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  • Articles: DFG German National Licenses  (637)
  • 1995-1999
  • 1975-1979  (637)
  • 1920-1924
  • 1905-1909
  • 1975  (637)
  • 1923
  • Physics  (470)
  • Biochemistry and Biotechnology  (167)
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  • Articles: DFG German National Licenses  (637)
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  • 1995-1999
  • 1975-1979  (637)
  • 1920-1924
  • 1905-1909
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  • 101
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Growth and acetate metabolism by Candida utilis (ATCC 9226) is reported for both acetate- and zinc-limited cultures in defined media. Acetate concentrations were varied from suboptimal to inhibitory levels in both types of media in differential shake flask culture and in batch and continuous cultures in stirred fermentors. Transient responses of steady-state cultures to small or large additions of concentrated sodium acetate, or to shifts in dilution rate or inlet acetate concentration are compared with one another and with simple mathematical models of growth and acetate metabolism. Exponential growth was observed during unrestricted growth (differential shake flask and batch cultures) with both types of media. Addition of acetate during unrestricted growth always caused lags and for larger pulses, lower specific growth rates were observed after exponential growth resumed. Inhibition by high acetate concentrations was much greater in acetate-limited than in zinc-limited cultures. During restricted growth (steady-state, continuous cultures), high acetate concentrations again consistently caused growth lags but stimulated, inhibited, or temporarily stopped acetage uptake. Qualitative agreement between the predictions of a simple mathematical model of acetate inhibition fitted to differential shake flask data and the observed transient data was surprisingly good.
    Additional Material: 12 Ill.
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  • 102
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This work concerns mathematical modeling of the rate of microbial growth on inhibitory levels of nutrients as affected by pH, concentration of the nutrients, temperature, cultivation method, and method of data analysis. Candida utilis (ATCC 9226) was grown with sodium acetate as growth-limiting carbon and energy source in mineral salts medium in shake flask and continuous cultures to study inhibition by excess acetate. Differential shake flask cultures were grown at low yeast concentrations at temperatures (T) of 25 and 30°C, pH's between 5.5 and 7.0, and acetate concentrations (S) between 0.25 and 3.0% (w/v). Growth data were exponential with correlation coefficients greater than 0.995 in 49 of 56 experiments; the lowest correlation coefficient was 0.986. Specific growth rates (μ) determined by graphical methods showed only fair correlation with those determined by regression analysis. Both sets of specific growth rate data were grouped at constant T and pH and fitted to the three parameter equation, \documentclass{article}\pagestyle{empty}\begin{document}$$\mu = \mu _m /(K_s + S + S + S^2 / K_i )$$\end{document}The improvement in use of the fitted equation instead of the mean value was significant with greater than 70% confidence in all (14 groups) and 90% confidence in only half of the data groups; the correlation does not improve with the increasing acetate inhibition at lower pH. Both defects in the model and insufficient data at each pH are responsible. A modified six parameters with hydrogen ion concentration(H+) as follows: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {\mu _m = \mu _m /(1 + K_2 /{\rm H}^ + + {\rm H}^ + /K_1 )} \\ {K_i = K_I (1 + {{K_3 } \mathord{\left/ {\vphantom {{K_3 } {{\rm H}^ + }}} \right. \kern-\nulldelimiterspace} {{\rm H}^ + }})} \\ {K_s = {\rm Contant}} \\ \end{array} $$\end{document} Specific growth rates calculated with the six parameter equation matched observed values in all groups of isothermal data better than the means with greater than 99% confidence. The six parameter model adequately represents effects of acetate and hydrogen ion concentrations under constant or slowly changing environmental conditions and balanced growth; although better models probably exist. Thus steady-stste and transient continuous culture experiments agreed with many published growth yields, but specific growth rates could only be predicted qualitatively from the model fit to the shake flask data. The data and present models could be incorporated into published models for transient growth at low nutrient concentrations to correlate and perhaps predict microbial growth kinetics over a much wider range of growth conditions than now possible.
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  • 103
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    Biotechnology and Bioengineering 17 (1975), S. 1065-1081 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dynamics of a system of two microbial populations having complementary metabolism are investigated by means of simple mathematical models of growth. Complementary metabolism as used here means that each population produces a substance - not present in the initial or feed medium - required by the other for growth. The simple models indicate that (1) something other than lack of the substrate or growth factor produced by its partner must limit the growth of at least one population and (2) the coexistence steady state of such populations in continuous culture is not stable with respect to large perturbations, though it is stable with respect to a wide range of perturbations.
    Additional Material: 9 Ill.
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  • 104
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    Biotechnology and Bioengineering 17 (1975), S. 1101-1108 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The behavior of 20β-hydroxysteroid dehydrogenase in a two-phase system consisting of an emulsion of water with an immiscible organic solvent was investigated. The effect of several organic solvents on the stability, activity, and kinetic profile of the enzyme was considered. The most suitable system for carrying out the enzymatic reactionproved to be water-butyl acetate.The production of high quantities of 20β-hydroxysteroids in 100% yield using catalytic amount of cofactor was achieved by coupling the 20β-, hydroxysteroid dehydrogenase and the alcohol dehydrogenase-catalyzed reactions.
    Additional Material: 4 Ill.
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  • 105
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    Biotechnology and Bioengineering 17 (1975), S. 1335-1347 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The inhibitory activity of tobacco mosaic virus (TMV) infection was assayed with the extracts of various callus tissues derived from the intact plants. Phytolacca americana callus was selected as a producer of the virus inhibitor and its cultural conditions in suspension were examined for cell growth and the inhibitor production. A modified liquid medium containing twofold concentrations of all components in that of Murashige and Skoog plus 2,4-D (1.0 mg/liter) and sucrose (6%), but without any vitamins and glycine was chosen for production of higher levels of the inhibitor. TMV infections in tobacco, bean, and tomato plants were markedly inhibited by the introduction of the disrupted whole broth of suspension cultured P. americana.
    Additional Material: 5 Ill.
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  • 106
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    Biotechnology and Bioengineering 17 (1975), S. 1369-1372 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: No Abstrast.
    Additional Material: 2 Ill.
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  • 107
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    Biotechnology and Bioengineering 17 (1975), S. 1391-1397 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: No Abstrast.
    Additional Material: 3 Tab.
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  • 108
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    Biotechnology and Bioengineering 17 (1975), S. 1467-1471 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new suspension culture system (Mini-AR) based on the Stoke's drag law for suspended particles is described. This apparatus can be utilized for the maintenance of mammalian kidney cells in both short- and long-term cultures.
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  • 109
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    Biotechnology and Bioengineering 17 (1975), S. 1545-1550 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 110
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    Biotechnology and Bioengineering 17 (1975) 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 111
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    Biotechnology and Bioengineering 17 (1975), S. 1599-1615 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A pure culture of Pseudoinonas putida was grown in both a batch and continuous culture using phenol as the limiting substrate. Of two substrate inhibition models examined, the Haldane function was found to statistically best describe the kinetics. The applicable kinetic constants were either measured (μM, KI) or estimated (KS) from the experimental data. Particularly in the continuous culture, wall growth was found to exert significant effects on the broth biomass concentration and phenol conversion, both of which decreased with increasing amounts of wall growth. These effects are opposite to those predicted by wall growth models and to experimental results of others using mixed culture (activated sludge) systems.
    Additional Material: 3 Ill.
