical addition reactions is discussed and the limitations of the SV3-21G basis set are highlighted. The theoretical prediction of activation energies for radical addition reactions would require much larger calculations, beyond the computational means of most research laboratories.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/mats.1994.040030507
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  • 8
    Electronic Resource
    Electronic Resource
    Slow-gelling Cr+3/polyacrylamide solutions for reservoir profile modification: Dependence of the gelation time on pH (1991)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 43 (1991), S. 1527-1532 
    Details
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Systematic studies of the gelation of both buffered and unbuffered aqueous Cr+3/polyacrylamide solutions show that the gelation time is a strong function of pH, increasing by about one order of magnitude per unit decrease in pH for polyacrylamides less than about 7.5% hydrolyzed. The gelation rate also depends strongly on the Cr+3 concentration, the degree of polymer hydrolysis, and temperature. At 25°C, gelation delays of more than 10 months have been obtained; the maximum delay observed at 60°C is about 1 month and at 90°C 1 d. The resistance of buffered gel solutions to change in pH results in significantly longer gelation times at 90°C and low pH than for identical unbuffered solutions; at lower temperatures, however, the differences are insignificant. Most importantly, the use of low pH to control the gelation time of Cr+3/polymer solutions provides an attractive, inexpensive substitute for the environmentally unacceptable Cr+6/reductant method currently employed for profile modification treatments.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1991.070430815
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  • 9
    Electronic Resource
    Electronic Resource
    Errata (1993)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Biomaterials 4 (1993), S. 363-363 
    Details
    ISSN: 1045-4861
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jab.770040412
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  • 10
    Electronic Resource
    Electronic Resource
    Polyethylene wear debris and tissue reactions in knee as compared to hip replacement prostheses (1994)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Biomaterials 5 (1994), S. 185-190 
    Details
    ISSN: 1045-4861
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: Differences in bearing surface conformity and wear mechanisms suggest that the polyethylene (PE) wear debris generated by total knee replacement (TKR) prostheses should be different than that in total hip replacement prostheses (THR). To address this issue, PE wear debris and the cellular response in periprosthetic tissues from 19 failed TKRs was compared to that from 24 failed THRs using polarized light microscopy and a semiquantitative grading system. The foreign-body inflammatory reaction in the THR cases was characterized by plump macrophages with a diffuse cytoplasmic birefringence when examined under polarized light, indicating the presence of multiple submicron particles of PE. The majority of the PE particles were 〈1 μm in size and only a small fraction of the total were 〉10 μm. The foreign-body inflammatory reaction in the TKR cases was characterized by giant cells with fewer macrophages. In the TKR specimens, the size range of PE particles was broader than in the hips. PE particles between 2 and 20 μm were frequent in TKR specimens; particles 〈1 μm in length were less common than in the THR specimens. Diffuse cytoplasmic birefringence was not a characteristic of the TKR cases. These histologic differences were so consistently distinct that the source of the specimen (i.e., from a THR or TKR) could be blindly determined by light microscopy. The size distribution of the PE wear particles in these cases indicate that THRs generate a higher number of submicron PE particles and relatively few large particles while TKRs generate a broader range of particles that includes fewer submicron particles. The observed differences in the cellular responses is likely a direct result of the differences in the spectrum of PE wear particles. These differences may in part account for differences in periprosthetic bone resorption and loosening in TKRs as compared to THRs. © 1994 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jab.770050302
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