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  • 2000-2004  (43)
  • 1990-1994  (21,703)
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  • Polymer and Materials Science  (37,631)
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  • 1
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The increasing requirements in wastewater treatment have led to the development of new wastewater treatment processes based on the know-how and experience in reaction and process engineering of the chemical industry. Due to their compactness, closed operation and high flexibility, these new processes show a large potential for process integration and significant cost reduction in particular for highly polluted industrial wastewaters.This paper discusses the HCR (high-performance compact reactor) - process, developed at the Mass Transfer Laboratory of the Technical University of Clausthal within the last decade. This process has been realized in more than 30 technical applications with a volume loading of up to 70 kg COD/m3 d and an energy consumption of about 0.4 kWh per kg CODelim.
    Additional Material: 10 Ill.
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  • 2
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 169-174 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nitrogen fixing Anabaena azollae strains isolated from four different Azolla cultures were characterized based on their total protein profile and RAPD profile to study the existing variation among them. As expected, the isolates showed almost similar protein banding patterns, but exhibited differences in 40-70 KDa protein subunits. Polymerase chain reaction of the DNA of the isolates, using four different primers, amplified specific sequences of DNA and showed clear polymorphism among the isolates. The RAPD profile generated the fingerprinting pattern characteristic of each strain based on the sequence of the primers used. Common band sharing observed between the strains A. azollae-RS-KK-SK-AM and A. azollae-RS-KK-SK-RP probably represents maternal inheritance of DNA to the progeny. The polymorphic bands were generated specifically for the isolates A. azollae-RS-KK-SK-RP and A. azollae-RS-KK-SK-AM with primers numbered 2 and 4, respectively, which could be developed as possible markers for these isolates.
    Additional Material: 1 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 175-183 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mature seed-derived callus from an elite Chinese japonica rice cv. Eyl 105 was transformed with a plasmid containing the selectable marker hygromycin phosphotransferase (hpt) and the reporter β-glucuronidase (gusA) genes via particle bombardment. After two rounds of selection on hygromycin (30 mg/l)-containing medium, resistant callus was transferred to hygromycin (30 mg/l)-containing regeneration medium for plant regeneration. Twenty-three independent transgenic rice plants were regenerated from 127 bombarded callus with a transformation frequency of 18.1%. All the transgenic plants contained both gusA and hpt genes, revealed by PCR/Southern blot analysis. GUS assay revealed 18 out of 23 plants (78.3%) proliferated on hygromycin-containing medium had GUS expression at various levels. Genetic analysis confirmed Mendelian segregation of transgenes in progeny. From R2 generations with their R1 parent plants showing 3:1 Mendelian segregation, we identified three independent homozygous transgenic rice lines. The homozygous lines were phenotypically normal and fertile compared to the control plants. We demonstrate that homozygous transgenic rice lines can be obtained via particle bombardment-mediated transformation and through genetic analysis-based selection.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 202-202 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 219-233 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The GRAM-positive bacterium Rhodococcus erythropolis K2-3 and the GRAM-negative Ochrobactrum anthropi K2-14 are capable of synergistically degrading 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB). The two strais execute this task in a symbiotic manner, but the nature of the interaction involved in the degradation is only partially understood as yet. An essential first step in elucidating the interaction is to be able to monitor the two strans separately, at the cellular level, within mixed populations. Therefore a method exploiting fluorescently labelled lectin probes was developed. Since Concanavalin A (Con A) binds specifically to R. erythropolis K2-3, it was selected and linked to the fluoresent dye Bodipy 630/650, which has an excitation maximum in the red part of the visible light spectrum. Forward light scatter (FSC) and DNA fluorescence from both strains were also measured to obtain simultaneous information about their physiological states. The three parameters were conveniently monitored by dual and triple excitation flow cytometry in conjunction with double fluorescent staining techniques. In addition, the strains were identified using an epifluorescence microscope. These techniques were found powerful tools for the population analysis of this mixed bacterial system.