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  • 112
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    Biotechnology and Bioengineering 17 (1975), S. 1627-1637 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Immobilized chymotrypsin catalyzes esterification of N-acetyltyrosine in a medium containing high concentrations of alcohols. The hydrophilic support and inclusion of glycerol protect the enzyme activity and allow catalysis to proceed in the presence of only 10% (v/v) water. The same equilibrium concentration of ester is obtained whether reaction proceeds from ester or from free acid. Hates of ester synthesis and hydrolysis are similar when measured under the same conditions, but are at least one order of magnitude slower than optimal rates of hydrolysis. Subtilisin Carlsberg in the free, unmodified form catalyzes ester synthesis at even lower water concentrations; optimal rates are obtained at 5-15% H2O.Hydrolytic enzymes can thus be utilized as catalysts of synthesis reactions in nonaqueous solvents where synthesis is thermodynamically favored over hydrolysis; in some cases this may provide economic and/or energetic advantages over conventional techniques.
    Additional Material: 3 Ill.
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  • 113
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    Biotechnology and Bioengineering 17 (1975), S. 1695-1696 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 114
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    Biotechnology and Bioengineering 17 (1975), S. 1717-1728 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dependence of the specific growth rate of Candida boidinii 11 Bh on methanol concentration follows Monod-type kinetics only in a narrow concentration range (0-0.8% v/v), with a saturation constant of about 19 mmol. With a further increase in methanol concentration of up to 3% v/v, the specific growth rate remains constant. Beyond this level, the growth rate gradually drops to zero, reaching the threshold value at 7.8% v/v. The specific growth rate is also strongly dependent on the size of the inoculum. The biomass yield decreases with an increase in the methanol concentration. Formaldehyde and formic acid, oxidative products of methanol, approximately 100 and ten times, respectively, more toxic to growth than the original substrate.
    Additional Material: 7 Ill.
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  • 115
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    Biotechnology and Bioengineering 17 (1975), S. 1775-1782 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In July the yield of protein extractable from potato haulm could be 600 kg/ha and the beginning of September it is 200 kg/ha. The yield of fiber containing 1 to 2% N is less affected by maturity. The annual waste of extractable protein, suitable for feeding nonruminants, is about 60,000 tons. The contribution that some small changes in conventional potato husbandry might make to minimizing this waste is discussed.
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  • 116
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 117
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    Biotechnology and Bioengineering 17 (1975), S. 1847-1852 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 118
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    Biotechnology and Bioengineering 17 (1975), S. 1-13 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Trichoderma viride QM 9414 growth characteristics on glucose were investigated in single stage continuous stirred tank reactor operation and growth parameters μmax, Ks, QO2 identified. Multistage stirred tank fermentors in series with the first stage utilizing glucose and the subsequent stages utilizing cellulose yielded results in general agreement with theoretical predictions. Significant increase in enzyme productivity over single stage fermentation was obtained in multistage operation.
    Additional Material: 7 Ill.
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  • 119
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    Biotechnology and Bioengineering 17 (1975), S. 51-68 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The requirements for enzymic cofactor recycling have been investigated in a system employing alcohol and lactate dehydrogenases. The interactions of various combinations of free dehydrogenases or dehydrogenases immobilized either to the same or separate supports, with free NAD, a soluble highmolecular weight derivative of NAD or an insoluble derivative of NAD have been examined.
    Additional Material: 8 Ill.
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  • 120
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    Biotechnology and Bioengineering 17 (1975), S. 129-142 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Rapid and extensive growth of Bacillus brevis ATCC 9999 was obtained in a complex medium containing yeast extract and peptone. Gramicidin S (GS) production in this medium reached 2.5 g/liter and 0.25 g/g dry cell weight. GS synthetase I production was also high in this complex medium. Chemically defined media were also developed for this strain. In a glycerol-ammonium sulfate-Tris-salts medium, the culture grew about 40% as well (rate and extent) as in complex medium. Although GS production was low (0.23 g GS/liter), peak specific activity of GS synthetase I was as high as on complex medium. Nutritional experiments showed that growth was stimulated by glutamine, methionine, proline, arginine, and histidine. Addition of these amino acids almost doubled the rate and extent of growth and GS production on a volumetric basis. However the increase in GS was due merely to the increased cell density; GS synthetase I specific activity was in fact decreased by the supplement. Complex medium is better than defined medium for GS and GS synthetase production due to increased cell density and a slower rate of synthetase disappearance.
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  • 121
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    Biotechnology and Bioengineering 17 (1975) 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 122
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    Biotechnology and Bioengineering 17 (1975), S. 203-210 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Enzymes can be sorbed on inorganic carriers followed by crosslinking with glutaraldehyde. In some cases superior results are obtained when the support is precoated with a porous layer of titanium oxide. Immobilized lactase prepared in this way retains essentially all its activity when stored under water at 23°C for long periods of time and loses activity only slowly while treating cheese whey at 55°C over the course of several weeks contact time. Furthermore, catalyst activity is unaffected by frequent sanitization. Optimum pH for these immobilized-lactase catalysts (enzyme produced from A. niger) is about 3.0 and optimum temperature is about 60°C. Amyloglucosidase catalase, L-asparaginase, and trypsin have also been immobilized by these techniques.
    Additional Material: 7 Ill.
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  • 123
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    Biotechnology and Bioengineering 17 (1975), S. 167-184 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Following previous work in which a mass and monoxenous culture of Vorticella microstoma had been successfully established (Water Res., 7, 615 lpar;1973) another species of Ciliata, Colpidium campylum was subjected to continuous cultivation using Alcaligenes faecalis as the sole bacterial food and asparagine as the limiting substrate. This work was primarily undertaken to reveal the interaction and biological oscillation between these two types of organisms which simulate theecological behavior of activated sludge.The fact that the bacteria tended to flocculate and/ or deflocculate depending on the protozoan populastion density was incorporated into the rate equations to account for the oscillation in individual population density of the predator-prey system The mathematical approach presented earlier by canal and other workers forbiological oscillation used a homogeneously of the bacterial food wasoverelooked in the earlier publication.
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  • 124
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    Biotechnology and Bioengineering 17 (1975), S. 277-278 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 125
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    Biotechnology and Bioengineering 17 (1975), S. 299-303 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: No Asbtract.
    Additional Material: 23 Ill.
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  • 126
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    Biotechnology and Bioengineering 17 (1975), S. 315-326 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Acid tolerant lactase (I), α-chymotrypsin (II), and acid phosphatase (III) were immobilized on chitin with glutaraldehyde. Pretreatments of the chit in with acid, alkali, ammonia, and pronase were compared with respect to release of titratable amino groups and ability to retain lactase activity. Shrimp chitin appeared to be more sensitive to pretreatment conditions and so effort was concentrated on crab. An acid-alkali pretreatment was selected as most practical and economical, and the properties of enzymes fixed on crab chitin were studied intensively. The pH optima of the fixed enzymes were shifted about one pH unit; the shift for I was toward more acid pH, for II was toward alkaline pH, and for III was toward acid pH. The retained activity of immobilized I was approximately 60% that of the native enzyme. A column in continuous operation with I on chitin-glutaraldehyde gave an apparent activity half-life of 27 days.
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  • 127
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    Biotechnology and Bioengineering 17 (1975), S. 375-398 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two models for predicting the behavior of cultures of microorganisms under both oxygen and carbon limiting conditions have been evlauated on a chemostat growing Candida utilis on a glycolysis suppressing glycerol medium. The work indicated that parameter values obtained under wholly oxygen limiting or wholly carbon limiting conditions successfully predict the behavior of the chemostat under the wide range of flow and substrate concentration conditions tested. Both models are satisfactory and hence it is deduced that the simpler one may be used with confidence. It was found that Monod kinetics were applicable to the growth rate dependence on oxygen concentration but that Contois kinetics were superior for the corresponding dependence on carbon substrate concentration.