    Additional Material: 7 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 235-274 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: A quite unconventional, innovative scientific methodology called “macroscopic pattern analysis” is presented in this paper. This approach is more adequate in the case of complex systems than the well-known microscopic, mechanistic approach. Complex systems are not only attracting more engineering interest, but their scientific treatment is increasingly wanted by society due to the manifold problems in Earth's ecosphere. The macroscopic pattern approach will be explained in depth and illustrated in some case studies from the ecosphere (sustainability, hurricanes and avalanches), where nature serves as a teacher for the solution of the sustainability problem. Then, a series of case studies on macropatterns are described showing the problem-solving capacity for anthropo- and technosphere: sustainability in society with an index of sustainability, the eco-social market economy with eco-tech as an instrument, biokinetics, bioreactor mixing and integrated bioprocessing with models, design of cars and houses and even quality of life as an attempt to quantify macropatterns.The innovations are briefly compared in their problem-solving capacity with known approaches such as the microscopic method in science, technology and society (free market economy), including the evaluation of other indices and cleaner production, industrial ecology and zero emission initiative. Finally, a deeper integration of sciences, ethics, arts and nature will be introduced based on the vision with macroscopic pattern analysis, where the different domains of human life are integratable to effect a reconciliation.
    Additional Material: 22 Ill.
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  • 9
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 17-29 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dynamic behaviour of biofilters intended to remove toluene and xylene from air was studied during transient states. Laboratory scale biofilters were filled with a mixture of peat, bark and wood and inoculated with a mixed microbial population. Toluene and xylene were applied both as single pollutants and as mixtures. Attention was focused on the evaluation of the following transients: the response of biofilters to step changes and peaks in pollutant concentrations, the effect of changes between single and multiple pollutant loadings and the response to shutdown periods.The biofilters demonstrated a good dynamic stability during transient states induced by change in inlet pollutant concentrations. Their time periods did not exceed three hours. No interaction between xylene and toluene degradation was observed during changes in loading with single pollutants or their mixture. The performance interruptions lasting less than 24 hours were found to have no significant influence on the removal efficiency of biofilters. When the biofilters were reacclimated after longer starvation periods, a short temporary decrease in efficiency whose minimum and duration were proportional to the length of a preceding shutdown period was observed. The longest starvation period (7 days) resulted in a reacclimation lasting 7 hours only. Adaptations of a microbial population to new operating conditions as well as sorption/desorption processes were suggested as the main factors influencing the dynamic reponse characteristics.
    Additional Material: 10 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 31-38 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: In this paper, the in vivo decolourization of the polymeric dye Poly R-478 by semi-solid-state cultures of Phanerochaete chrysosporium BKM-F-1767 (ATCC 24725) was investigated, employing corncob as a support. In order to stimulate the ligninolytic system of the fungus, the cultures were supplemented with veratryl alcohol (2 mM) or manganese (IV) oxide (1 g/l).Maximum manganese-dependent peroxidase (MnP) and lignin peroxidase (LiP) activities of around 2,000 U/l and 400 U/l were attained by the former, whereas the activities reached by the latter were of about 1,500 U/l and 200 U/l, respectively. Furthermore, laccase activity (around 150 U/l) was only detected in manganese (IV) oxide supplemented cultures.The polymeric dye Poly R-478 (0.02 w/v) was added to three-day-old cultures. A percentage of biological decolourization of about 85% was achieved using cultures supplemented with veratryl alcohol, whereas MnO2 cultures showed a rather lower percentage of around 58% after nine days of dye incubation. Moreover, a correlation between MnP activity and Poly R-478 decolourization could be observed, indicating that this enzyme is mainly responsible for dye degradation.In the present work, the in vivo decolourizing capability of the ligninolytic complex secreted by P. chrysosporium was investigated under the above-mentioned cultivation conditions, employing a model compound, such as the polymeric dye Poly R-478.
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  • 12
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 187-187 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 189-201 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Desulfovibrio vulgaris strain PY1 was isolated from a 3-chlorobenzoic acid (3CBA) degrading anaerobic enrichment culture, using anaerobic Percoll density centrifugation. When grown on pyruvate (20 mM), in the absence of sulphate and under strict anaerobic conditions, this organism converted not only the co-substrates benzoate (BA), 3-amino-BA and 3CBA to the corresponding alcohols but also ten other different halogenated benzoic acids, viz., 4-Cl-, 3-Br-, 4-Br-, 3-I-, 3-F-, 4-F-, 2,4-di-Cl-, 2,5-di-Cl-, 3,4-di-Cl- and 3,5-di-Cl-BA. This was verfied with HPLC and GC/MS spectrometric analyses. The yields of the co-substrate converted after 30 days of growth were between 20% and 88%, depending on the compounds which had been added at initial concentrations of 500 μM. Sulphate, sulphite, thiosulphate and disulphite inhibited the formation of 3-Cl-benzyl alcohol (3CBOH), i.e. a 97 to 99% inhibition, and nitrate and sulphur had no effect (a 7-10% inhibition). In cell-free extracts, the reduction of 3CBA to 3CBOH required strict anaerobic conditions, pyruvate or H2 as electron donors and the addition of methylviologen (MV), FAD, FMN or ferredoxin as electron carriers. The specific activity of the reduction of 3CBA to 3CBOH in crude extract was 5.3 nmol/(mg protein min). The reaction was not inhibited by additions of sulphate or sulphite (5 mM), but was completely inhibited at concentrations of 10 mM 3CBA or 50 mM BA. A carboxylic acid reductase (aldehyde dehydrogenase), which acted on non-activated 3CBA and was responsible for the reduction of 3CBA to 3-Cl-benzaldehyde, was found in the solube fraction (94% of the total activity). These results demonstrate that strain PY1 was able to effectively reduce a wide range of halogenated benzoic acids to the corresponding alcohols.