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  • 128
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    Biotechnology and Bioengineering 17 (1975), S. 433-439 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 129
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    Biotechnology and Bioengineering 17 (1975), S. 445-449 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 130
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    Biotechnology and Bioengineering 17 (1975), S. 99-106 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method of calculating the conversion in Rony's hollow fiber reactor is outlined. It, is assumed that, the kinetics are of Michaelis-Menten type and that diffusion within the hollow fiber, as well as through its wall, should be taken into account. The normalization of the Thiele modulus suffices to unify the treatment of internal diffusion and the pseudosteady state hypothesis is found to be valid under almost all conditions.
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  • 131
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    Biotechnology and Bioengineering 17 (1975), S. 119-128 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Immobilized glucoamylase, invertase, and β-galactosidase were prepared by using 2-hydroxyethyl acrylate and dimethylacrylamide under γ-ray irradiation. In the case of 2-hydroxyethyl acrylate, the monomer-enzyme solution was changed to the gel by irradiation of less than 1.0 Mrad, but it was difficult to eliminate enzyme leakage from the gel. When leakage was eliminated by increased irradiation, the activities of the gels were very low. In the case of dimethylacrylamide, the monomer-enzyme solution was changed to a gel by irradiation of 1.0 Mrad; leakage could be eliminated by irradiation of 2.0 Mrad. This gel possessed very high activity. In the case of acrylic acid-sodium acrylate, the monomer-enzyme solution could not be changed to a gel. In preparing gels, high concentrations of enzyme protein had a tendency to obstruct gelation.
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  • 132
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    Biotechnology and Bioengineering 17 (1975), S. i 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 133
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    Biotechnology and Bioengineering 17 (1975), S. 211-226 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method of solution to the problem of enzyme effectiveness factor has been presented. For a rapid estimation of the same, a graphical procedure is discussed which is sufficiently accurate for many practical situations. Applications to systems with rate dependent on position in the pellet and substrate and product inhibition is discussed. The case of concentration dependent diffusivity (facilitated diffusion) can also be solved by a simple transformation.
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  • 134
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    Biotechnology and Bioengineering 17 (1975), S. 253-270 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Macroreticular polystyrene beads may be converted into suitable supports for covalent binding of enzymes. In many respects the supports are physically similar to controlled pore glass (CPG). Our results for immobilized glucoamylase were very similar to published results using CPG as a carrier. The characteristics of immobilized papain were less satisfactory. The product exhibited a Z-shaped activity-time profile suggestive of the involvement of multiple mechanisms.
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  • 135
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    Biotechnology and Bioengineering 17 (1975), S. 1421-1433 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Enzymatic hydrolysis of insoluble amorphous cellulose by Trichoderma viride cellulase was investigated in a batch reactor at several substrate concentrations and three enzyme levels. The reactions were carried out at 50°C and pH 4.8. Enzyme was rapidly adsorbed onto solids on contact, then gradually returned to the liquid phase as the reaction proceeded. A kinetic model that considered the fast adsorption which was followed by the slow reaction, and subsequent product inhibition was developed to interpret the experimental observations. The resulting equation successfully correlated the data for up to 70% conversion. The methods for determining the kinetic parameters are discussed.
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  • 136
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    Biotechnology and Bioengineering 17 (1975), S. 1443-1453 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A process for the utilization of modified whey syrups in wine alcohol fermentations is described. Palatable wines containing 10-12.5% alcohol were produced when various strains of S. cerevisiae var. ellipsoideus were fermented with hydrolyzed whey permeate syrups and grape juice concentrates. Experimental control of final alcohol and residual sugar levels in the wines by various chaptalization techniques is discussed. The possibility of utilizing this process in areas where both whey and grapes are abundant is mentioned.
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  • 137
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    Biotechnology and Bioengineering 17 (1975), S. 1109-1118 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The influence of CO2 on the formation of α-amylase by Bacillus subtilis NCIB 8646 growing in continuous and batch cultures was investigated.Different levels of CO2 examined in the batch cultures stimulated the formation of α-amylase, with the highest activity being obtained using 6% CO2(V/V). The additions of CO2 inhibit the growth and division ofvegetative cells of B.subtilis when CO2 is present in a concentration of more than 3%(V/V).In chemostat cultures, air containing 8% CO2 (V/V) increased the specific enzyme productivity almost three times over the control, without affecting the cell growth.An attempt is made to correlate the obtained results withthe already established theory for the regulation of the α-amylase synthesis.
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  • 138
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    Biotechnology and Bioengineering 17 (1975), S. 1137-1156 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Purified enzymes and cell-free homogenates encapsulated by liquid-surfactant membrane have been shown to retain their catalytic activity (see previously published literature). This paper describes the preparation and properties of liquid-surfactant membrane-encapsulated whole cells of Micrococcus denitrificansATCC 21909. Batch and continuous studies with this model system have demonstrated that encapsulated viable cells reduce nitrates and retain their catalytic activity over anextended period of time. In batch operation, the reactivity of the encapsulated whole cells has been investigated under a variety of experimental conditions. The system is capable of reducing NO3- or NO2-. Data obtained indicate that encapsulated live cells have a broad pH and temperature optimum range. The encapsulated cells remain viable and do not “escape” into the external aqueous phase, even after five days of constant stirring with nitrate-containing simulated wastewater. Pulsed substrate addition experiments have demonstrated that the encapsulated cells also effectively reduce NO2- with no significant reduction in activity, even after 5.5 days of incubation at 30°C. The membrane selectivity for ion transfer has been achieved by incorporating oil-soluble ion exchangers in the membrane. Because of the protection of the liquid membranes, the catalytic reduction of NO2- by the encapsulated whole cells is not inhibited by 1 × 10-4 M mercuric chloride, which is otherwise extremely toxic to the cells, when present in the external aqueous phase. Continuous reduction of 20 ppm of NO2- by liquid membrane-encapsulated whole cells has been demonstrated in a constantly stirred reactor over a test period of about one week. In this paper we will discuss the reduction of NO3-and NO2- by the liquid membrane-encapsulated whole cells of M. denitrificansATCC 21909 mainly in batch runs undera variety of experimental conditions, such as cell and substrate concentrations, product and inhibitor permeation, pH and temperature, effect of oil-soluble ion exchangers on the substrate diffusion, etc.
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  • 139
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    Biotechnology and Bioengineering 17 (1975), S. 1291-1299 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Fermentations with mixed cultures of the cellulolytic fungus Trichoderma viride and the yeast Saccharomyces cerevisiae or Candida utiliswere examined. The fermentations were carried out in an aerated 5 liter fermentor with NaOH treated barley straw as the cellulose source (2-4%). Yeast was inoculated 24-32 hr after the fungus and the growth of the two organisms was followed through the production of CO2 and cell protein. In comparison with fermentations with T. viridealone, the production time for maximum yields of cellulases and cell protein was reduced by several days, depending on the straw concentrations. The protein content of the growth product was 21-22% and the amino acid composition of the product resembled that of T. viride alone.
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  • 140
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    Biotechnology and Bioengineering 17 (1975), S. 1323-1333 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A simple method for immobilizing amyloglucosidase by adsorption on inorganic carriers is described. Amyloglucosidase was adsorbed on acid-activated molecular sieve and on alumina. The immobilized enzyme preparations exhibited 50-100% of the initial activity and possessed high temperature stability. A prolonged working life span was achieved, which could possibly satisfy requirements for industrial application.
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  • 141
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    Biotechnology and Bioengineering 17 (1975), S. 1365-1367 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: No Abstrast.
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  • 142
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    Biotechnology and Bioengineering 17 (1975), S. 1379-1382 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: No Abstrast.
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  • 143
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    Biotechnology and Bioengineering 17 (1975), S. 1387-1389 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: No Abstrast.
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  • 144
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    Biotechnology and Bioengineering 17 (1975), S. 1401-1419 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pancreatic lipase has been immobilized onto stainless steel beads by adsorption followed by crosslinking, and onto polyacrylamide by covalent bonding. The activities of the two types of immobilized enzyme toward the particulate substrate, tributyrin emulsion droplets, were determined experimentally, and rate constants based on Michaelis-Menten kinetics were calculated. The activity of the stainless steel-lipase was determined for various flow conditions and for various support sizes by the use of a differential fluidized bed recycle reactor. The rate constants calculated indicate that the experimental reaction rate is free from mass transfer influences, since the observed Michaelis constant does not vary with the fluidization velocity or with the support particle size. In addition, the Michaelis constant of the stainless steel-lipase was found to be equal to that of the free enzyme, suggesting that adsorption and subsequent crosslinking does not alter the enzyme-substrate affinity. The emulsion substrate mass transfer rates, calculated from the filtration theory, indicate that each substrate particle which contacts the immobilized enzyme is hydrolyzed to a significant extent. Theexperimentally determined kinetic rate constants may be used directly to predict the size of integral fluidized bed reactors.
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  • 145
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    Biotechnology and Bioengineering 17 (1975), S. 1485-1514 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: L-Sorbose is oxidized to 2-keto-L-gulonic acid (KGA) via the following sequence of reactions which we call the “sorbosone pathway”: L-sorbose ⇌ L-sorbosone → KGA. The first step is reversible and is mediated by enzymes found in a soluble fraction obtained from Pseudomonas putida ATCC 21812. Although no cofactor requirements were found for the forward reaction, the reverse reaction clearly required NADH. Enzymes for this NADH-dependent synthesis of L-sorbose could be differentiated on the basis of molecular weights. The second step in the sorbosone pathway is catalyzed by a particulate enzyme found in extracts from P. putida and Gluconobacter melanogenus IFO 3293. The rate limiting reaction in the sorbosone pathway is the synthesis of L-sorbosone. In addition to P. putida, Klebsiella pneumoniae (ATCC 27858) and Serratia marcescens (ATCC 27857) also contain the enzymes which catalyze the reactions of the sorbosone pathway. Two of the bacteria studied, P. putida and G. melanogenus, also contain an enzyme involved in the further metabolism of KGA to L-idonic acid. This enzyme, referred to as KGA-reductase, is found in the soluble fraction of cell-free extracts and is dependent on NADH or NADPH.
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  • 146
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    Biotechnology and Bioengineering 17 (1975), S. 1551-1554 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Tab.
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  • 147
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    Biotechnology and Bioengineering 17 (1975), S. 1591-1598 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The batch growth curves of Laclobacillus delbreuckii exhibit several exponential phases. From the results of a series of shaker flask experiments, the position of the slope changes in the growth curve and the overall bacterial yield is affected by the initial amount of yeast extract in the medium. It is postulated that this behavior is due to several growth enhancing substances that are initially in the yeast extract and are consumed by the bacteria during the course of the fermentation. Using a Monod-type expression to represent the effect of growth enhancing components in a proposed growth rate expression, a mathematical model of the system is set up and solved on the analog computer.
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  • 148
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    Biotechnology and Bioengineering 17 (1975), S. 1639-1662 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Simultaneous removal of organic materials and recovery of protein in the form of bacterial cells from a simulated high strength biodegradable wastewater was studied using thermophilic aerobic microorganisms. A naturally occurring mixed culture of thermophilic microorganisms was obtained from soil, wastewater, hay, silage, etc. A chemically defined medium containing glucose along with other essential nutrients was employed as the feed. The kinetic behavior of the culture was studied in a continuous culture at an optimum temperature of 58°C. Studies were also performed on the effects of solids retention time (SRT) on the observed cell yield and the protein and ash content of the harvested biomass. An economic analysis of the process or single cell protein recovery was given.
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  • 149
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    Biotechnology and Bioengineering 17 (1975), S. 1697-1703 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 150
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    Biotechnology and Bioengineering 17 (1975), S. 1729-1747 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetics of whole-cell lactase of Escherichia coli immobilized in spherical agar gels was determined under the influence of interparticle mass transfer in a fixed bed reactor. The dependence of the pseudokinetic parameters (K′m and v′max) fluid conditions was in accordance with the prediction derived from combinedeffects of kinetics and mass transfer. Within the limited conditions of theexperiments, it was observed that the apparent Michaelis constant could be represented by the following simple equation, K′m/Km = 1 + (φ/kLa)(vmax/Km).The mass transfer coeflicient (kL) needed in the theoretical analysis was determined in correlation with particle size (0.12-0.45 cm) and liquid flow rate (0.30-12.0 cm/min) using the more stable enzyme, cell-bound invertase of Saccharomyces pastorianus, as the material to be entrapped in the gelatinous particles. The relationship was expressed in the following dimensionless equation, (1-φ)Sh = 2 + 0.6Re1/2Sc1/3, except that marked deviation resulting in the reduction of kL was noticed with a Reynolds number less than 0.8.
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  • 151
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    Biotechnology and Bioengineering 17 (1975), S. 1783-1795 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Subtilisin BPN′ was immobilized to porous glass via isothiocyanate coupling. The pH optimum of the enzyme was shifted to the alkaline side on binding. This effect was more pronounced with ethyl lactate than with N-tosyl arginine methyl ester (TAME). Presumably, the shift is a reflection of the negative charge on the surface of the glass. The Michaelis constant and Vmax of soluble subtilisin BPN′ with TAME were two and one orders of magnitude, respectively, lower than with ethyl lactate. Vmax, calculated per g of active enzyme, with TAME as the substrate was not affected by immobilization, while Vmax with ethyl lactate decreased greater than tenfold. The apparent KM decreased on immobilization with ethyl lactate as substrate and increased with TAME. Results are explained in terms of diffusional resistance and a possible attraction of ethyl lactate to the glass surface. Active site titration indicated that about 25%, of the immobilized enzyme was active.
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  • 152
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    Biotechnology and Bioengineering 17 (1975), S. 1827-1828 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 153
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    Biotechnology and Bioengineering 17 (1975), S. 457-460 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Tab.
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  • 154
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    Biotechnology and Bioengineering 17 (1975), S. 465-479 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The use of another air operated extreme pressure hydraulic pump fitted with either a needle valve or a simple microbore tube is described, together with the figures obtained for the soluble protein released from suspensions of commercially obtained baker's yeast (Saccharomyces cerevisiae). The theory of the mechanism is also discussed.
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  • 155
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    Biotechnology and Bioengineering 17 (1975), S. 599-605 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 156
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    Biotechnology and Bioengineering 17 (1975), S. 617-619 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 157
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    Biotechnology and Bioengineering 17 (1975), S. 625-627 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 158
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    Biotechnology and Bioengineering 17 (1975), S. 695-701 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Six enzymes associated with the activities of the nucleus (thymidine kinase), mitochondria (succinate dehydrogenase), lysosomes (acid phosphatase), peroxisomes (catalase), (cytosol lactate dehydrogenase), and the intermembranal mitochondrial space (alkaline DNase) were assayed at 2 hr intervals over the division cycle of repetitively resynchronized HeLa cells. The results indicated a high degree of reproductibility for cells synchronized by the method of perpetual resynchronization and may be of direct use to those interested in subcellular organellogenesis.
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  • 159
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    Biotechnology and Bioengineering 17 (1975), S. 481-497 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Using whole cell invertase of Saccharomyces pastorianus, entrapped in spherical agar pellets, sucrose hydrolysis was carried out in a continuously fed fluidized bed reactor. The effective rate of reaction determined experimentally for the catalytic pellet was correlated with particle radius (R), intraparticle concentration of enzyme (Ep) and external concentration of substrate (SR).The results were elucidated by theoretical analysis incorporating internal mass transfer resistance. At high degrees of diffusional resistance, the effectiveness factor was successfully estimted from Bischoff's equation. A dimensionless number, mA = R(k2Ep/KmD)0.5(Km/(Km + SR)), was used conveniently to predict the effectiveness factor in those cases wher the intraparticle diffusional effect was less significant. This number was employed to determine critical pellet size for an optimal reaction.The relationship between the properties of the pellet (size and intraparticle enzyme activity) and its apparent kinetic constants (k′2 and K′m), estimated according to Lineweaver-Burk, are discussed.