    Additional Material: 3 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 203-218 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The recent upsurge in information technology has provided the international community with an easy access to professional journals (e.g. Electronic Journal of Biotechnology at http://www.ejb.org; etc.), discussion groups (e.g. bioenergy@cret.org; digestion@crest.org; etc.) and recently to electronic international conferences (e.g. ICIBS; http://www.cid.harvard.edu/cidbiotech, etc.) as well as a series of biotechnological information material (e.g. http://www.psrast.org, etc.) to stay in contact and receive up-to-date information in biotechnology. There is no doubt that this new technology will be more cost effective in future and reach more people in communities around the globe.This review reports on one such an electronic conference aiming at bridging the communication gap between developed and developing countries. This conference dealt with integrated biosystems and has provided an excellent forum for more than 100 active participants from all regions of the world. As has been demonstrated in this review, the conference was able to show the very different approaches towards the use of biotechnology in developed and developing countries, cold and tropical climate regions owing to their different ecological, economical and societal problems. It also demonstrated very clearly that the field of molecular genetics and/or genetic engineering is not a priority issue in developing countries, but rather the need for clean technologies, multiproduct formation through socio-economic integrated biosystems, e.g. incorporating microbial waste management into agro-industries, in human activities and their roles in creating better health conditions, a better environment and sustain development.It is hoped that this review will lead to a greater use of the electronic facilities available to inform and educate both the northern and the southern communities more readily of their needs and requirements to improve understanding and efforts for a sustainable future.
    Additional Material: 4 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 275-288 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The purpose and scope of this article is to introduce capable zeolites into downstream processing of natural compounds, especially flavour compounds like 2,5-dimethyl-4-hydroxy-3(2H)-furan-3-one (Furaneol®Furaeol is a registered trademark of FIRMENICH, Ch). The synthesis and the recovery of Furaneol from L-rhamnose are presented. Therefore adsorption isotherms of the zeolites ZSM5 and DAY with varying modules have been determined and adsorption experiments using model and reaction mixtures of Furaneol synthesis were performed and will be discussed.
    Additional Material: 11 Ill.
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  • 16
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: A fermentation process for manufacturing 1,4-piperazinium-(L,L)-dilactate from renewable raw materials and a method for processing this product into L,L-dilactide are described. Lactic acid fermentation with Lactobacillus paracasei was modified in such a way that pH control occurred by using an aqueous solution of piperazine as a correcting agent instead of sodium hydroxide solution. The production of a stoichiometrically composed piperazinium lactate was possible when the pH was 5.0. From 5.0 kg of glucose and 2.15 kg of piperazine, 6.65 kg of 1,4-piperazinium-(L,L)-dilactate were formed in the fermentation process. Separation from fermentation broth, purification and concentration of the product in aqueous solutions were carried out by means of ultrafiltration, nanofiltration and electrodialysis. Total product retention by the membranes used was about 33%. The crystalline salt was obtained by vacuum evaporation. Processing of the 1,4-piperazinium-(L,L)-dilactate into L,L-dilactide was performed in a special glass reactor. A product yield of 70% was achieved. The purified product was characterized by elementary analysis, as well as solubility behaviour, polarity and spectroscopic data. An overall process consisting of the stages fermentation, purification and concentration of piperazinium dilactate as well as cyclization of the latter to dilactide is described.