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  • 160
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    Biotechnology and Bioengineering 17 (1975), S. 527-539 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dynamic characteristic of dissolved oxygen probes is usually modeled as being equivalent to a single diffusion layer. Other workers have shown that in response to a downstep in oxygen tension a polarographic probe initially follows single diffusion layer dynamics but that during the last 10% of response the probe deviates significantly from this behavior.Probe response to a series of downsteps of various magnitudes after exposure to calibration gases for 1, 2, and 3 min was recorded. When the probe membrane was new the response behavior was found to be largely independent of the step size as well as the exposure duration.The deviation fro the single diffusion layer model was explained in terms of lateral diffusion of oxygen from the anodic compartment to the cathode. By use of a model incorporating the lateral diffusion, probe response to a general oxygen tension-time function was calculated.
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  • 161
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    Biotechnology and Bioengineering 17 (1975), S. 571-583 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Biokinetic parameters are usually calculated from slopes and intercepts taken from plots of experimental data. One response at an item is plotted and used for parameter estimation. Aside from problems that may be caused by transformations made when the data are plotted, this approach has the weakness of not using all the data simultaneously when there is more than one response. This paper shows how multiresponse biological data can be handled to get parameter estimates that are much more precise than those obtained using conventional methods.
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  • 162
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    Biotechnology and Bioengineering 17 (1975), S. 925-938 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The changes in several parameters of the candicidin fermentation (total, mycelium-associated, and extracellular product formation; growth rate; DNA content; glucose utilization; dissolved oxygen in the broth; and oxygen uptake rate) during the trophophase-idiophase transition are compared with previously reported data for the polyene macrolides, candidin and candihexin. The maturation time, tm, and the productformation rate constant, kp, have been calculated for each of the three polyene macrolides using a simple mathematical model. Slow-feeding of glucose, which resulted in candidin and candihexin overproduction has been shown to increase the polyene formation rate constant and toretard trophophase to idiophase transition (longer maturation time). The opposite effect is achieved by repeated feeding of soybean meal. The values of the maturation times and polyene formation rates obtained were used to predict the production of polyene macrolide antibiotics in batch cultures.
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  • 163
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    Biotechnology and Bioengineering 17 (1975), S. 997-1018 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model was developed to simulate, on a digital computer, the continuous fermentation of whey lactose to lactic acid with neutralization by ammonia. The simulation predicted the retention times for experimental test and the use of two stages for greatest efficiency. In the experimental tests, Lactobacillus bulgaricus was inoculated into whey in a 14-liter continuous fermentor at 44°C and with automatic pH control. A series of steady-state conditions was managed nonaseptically for 42 days without evident contamination and with an actual increase in the efficiency of conversion. Lactic acid was produced predominately' throughout the period, with less than 0.2% of other compounds. The product contained approximately 8 times as much crude protein (N × 6.25) as the original whey. In a single-stage fermentation at pH 5.5, a retention time of 15 hr resulted in a residual lactose concentration of 0.7%; and little improvement was realized by increasing the retention time. Increasing the pH to 5.8 resulted in a significant improvement, but further increasing the pH to 6.0 resulted in only a small additional gain. By the employment of two fermentors in series at pH 5.5 with a total retention time of 31 hr, the residual lactose was reduced to less than 0.1%. Lactic acid was produced as a function mainly of maintenance rather than growth metabolism.
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  • 164
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    Biotechnology and Bioengineering 17 (1975), S. 1029-1050 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A hollow fiber module was used as a reactor for conversion of ethanol to acetaldehyde in the presence of horse liver alcohol dehydrogenase as catalyst. Mass transport rates for NAD+, the overall acetaldehyde generation rate, catalyst effectiveness factors, and the overall order of the reaction with respect to NAD+ concentration were measured. A coupled-substrate reactor with continuous in situ regeneration of cofactor was also examined. Two substrates of opposite redox state were added simultaneously to the feed stream. NADH and acetaldehyde concentrations were monitored in the effluent stream. The cofactor recycle number, or ratio of moles of product to moles of NADH produced, exceeded 10,000 under certain conditions. While decreasing the NAD+ concentration in the feed stream decreased reactor productivity somewhat, it greatly enhanced the ratio of product formed per mole of NAD+ fed to the reactor. It is suggested that high cofactor costs in dehydrogenase reactors may be overcome with efficient in situ regeneration and secondary recovery and recycling of cofactor from the process stream.
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  • 165
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    Biotechnology and Bioengineering 17 (1975) 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 166
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    Biotechnology and Bioengineering 17 (1975), S. 1455-1465 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetic properties of α-galactosidase of Mortierella vinacea were investigated in detail using PNPG (p-nitrophenyl-α-D-galactopyranoside) as a substrate. Consequently, the enzyme was markedly inhibited not only by the substrate, but also by the galactose hydrolized. The initial rate of reaction at sufficiently high substrate concentrations, however, did not fall to zero and did approach a finite value. Galactose behaved as a mixed inhibitor and was neither totally competitive nor totally noncompetitive. A rate equation was obtained from a generalized equation derived from a kinetic model which took both the inhibitions into consideration. The constants used in the equation were appropriately estimated. The calculated rate agreed fairly well with the observed initial rate. Moreover, the PNPG hydrolysis progressing in a batch system was found to be approximately representable by simple first order kinetics in which the rate constant was dependent on the initial substrate concentration.
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  • 167
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    Biotechnology and Bioengineering 17 (1975), S. 1515-1528 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To describe axial dispersion, particle film mass transfer, intraparticle diffusion, and the chemical reaction of the substrate for enzymes immobilized in porous particles in packed columns, we have developed mathematical models for first- and zero-order limits of Michaelis-Menten kinetics. Steady-state solutions were derived for both long and short column boundary conditions and for plug flow. Theory was compared to experiments of hydrolysis of sucrose catalyzed by invertase bound to porous glass particles. Steady-state conversions were measured for a range of flow rates. Pulse response experiments with inert packing were used to determine values of bed void fraction and particle porosity.
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  • 168
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 127-135 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fracture surfaces of an oriented polystyrene (by stretching 150% at 280°F) show many of the same features observed in the fracture of ordinary polystyrene: craze formation followed by quasi-viscous separation of the craze layer or by quasi-brittle fracture along the craze boundary. In cleavage fracture along the direction of orientation, advance fractures are initiated in flat areas covered, if at all, by an extremely thin layer of craze: the initiation of the “crazeles” fractures appears to arise from the orientation of the molecules rather than the presence of impurity particles.
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  • 169
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 43-57 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We describe a new technique for producing fibrous crystals from shear-induced crystallization of polymer solutions and polymer melts. Our technique makes use of a modified version of the 4-Roller apparatus originally developed by G. I. Taylor to study the formation of emulsions. This apparatus generates a planar extensional flow field in which macromolecules are extended more easily than in flow fields with transverse velocity gradients.
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  • 170
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 73-86 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Extrudates of solid linear polyethylene prepared under proper pressure and temperature conditions have a high c axis orientation along the extrusion direction, with lamellar crystals and amorphous layers stacked alternately along the extrusion direction. Kink bands were formed by compressing the oriented extrudate at room temperature along the extrusion direction. Inspection of the kink bands by wide-angle and small-angle x-ray diffraction and electron microscopy revealed that the fiber axis was rotated from the original axis direction by 70-75° and that the lamellar crystals were inclined to the fiber axis in the kink band by 55-60° and stacked nearly parallel to the kink boundary. The superstructural change during the formation of the kink band could not be interpreted in terms of uniform c axis shear alone. In addition to such a mechanism, it was necessary to take into account intermicrofibril and/or intercrystallite slip.
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  • 171
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 137-149 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The complex compliance in extension of gels of poly(vinyl chloride) (PVC) in di(2-ethylhexyl) phthalate (DOP) and in tricresyl phosphate (TCP) was measured over the frequency range from 0.6 to 0.006 cps and the temperature range from -66 to 65°C: the weight fractions of DOP and TCP in the gels were 0.32, 0.40, 0.49, and 0.59. Measurements were carried out in an apparatus using forced low-frequency longitudinal osillations. Data for the gels could not be combined by the method of reduced variables, since there were gradual changes with decreasing temperature, attributable to an increase in crystallinity. Application of the reduction method of Ninomiya and Ferry for solutions of crystalline polymers was found to be successful. The apparent melting temperatures (T′m) were obtained from the temperature dependence of the vertical shift factors. An apparent heat of fusion of ca. 120 cal/mole of monomer unit was found. This melting range was in agreement with that of secondary crystallinity in plasticized PVC reported in calorimetric studies by Juijn. With decreasing temperature, two phenomena occurred in the temperature range from Tg + ca. 80°C to Tg: the vitrification of a concentrated amorphous solution and the slight crystallization of the polymeric component. The larger the difference between Tg and T′m the broader the primary dispersion zone on the frequency scale. This broadening effect was explained as due to the difference in dependence of Tg and T′m on plasticizer concentration, without any need to consider any specific interaction between plasticizer and PVC.
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  • 172
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 223-241 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Certain inorganic nitrate salts are quite soluble in the polymers studied, namely, cellulose acetate, poly(vinyl acetate), poly(vinyl alcohol), poly(methyl methacrylate), and poly(methyl acrylate). Large effects upon the glass-transition temperature were observed in those systems where the transition could be readily measured. Large shifts in the infrared spectra of both the inorganic nitrate salts and in the polymer carbonyl and ester ether frequencies have been observed. These observations have been interpreted in terms of complex formation between these polymers and salts in the solid state. The proposed structure of the complex explains the nature of the infrared shifts both for the nitrate salts and the polymers as well as explaining the concentration effects observed. Effects of the solvating environment upon the salt and polymer spectra remain unexplained. The large glass-transition effects are a result of the degree of solubility of the salts in the polymers and the interactions between them. However, the reason why, in some cases, the change in the transition temperature as a function of concentration goes through a maximum is unclear.
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  • 173
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 263-274 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The deformational, swelling, and potentiometric behavior of poly(methacrylic acid) gels was measured as a function of the degree of crosslinking, ionic strength, and degree of ionization. The comparison of the stress-strain behavior with theoretical relations derived in the preceding part has shown that the relations are valid only if an increase is assumed in the number of monomeric units in the statistical chain segment with increasing degree of neutralization of the gel. This dependence is affected by the salt content in the swelling solution and is also dependent on the activity coefficient of counterions. The pK0 values for an undissociated gel approach pK0 = 5.0 and increase somewhat with degree of neutralization. The swelling equilibria are in qualitative agreement with theoretical assumptions; their quantitative agreement depends on the activity coefficient of counterions.
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  • 174
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 333-338 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of n-hexatriacontane irradiated in the crystalline and molten states were compared as regards the GPC chromatograms of the partially crosslinked products. From differences in the elution volumes it could be inferred that there is a greater trend for random linking along the chain in the sample irradiated in the melt as opposed to preference for end-type linking in the samples irradiated as crystals. In the course of this work the applicability of the GPC technique for detecting short (methyl) branches and for distinguishing between the position of these branches along the chain has also become apparent.
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  • 175
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Partial molar excess free enthalpies (or excess chemical potentials) at infinite dilution were obtained over a large temperature range by gas chromatography. Data on n-alkenes in Apiezon M are interpreted by the Prigogine-Patterson theory; data on normal and branched alkanes in squalane and polydimethylsiloxane (PDMS) are discussed in terms of the Prigogine-Patterson theory and the solution theory of Flory, Orwoll, and Vrij. For the alkane-PDMS systems heats of dilution and partial excess heat capacity data are given.The aim of this work is to get some insight in the applicability of these solution theories to mixtures of fluids, the properties of which may slightly violate the basic assumptions of these theories. It is shown that orientational order in and a large cross-sectional chain diameter of the polymer solvent do not affect their applicability to the partical molar excess free enthalpies of apolar mixtures, whereas large dissimilarities between the force fields around the segments of the mixture components and/or dissimilar chain flexibilities detract from the applicability of these theories (alkanes in PDMS).Special attention has been paid to the effects of dissimilar size and shape of the segments of the mixture compounds on the magnitude of the interchange interaction parameter. It is shown that the multiple-connected segment model after Lichtenthaler et al. does not warrant a reliable combinatorial contribution. Comparison of the interaction parameters obtained for n-alkanes in n-alkanes, Apiezon, squalane, and polyisobutylene and for branched alkanes in squalane reveals that the magnitude of this parameter is affected by small end-effects due to the relative weakness of methyl-methylene interactions.
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  • 176
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 437-441 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 177
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 477-492 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of base stacking interactions on the conformation of poly(9-vinyladenine) (PVAd) was investigated by osmometry, intrinsic viscosity, and light-scattering measurements. At neutral pH, ideal solution behavior (θ conditions) for this polymer was observed at 26 and 40°C. Intrinsic viscosity measurements revealed a conformational transition on heating from 26 to 40°C, while the ultraviolet absorbance of the solution was insensitive to the change. The transition was accompanied by an inversion in sign of the entropy parameter from negative to positive and an increase in the partial specific volume. At 40°, the variation of intrinsic viscosity with molecular weight corresponded to a random coil conformation, but the characteristic ratio, r̄02/nl2 = 8.6 ± 0.2 indicated that the unperturbed dimensions were smaller than usually observed for comparable vinyl polymers. At 26°, a rare macromolecular phenomenon was found, the intrinsic viscosity-molecular weight relation and the estimated r̄02/nl2 of 6.0-6.8 suggested that the PVAd was in a very highly compacted coil conformation, approaching a semirigid sphere. It is proposed that this effect be named the introversion phenomenon. Unlike polyadenylic acid, whose unperturbed dimensions increase with decreasing temperature due to nearest-neighbor base stacking, the results reported here suggest that both nearest-neighbor and long-range intramolecular base stacking occur in PVAd. The different stereochemical arrangements of bases in PVAd and Poly A are probably responsible for the opposite behavior observed.
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  • 178
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 533-566 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The deformation of polyethylene in terms of structural processes has been investigated by low-and wide-angle x-ray diffraction in the case of low-density and, to a lesser extent, high-density polyethylene. The samples possessed a range of simple textures which enabled the deformation processes to be identified. The results are interpreted in terms of a model of stacks of lamellae which have axes along the original draw direction and which deform by lamellar slip, chain slip, and lamellar separation. In most cases these processes accounted for the macroscopic strain but in some cases discrepancies were observed which could be accounted for by inhomogeneous deformation or by the effects of a distribution of lamellar thicknesses. Attempts were made to identify fibrillar slip, without success. The relative contributions of the various deformation processes are examined as a function of temperature and sample treatment by defining a compliance constant for each process. Below room temperature, the results are consistent with expectations based on the α and β mechanical relaxations, whereas the unusual effects at high temperatures are attributed to gradual melting. The compliance constants are also found to depend on the annealing temperature of the sample, and are used to predict the mechanical anisotropy. The volume changes accompanying lamellar separation are examined. They were less than expected in low-density polyethylene, but satisfactory agreement was obtained in high-density polyethylene. A general relation is suggested between volume changes and the lateral development of the lamellae. Hence in narrow lamellae the interlamellar layer can contract laterally whereas the greater constraints imposed by wide lamellae lead to void formation. Other effects examined include the reversibility of the processes which is most marked in the case of chain slip and which is explained by the presence of restoring forces in the amorphous regions including the fold surface. Finally, the differences between low- and highdensity polyethylene are highlighted, emphasizing the part played in the deformation by the amorphous component.