    Additional Material: 9 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 161-168 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Five different chemical reagents and γ-rays were tested for the sanitization of immobilized biocatalysts with high penicillin G acylase (PGA) activity. The most effective chemical reagents were N-cetyl-N,N,N-trimethylammonium bromide (CTAB) and 2-isopropyl-5-methylphenol (thymol). The optimum concentration of CTAB for the treatment of the immobilized enzyme was 0.25% [w/v] and 1 h, for immobilized cells 0. [w/v] and 3 h. The optimum concentration of thymol for the immobilized enzyme was found to be 0.1% [w/v] and 1 h, for immobilized cells 0.27% [w/v] and 2 h. The optimum dose of γ-rays for the sanitization of the immobilized enzyme was established as 3.2 kGy, for immobilized cells as 4.5 kGy.
    Additional Material: 5 Tab.
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  • 18
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 19
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 53-64 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: An advanced primary treatment process for a municipal waste water was systematically studied, using a bio-flocculation-adsorption, sedimentation and stabilzation process (BSS). It was shown that the organic removal efficiency was higher than that of the traditional primary treatment processes but lower than that of the traditional secondary treatment processes. Both adsorption and bio-flocculation played an important role in the removal of pollutants. The activated sludge within the bio-flocculation-adsorption tank could be considered a bio-flocculent which improved the quality of the effluent from the primary treatment process. As the effluent of the BSS process did not meet the requirements for a typical secondary effluent, the process may be regarded as an advanced (or enhanced) primary treatment process, suitable for waste water containing a high concentration of suspended solids and colloidal particles.
    Additional Material: 7 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 67-73 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The concentration of airborne fungal spores and bacteria as related to room temperature, humidity and occupancy levels within a library building in Singapore was determined. Measurement of indoor air quality with respect to microorganisms is of particular importance in tropical environments due to the extensive use of air-conditioning systems and the potential implications for human health. This study has revealed a number of interesting relationships between the concentrations of fungal spores and bacteria in relation to both environmental and human factors. The levels of fungal spores measured in the indoor environment were approximately fifty times lower than those measured outside, probably because of the lowered humidity caused by air-conditioning in the indoor environment. The variation in fungal spore concentration in the outdoor environment is likely to be due to the diurnal periodicity of spore release and the response to environmental factors such as light temperature and humidity. The indoor concentration of fungal spores in air was not clearly correlated to concentrations measured in air outside of the library building and remained relatively constant, unaffected by the difference in the numbers of occupants in the library. In contrast, the indoor concentrations of bacteria in air were approximately ten times higher than those measured outdoors, indicating a signficant internal source of bacteria. The elevated levels of indoor bacteria were primarily attributed to the number of library occupants. Increased human shedding of skin cells, ejection of microorganisms and particulates from the respiratory tract, and the transport of bacteria on suspended dust particles from floor surfaces probably accounts for the strong positive correlation between occupancy levels and the concentration of bacteria in internal air.
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  • 21
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 22
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 96-96 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 23
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 87-96 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Preliminary results on the novel use of the bacterium Thiobacillus ferrooxidans (ATCCJ 3598 and ATCC33020) for the micro-machining (or biomachinig) of metals are reported. Biomachning is a controlled microbiological process to selectively form microstrucutures on a metal work-piece by metal removal (or dissolution) using microorganisms. Applying copper and mild steel as work-pieces, it was shown that the mass removed increased proportionately with machining time. In another experiment, the work-pieces were coated with organic photo-resistive materials to mask (i.e. protect) certain regions of the metlas, thereby defining the microstructure to be formed. The unmasked regions were successfully biomachined; the final machined profile was shown to be similar to the coating image on the original metal. Although biomachining proceeded at a slower rate than chemical machining, the undesired leaching of the metal in the region under the masked area (termed undercutting) was not as severely encountered when compared with the latter. This work demonstrates the potential use of microorganisms for the biomachining of metals. As a “green process”, the innovative use of T. ferrooxidans for the micro-machining of metals opens up the possibility of biomachining as an alternative to conventional metal processing.
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  • 24
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: During the microbial treatment of a sandy model soil artificially contaminated with polycyclic aromatic hydrocarbons (PAHs), a large residual pollution was found. The remainig PAHs were sorbed into the micropores of the soil and were therefore not bioavailable. Using a lab-scale precolator, the microbially pretreated soil was subjected to aftertreatment with surfactants with the aim of further degradation of its pollution. Two commercial nonionic surfatants of the polyethoxylate type, Präwozell F1214/5 N and Sapogenat T-300, were used. The surfactants differ both in their physicochemical properties (CMC value, PAH solubilization capacity, adsorption onto soil) and in their microbial degradability. During aftertreatment under permanently aerobic conditions, only a weak PAH accumulation in the liquid phase was observed, which was due to a low solubilization rate as well as to simultaneous microbial degradation of the dissolved PAHs. Temporary anaerobiosis successfully suppressed the microbial degradation of both the surfactant and the solubilized PAHs, resulting in a more intensive PAH accumulation. But the PAH content of the soil - the essential criterion for evaluating the efficiency of surfactant application - was not decreased to a larger extent with surfactants than without them. To find out why the surfactants failed to act, the surfactant and hydrocarbon distribution among the liquid and solid phases was studied in mixtures of phenantherne-spiked solis and Präwozell-containig liquids; at heavy phenanthrene loading, the aqueous phase was saturated with PAH; at weak loading, it was unsaturated. Model-aided data analysis showed that the soil may contain PAH in two fractions: strongly sorbed into soil pores and, in the case of heavy loading, also weakly attached to the soil surface. The latter is easily extractable, resulting in a PAH-saturated liquid, while strongly adsorbed PAH is only partially dissolved due to competition between the micelles and the soil pores for the PAH. The microbially pretreated soil contains only strongly bound PAHs, which are as difficult to extract by surfactants as they are poorly accessible for microbes.
    Additional Material: 8 Ill.
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  • 25
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Autochthonous bacteriocenoses in semiarid soils in Patagonia were found to be capable of rapidly adapting to high contamination with crude oil. This adaptation at community level is due to the selective enrichment of hydrocarbon-utilizing bacteria always present in these soils. Immediately after a heavy contamination with crude oil, the authochthonous bacteriocenosis contained about 28% hydrocarbon-utilizing bacteria which could be classified into eight ecotypes with characteristic metabolic profiles. Mainly n-alkanes were used as growth substrates of representative strains. After seven months' exposure to crude oil, the bacteriocenosis consisted almost entirely of hydrocarbon-utilizing bacteria. At least fourteen ecotypes were distinguishable, and the majority of representative strains were able to metabolize a broad spectrum of aliphatic and aromatic hydrocarbons. Corresponding to the significant alteration of the physiological diversity, drastic changes to the taxonomic diversity were also found. Whereas at the beginning of the study the autochthonous bacteriocenoses were dominated by GRAM-positive genera of the Actinomycetales (Dietzia, Gordona, Nocardia, Rhodococcus, Streptomyces) with high ecological potency, after just two months' exposure to crude oil, GRAM- negative bacteria (especially Pseudomonas stutzeri) became predominant within the hydrocarbon-utilizing bacteriocenoses accompanied by some GRAM-positive genera of the Actinomycetales with a significantly lower abundance. These findings underline the importance of Pseudomonas and some genera of Actinomycetales for processes of natural attenuation and the technically supported in situ bioremediation of soil polluted by crude oil in Patagonia.
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  • 26
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 149-159 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Some parameters of the production of an alkaline protease by Rhizopus oryzae in the solid state fermentation of wheat bran were optimized. Using the optimum parameters of an inoculum age of 7 days, an incubation time of 9 days, an amount of CZAPEK-DOX (liquid medium) of 6 ml/g bran and an incubation temperature of 33°C, an activity of 50 U/g bran was achieved. The initial pH of the CZAPEK-DOX medium had little effect. Re-incubation of mouldy bran with only fresh CZAPEK-DOX yielded 3 times total activity compared to single-cycle fermentation. As for the effect of the amount CZAPEK-DOX medium, the water constituent contributed more to activity increase than did the salt component. The ARRHENIUS activation energies were 23 and 7.9 kcal/mole below and above the optimum of 33°C, respectively. In all the studies, along with protease production, variation of protein content and specific activity were also observed. Attempts were made to explain the effects and also gauge their implications for large-scale production.
    Additional Material: 4 Ill.