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  • 179
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 599-605 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 180
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 663-666 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 181
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 675-682 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the preceding paper, general equations were established for the motions of chains confined to a tetrahedral lattice. In the present paper, bond orientation correlation and autocorrelation functions are explicitly calculated for the case where only three-bond elementary motions are considered. Effects due to the chain end are analyzed and the relaxation time distribution function is established. The expressions obtained reflect the influence of the chain structure. Finally, to characterize the dynamic behavior of chains in orientation relaxation experiments, the notion of an independent kinetic segment is proposed.
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  • 182
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1167-1176 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study of the morphology of thermally induced crystallization in poly(N-vinylcarbazole) has shown the formation of folded chain lamellae. Diffraction analysis of multiple and single lamellae indicates a paracrystalline structure with hexagonal symmetry about the chain axis and an interchain spacing of 12.00 Å. No sharp reflections due to chain axis periodicity were observed and the chain axis period was calculated from the crystalline density extrapolated to 100% crystallinity. This gave a chain axis period/monomer unit of 2.16 Å consistent with an isotactic 3/1 screw axis and a basic trigonal structure with a = 12.00 Å and c = 6.47 Å.
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  • 183
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1215-1231 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscoelastic properties of chain molecules varying in flexibility and length have been calculated by use of the bead-spring model theory of Zimm. In the evaluation of the hydrodynamic interaction parameter, the number of springs in the bead-spring model, N, has been selected from the range in which the properties predicted by the theory are insensitive to the value of N. The results for limiting viscosity number agree with those predicted by the Yamakawa-Fujii theory of the limiting viscosity number of wormlike chains. The theory also fits the experimental data of Johnson on a sample of polystyrene of molecular weight 860,000 in theta solvents at infinite dilution. The viscoelastic properties of some moderate molecular weight deoxyribonucleic acid solutions are predicted to deviate from the non-free-draining behavior toward the free-draining behavior.
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  • 184
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1269-1274 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Earlier work showed that heating causes poly(diethylsiloxane) to undergo a first-order transition from a semicrystalline solid to a more mobile viscous - crystalline material. The latter is composed of two phases and analogies between polymer and liquid crystal morphology and behavior have been made. The viscous - crystalline phase in PDES appears to be unique since the literature is devoid of other documented examples. In this study, spin - lattice and spin - spin relaxation times were measured over a wide temperature range. They show a glass transition at 138°K, a crystal - crystal transition at 206°K, and a transition around 250°K which results from translational motion of the polymer chains with respect to each other. This motion is observed in the amorphous phase at a lower temperature than in the crystalline phase. Translational motion in the crystalline phase is observed on melting of the crystallites. The spin - spin data permitted monitoring of the molecular motions in each phase and the data suggest that these phases exert some influence on the molecular motions of each other. The viscous - crystalline phase in PDES may represent a unique model for studying and understanding “precrystalline” behavior and structure in amorphous solids.
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  • 185
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1333-1346 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Real and imaginary parts of the dielectric constant of wet and dry polyglycine have been measured for several temperatures over a wide range of frequencies. A simple, rather crude model, proposed earlier for nylon 66, fits the experimental data rather well, but the blocking coefficient p is larger and adsorption effects are more important.
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  • 186
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1377-1386 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of dielectric relaxation have been made for a series of solutions of poly(methyl methacrylate) in toluene. A range of concentrations between 2% and 20% was used for a number of polymers of differing molecular weights. The dispersion was studied over the frequency range 103-106 Hz for temperatures between -90°C and +20°C. It has been found that both the distribution of relaxation times and the activation energy increase with increasing concentration. The magnitudes of the effects vary with molecular weight. A significant observation is that the increase in dielectric constant with concentration is not linear.
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  • 187
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1417-1446 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting behavior of restrained isotactic polypropylene fibers is examined quantitatively in terms of the influence the anisotropic structural state of the polymer has on the observed properties. Two endotherm peaks are observed to occur in some of the samples. The formation and location of the multiple peaks are determined by the orientation of the noncrystalline chains, and is independent of the fabrication path used to achieve that orientation. Above a certain minimum orientation of the noncrystalline chains, multiple endotherm peak formation occurs. The high-temperature endotherm (T2M) extrapolates to an ultimate melting point for fully oriented noncrystalline chains of 220°C, while the lower-temperature endotherm (T1M) extrapolates to an ultimate melting point of 185°C. Noncrystalline chain orientation influences the endotherm temperature through its changing configurational entropy. It is shown quantitatively that the noncrystalline polymer must be considered as plastically deformed, since rubber elasticity theory is not followed as predicted. The melting behavior of isothermally crystallized samples are also reported to further elucidate the nature of the observed endotherms.
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  • 188
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Further stress relaxation experiments, mostly at 50°C, are reported on mixtures of crosslinkable ethylene-propylene terpolymer with saturated ethylene-propylene copolymer (molecular weights 3.6 and 45 × 104) containing up to 50% by weight of copolymer, crosslinked by sulfur to leave the saturated copolymer unattached and free to reptate in the copolymer network. Stress relaxation was measured in small simple elongations (stretch ratio about 1.15) on samples which had been extracted to remove a large part of the unattached copolymer and dried. The relative increase in modulus at long times (104 sec) increased with the proportion extracted; at short times (1 sec), extraction of the lower molecular weight copolymer increased the modulus to about the same extent but extraction of the higher molecular weight copolymer affected it very little. The relaxation modulus of the copolymer extracted from sample 50H (50% copolymer of high molecular weight), obtained by difference, agreed with that for the total copolymer except for a small difference probably attributable to molecular weight selectivity in the extraction. Stress relaxation was measured on sample 50H at six higher elongations up to a stretch ratio of 3. The dependence of stress on time and strain was consistent with an analysis based on the following assumptions: (a) linear additivity of the network and unattached copolymer contributions, (b) strain-time factorization of the stress contributions from the individual components, (c) a strain dependence for the unattached component corresponding to the presence of a Mooney-Rivlin C2 term only, (d) a strain dependence for the network component which does not follow the Mooney-Rivlin equation but is dominated by a simple neo-Hookean term.
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  • 189
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1705-1719 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chain characteristics of a linear sulfonate-containing homopolymer, sodium poly(3-methacryloyloxypropane-1-sulfonate), in aqueous salt solutions (ionic strength, Cs = 0.01N to 5N NaCl) have been investigated by light scattering and intrinsic viscosity. The molecular weight (M̄w)-viscosity relation can be well described by the Mark-Houwink and the Stockmayer-Fixman equations. The coil is highly expanded even in the most concentrated NaCl solution (6N), and no 1:1 electrolyte was found to precipitate this polymer.A linear relation was observed between the viscosity expansion factor, α3η, and (M̄w/Cs)1/2. Examination of the data in terms of theories for excluded volume and hydrodynamic interaction suggests that the coil experiences dominant hydrodynamic interaction, corresponding to a nondraining coil, and the second virial coefficient and coil expansion at high Cs can be correlated by the Flory-Krigbaum-Orofino equation. Results for this polymer are compared with those for other polyelectrolytes, and are discussed in terms of chain structure, flexibility, and hydrophobicity.
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  • 190
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1783-1787 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When a mixture of two monodisperse samples of poly-α-methylstyrene is thermally degraded, the components behave independently, as a first approximation, as shown by GPC and rate of volatilization data. The ratio Mw/Mn, before approaching the ultimate value of 2.0, first goes through a minimum at a much lower value.