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  • 27
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 28
    Electronic Resource
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 29
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Because of the growing utilization of renewable raw materials, the technical use of lignocellulosic fibres from wood and other annual plant materials is becoming increasingly important. The conventional production process of fibreboards is characterized by high-energy consumption and use of ecologically insecure synthetic lesins. Approximately 40 to 45% of the total energy expenditure are used for the thermo-mechanical pulping. Because of high plastication temperatures, an inactive lignin crust on the fibre surface is formed. For that reason, for glueing of the fibres, urea formaldehyde and melamin resins are usually used. The costs for the resin amount to approximately 50% of the entire material costs. In addition, environmental problems are caused. The aim of our investigation is the reduction of energy and resin consumption by enzymatic modification of wood chips and the enzymatic activation of the inherent bonding strength of the material. The first industrial use of fungi for the modification of wood was in the production of “Myco wood”. Pleurothus ostreatus and Trametes versicolor were applied for nonsterile delignification of beech wood. The present investigation of the authors deals with the mycological pre-treatment of wood chips in order to reduce the energy consumption during wood pulping. The screening results favour the brown rotter Gleophyllum trabeum for pinewood (Pinus silvestris) and the white rotter Trametes hirsuta for beech (Fagus silvatica). Both species show resistance against mould fungi. The use of submerged inoculum of these fungi has the advantage over wheat inoculum that the lag phase is less than 12 hours and that the addition of nutrients or fungicides is not necessary. Short-time wood chip incubation results in a 40% decrease of energy consumption during thermo-mechanical pulping and in improved fibreboard properties. Lignin reduction could not be determined by gravimetrical and x-ray microanalysis.Comparative investigations of fibre incubation using laccase, a submerged culture of Trametes versicolor and rape straw fibres show a high increase in bending and tensile strength and an improvement in the hygroscopic properties of glue-free fibre boards for the last two incubation kinds. Similar effects have been obtained incubating pine wood fibres for the production of fibre sheets with enzyme medium of Trichoderma reseei.
    Additional Material: 4 Ill.
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  • 30
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 335-350 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: During the 20th century, important relationships developed between the oil industry and both microbiological and biotechnological research. Basic microbiological research has played an important role in both the exploration and production sectors of the oil industry, but as the maturity of the industry has progressed, such contributions have been relegated with respect to their importance. With respect to refining and petrochemicals manufacture, process routes have been extensively researched, but only rarely have the biotechnological solutions developed satisfied the economic criteria that resulted in major investment. In fact, situations exist where investment has occurred, but project life was unrealistically short, suggesting a need for extreme caution when evaluating biotechnological processes for the oil industry. However, as far as engineered processes for both biotreatment and bioremediation are concerned, the fundamental research that has underpinned other areas of hydrocarbon microbiology will finally prove to be of both technical and economic value, in ensuring that the essential needs of treatment, rather than disposal, and restoration, rather than environmental destruction, can be satisfied by the oil and other industries involved in both geochemical manipulation and natural resource exploitation.
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  • 31
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The influence of different growth-limiting factors - namely the sources of carbon, nitrogen and phosphorus and the dilution (growth) rate - on the ice-nucleation activity of Pseudomonas syringe CCM 4073 was studied. A higher ice-nucleation activity was observed at a lower dilution (growth) rate (D = 0.1 h-1) than at a higher dilution (growth) rate (D = 0.3 h-1). Remarkable differences in ice-nucleation activity were found in its dependence on the growth-limiting factor. The highest ice-nucleation activity was observed under carbon limitation (T90 = -2.7°C), a medium activity under nitrogen limitation (T90 = -5°C) and lowest activity under phosphorus limitation (T90 = -12.3°C). After the addition of excess nitrogen or phosphorus to steady-state cultures, the ice-nucleation activity was restored.