    Additional Material: 3 Ill.
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  • 191
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1809-1817 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The overall rate of crystallization of isotactic polystyrene from dilute solutions, 1% by weight, in trans-decalin and benzyl alcohol was studied as a function of temperature using dilatometry. These solvents were chosen because the dissolution temperatures of crystalline isotactic polystyrene are practically the same in both solvents. The overall rate of crystallization as a function of crystallization temperature showed a maximum in both solvents at about 50°C. At lower crystallization temperatures the rate of crystallization is much lower. The overall rate of crystallization of isotactic polystyrene in benzyl alcohol is far larger than in trans-decalin at the same undercooling throughout the temperature range, which is in apparent contradiction to present crystallization theories. At very large undercooling (Tc lower than about 0°C) the solutions of isotactic polystyrene in both solvents quickly become “rigid” gels. Surface replicas of freeze-etched gels indicate that a fringed micelle type of crystallization takes place at these low temperatures. The transition from folded chain crystallization to fringed micelle crystallization may be due to a stiffening of the polymer chain below about 50°C, with a reduced rotational mobility of the phenyl groups on the chain. If very dilute solutions, below 0.5% by weight, are crystallized at these low temperatures no gels were formed but fibrous crystals are produced which could be observed under the polarizing microscope.
    Additional Material: 6 Ill.
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  • 192
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1849-1854 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
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  • 193
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1871-1879 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanical properties (Young's modulus, ultimate tensile strength, deformation processes) of extended-chain polydiacetylene crystals are investigated. The properties observed are similar to those of metal and ceramic whiskers. The elastic modulus is strain-dependent and the ultimate tensile strength increases with decreasing crystal size. The maximum tensile strength observed was 1700 Nmm-2. The ultimate tensile strength seems to be controlled by the presence of a small number of defects near the surface at which fracture nucleates. Irreversible deformation of the crystals was observed to occur by crack propagation normal and parallel to the direction of the macromolecules. The observed mechanical behavior corresponds to exceptionally high per-chain properties. The per-chain modulus obtained for these crystals is nearly as high as that of diamond. A chain-aligned polyethylene fiber with the same per-chain mechanical properties would have an ultimate strength as high as 0.9 × 104 Nmm-2.
    Additional Material: 3 Ill.
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  • 194
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1913-1923 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Contraction experiments were performed on hot-stretched polystyrene during isothermal annealing and tempering. Activation energy spectra were obtained from the experimental data using the Primak theory. In the case of isothermal annealing the theory of Kimmel et al. with shift factors was used. There is an appreciable difference between this spectrum and that obtained from the tempering experiment by the original theory without shift factors. These two spectra should be the same according to the theory. In order to resolve the conflict, we have included a correlation between activation processes in the fundamental equation of the Primak theory. A new formula for calculating the activation energy spectra was obtained. For isothermal annealing, it can be written the same as that of Kimmel et al. The shift factor is also included in the formula for tempering. The activation energy spectra obtained by the new formula gives good agreement between the two methods.
    Additional Material: 6 Ill.
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  • 195
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1939-1944 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Observations by transmission electron microscopy suggest that surface-controlled recrystallization of polyethylene occurs by the solid state nucleation and growth of new crystals with (110) or (110) planes parallel to the free surface. The nucleation site of these crystals is the free surface. The growth process involves the migration of [002] tilt boundaries suggesting that these boundaries have high mobilities. The migration process may occur by the lateral rearrangement of the macromolecules in the [002] tilt boundary.
    Additional Material: 6 Ill.
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  • 196
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2129-2134 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The peel strength found in the trousers-type peeling process is treated for the case in which the adherends, assumed to be flexible but inextensible are bonded by rubbery viscoelastic adhesives.Taking into consideration energy dissipation during deformation of the adhesive, Griffith's criterion is extended to the peeling of viscoelastic materials. For the peeling force per unit width f it is deduced that 2f = Γ + u′h, where T is twice the surface energy, u' is the energy dissipation per unit volume of adhesive, and h is the thickness of the adhesive layer. Values of u' obtained from peeling tests for various thicknesses are compared with those from the tensile tests and found to agree with the above relation. The deduction that the peel strength is independent of the thickness for adhesives with no energy dissipation is also verified experimentally.
    Additional Material: 4 Ill.
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  • 197
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2289-2298 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The low-frequency (10-3 to 5 × 10-1 Hz) dynamic mechanical properties were obtained over the temperature range of 25 to 96°C for 1,5-trans-polypentenamer networks prepared in the presence of 0,0.01, 0.02, 0.04, 0.1, 0.2, and 0.4% dicumyl peroxide. For comparison, similar properties of 1,4-polybutadiene crosslinked with 0.02% dicumyl peroxide were also measured. Superimposed curves for the components of the dynamic compliance, Jp′ and Jp″, reduced to 25°C were obtained and the retardation spectra L were calculated over a range of four logarithmic decades deep in the rubberlike region. It was found that networks containing 0.04 and 0.1% DCP have a small loss maximum Jp″ in the reduced frequency region log ωaT between -2 and 0 which can be assigned to relaxations of untrapped entanglements. The values of (Jp′ - 1/ωη) for very lightly crosslinked polypentenamer networks approached equilibrium very slowly compared to 1,4-polybutadiene crosslinked to the same degree, which suggests the participation of very long retardation times of this polymer which is also probably reflected in the comparatively high values of C2 of the Mooney-Rivlin equation.
    Additional Material: 4 Ill.
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  • 198
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2331-2343 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic mechanical properties of a number of ultra-highly drawn polyethylenes have been studied over a wide range of temperature. It is shown that the materials possess low temperature Young's moduli as high as 1.6 Mbar, a figure which approaches the theoretical and experimental values for the c-axis crystalline modulus of this polymer.The α and γ relaxation processes are still clearly discernible even at highest drawn ratios (ca. 35) and a quantitative analysis of the results, using structural data obtained from broad line nuclear magnetic resonance (NMR) measurements, suggests that the data are consistent with a modified series model.
    Additional Material: 10 Ill.
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  • 199
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2385-2390 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the initial stage of the development of transcrystallinity, nuclei appear sporadically on the substrate. The growth rate and melting temperature of the transcrystalline region are found to be the same as those of spherulites nucleated in the bulk of the polymer. Nucleation densities ns at the interface, and nb in bulk, for the crystallization of isotactic polypropylene, poly(ethylene oxide), and poly(butene-1) in contact with various substrates, have been measured by counting the number of spherulites generated. Despite variations in the results from various causes, the quantities ns and ns/nb are useful parameters for characterizing the nucleating ability of various substrates.
    Additional Material: 2 Ill.
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  • 200
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    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2391-2400 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the melt crystallization of isotactic polypropylene, poly(ethylene oxide) and poly(butene-1) in contact with substrates, the existence of a fixed number of nucleating sites on the substrate surfaces has been established. When these sites become active successively (the transient in the number of nuclei is long) during crystallization, pseudohomogeneous nucleation on the substrate occurs. Nucleation rates for poly(butene-1) and poly(ethylene oxide) on substrates and in bulk have been measured. These data can be used for comparing the nucleating ability of substrates. Estimates of the variation of bulk nucleation rates from one volume element to another as well as for repeated crystallization within a given volume element have been included. Finally, the temperature coefficients of heterogeneous nucleation rates have been combined with the temperature coefficient of spherulitic growth rate of poly(butene-1), to yield values of the interfacial energy parameters appearing in the theory of heterogeneous nucleation. The quantitative characterization of the nucleating ability of substrates by this method is an improvement over the mere use of nucleation densities or nucleation rates.
    Additional Material: 4 Ill.
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