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  • 32
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 33
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 65-65 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 34
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 35
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 41-52 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Studies were carried out to evaluate the feasibility of using coffee industry residues, viz. coffee husk, coffee leaves and spent coffee ground as substrates in solid state fermentation (SSF) to cultivate edible mushrooms Pleurotus. Eight strains of Pleurotus ostreatus and two strains of Pleurotus sajor-caju were screened on a medium prepared from aqueous extract of coffee husk and agar. Based on best mycelial growth (9.68 mm/day) and biomass production (43.4 mg/plate in 9 days at 24°C), the strain P. ostreatus LPB 09 was selected for detailed studies. SSF was carried out using these substrates under different moisture conditions (45-75%) and spawn rates (2.5-25%). In general, although a 25% spawn rate appeared superior, the 10% spawn rate was recommended for all the three substrates in view of the process economics, as there was not any significant difference in the increase with 10 to 15%. The ideal moisture content for mycelial growth was 60-65% for coffee husk and spent coffee ground, and 60-70% for coffee leaves. The biological efficiency (BE), which is defined as the ratio of the weight of fresh fruiting bodies to the weight of dry substrate, multiplied by 100, and which indicates the fructification ability of the fungus for utilizing the substrate, was best with coffee husk. With coffee husk as the substrate, the first fructification occurred after 20 days of inoculation, and the biological efficiency reached about 97% after 60 days. When coffee leaves were used as the substrate, no fructification was observed even upon prolonged cultivation. With spent ground as the substrate, the first fructification occurred 23 days after inoculation and the biological efficiency reached about 90% in 50 days. There was a significant decrease in the caffeine and tannin contents (61 and 79%, respectively) of coffee husk after 60 days. It was remarkable to observe that caffeine was adsorbed onto the fruiting body (0.157%), indicating that it was not completely degraded by the fungal culture. However, no tannins were found in the fruiting body, indicating that the fungal strain was capable of degrading them. The results showed the feasibility of using coffee husk and spent coffee ground as substrates without any pre-treatment for the cultivation of edible fungi in SSF, and provided one of the first steps towards an economical utilization of these otherwise unutilized or poorly utilized residues.
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  • 36
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 75-81 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Serratia marcescens biovar A2/A6 is able to produce a red pigment as a secondary metabolite which has antimicrobial activity. This paper describes its growth and biopigment formation in batch cultures, in media containing different concentrations of lactic acid and beef extract as carbon and nitrogen sources, respectively. An unstructured model has also been developed to describe its growth, lactic acid uptake and biopigment formation. The comparison of simulated and experimental data shows that the proposed model predicts reasonably well the system behaviour over a range of conditions.
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  • 37
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 97-98 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 38
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 39
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 334-334 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 40
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The impact of hydrocarbon remediation on several enzyme activities (catalase, dehydrogenase, lipase, protease, urease, alkaline phosphomonoesterase, fluorescein diacetate hydrolysis) and microbial properties (biomass-C, respiration, N-mineralization, qCO2, microbial counts) was evaluated in a laboratory study over a period of 10 weeks. A pristine soil was contaminated with diesel oil (10 mg/g soil) or with a mixture of phenanthrene and naphthalene (total amount 1 mg/g soil) and supplemented with inorganic nutrients to give a C:N ratio of 20:1. The corresponding controls consisted of uncontaminated nutrient-supplemented soil. Oil contamination caused a significant initial increase of all biological parameters measured. In the presence of PAHs, biomass-C, respiration, protease activity and heterotrophic counts were significantly enhanced, while urease activity was depressed. N-mineralization was initially, however, reversibly inhibited in the presence of oil and PAHs.The measured parameters behaved differently over time: Biomass-C, respiration and alkaline phosphomonoesterase activity reached a maximum activity after about 2-5 weeks, corresponding to the period during which the majority of hydrocarbons disappeared, and declined thereafter to the background level. Activities of catalase and dehydrogenase also followed this pattern, however, were characterized by fluctuations. Activities of lipase, protease, urease and fluorescein diacetate hydrolysis increased and remained almost constant throughout the incubation period.
    Additional Material: 10 Ill.
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  • 41
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 351-368 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The action resonance theory (ART), a hypothesis based on a logical extension of EINSTEIN's theory of Brownian movement, suggests that the genotype × environment interaction can be modelled as forceful encounters of the gene-products of an organism with its environment. This model has implications for molecular and cell biology, morphogenesis, evolutionary development via mutation, the mechanism of natural selection and overall function of ecosystems, extending SCHRÖDINGER's programme for molecular biology. Action, a thermodynamic property with the same physical dimensions as angular momentum and PLANCK's quantum of action, is proposed to be reversibly generated as a result of the molecular exchange of quanta, which become resonant at equilibrium, corresponding to an optimum degree of entropy and action for living systems. Because the theory can potentially predict solutions to unsolved problems such as the folding of proteins it has strong implications for successful genetic modification of organisms and for biotechnology in general; the design of a programme of research to test this theory is proposed. A key element in this research programme, improving productivity and sustainability, would be the need to select genetically modified strains in the ecological environment or niche in which they are required to function.
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  • 42
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 43
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Continuous counter-current chromatographic processes have been successfully used in the petrochemical and sugar industry over the last 30 years. Only recently has simulated moving bed (SMB)-technology attracted widespread interest in the pharmaceutical industry, mainly as a very efficient system for chromatographic enantioseparation. The application of this technique to the downstream processing of biotechnological products requires some specific changes to meet the special demands of bioproduct isolation. Production processes are set up on an multi-ton scale, for example, for the purification of fructose with both yield and purity higher than 90%. Examples for other mono- and oligosaccharides are reported. In the purification of fatty acids or fat soluble vitamins, SMB technology under supercritical fluid conditions gives additional benefits and increases the productivity by a factor of four when a pressure gradient is applied. Another field of operation is the isolation of drug compounds from natural sources where different batch- and SMB-chromatographic steps could be successfully combined. First examples are reported for cyclosporine A and paclitaxel isolation. Finally, step-gradient elution modes can be used continuously, as demonstrated for the isolation of monoclonal antibodies.
    Additional Material: 6 Ill.
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  • 44
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 57-65 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Positive und negative Photostrukturen wurden in einem Polyimid (PI) aus 4,4′-Biphthalsäureanhydrid (BPA) und 4,4′-Diamino-3,3′-dimethyldiphenylmethan (DADMDPM), PI(BPA/DADMDPM) erzeugt, nachdem dieses mit Michlers Keton (MK) bzw. Benzophenon (BP) dotiert und einer ultravioletten Strahlung von 400 ± 50 nm ausgesetzt und naß entwickelt wurde. Das Prinzip der positiven Abbildung basiert auf dem Photokupplungseffekt von MK mit PI, der die Löslichkeit des Polyimids erhöht und so die Entwicklung eines Positivmusters ermöglicht. Die Erzeugung negativer Muster wird durch intermakromolekulare Wasserstoffbrücken zwischen der Carbonylgruppe des Imid-Rings und der Hydroxygruppe, die bei der photoinduzierten Kupplung von Benzophenon mit dem Polyimid gebildet wird, bewirkt. Die lithographische Auswertung zeigt, daß der mit MK dotierte, positive Polyimidfilm nicht in der Lage ist, brauchbare Muster zu erzeugen, da die UV-Wellenlängen von MK absorbiert werden, wodurch die Photokupplung in den tieferen Schichten des Films verhindert wird. Andererseits können in dem 0,6 μm dicken, mit Benzophenon dotierten Polyimidfilm sogar 2 μm schmale Linien aufgelöst werden.
    Notes: Positive and negative photostructures are formed after the polyimide (PI) of 4,4′-biphthalic anhydride (BPA) and 4,4′-diamino-3,3′-dimethyldiphenylmethane (DADMDPM), PI(BPA/DADMDPM) is doped with Michler′s ketone (MK) and benzophenone (BP), respectively, and is subjected to UV light (400 ± 50 nm) irradiation and solvent development. The principle of positive feature formation is based on the photocoupling of MK with PI, which increases PI solubility and thus enables a positive pattern to be developed. The phenomenon of negative photopatterning results from intermacromolecular H-bonding between the carbonyl group of the imide ring and the hydroxy group which is formed in the photoinduced coupling reaction between BP and PI. Lithographic evaluation shows that the MK-doped positive-acting PI film cannot form useful patterns because UV wavelengths are strongly absorbed by MK, which limits the depth of photocoupling in the film. On the other hand, 2-μm-wide lines can be resolved in the BP-doped negative-acting 0.6-μm-thick PI film.
    Additional Material: 5 Ill.
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  • 45
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 101-113 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polyhydrazid/Polyamid-Blends (PEHZ12/PA6) wurden durch Niedrigtemperatur-Polykondensation von 4,4′-Dichlorformyl-α,ω-diphenoxydodecan und Terephthaloyldihydrazid (TDH) zu Poly(etheraroylhydrazid) in Gegenwart von Polyamid 6 synthetisiert. Die DSC-Analysen lassen vermuten, daß die zwei Polymerkomponenten nicht wechselwirken. Bei der Extraktion des PA6-Anteils der Blends mit Ameisensäure zeigt die Charakterisierung des PEHZ12-Extraktionsrückstands aber, daß zumindest bei bestimmten Zusammensetzungen Wechselwirkungen zwischen den Komponenten auftreten. Modellreaktionen erlauben die Annahme, daß die PEHZ12-Polymerisation zwischen den Amino-Endgruppen des PA6 und den wachsenden PEHZ12-Polymerketten abläuft.
    Notes: Poly(etheraroylhydrazide) is synthesized in the presence of PA6 by means of low-temperature condensation polymerization of 4,4′-dichloroformyl-α,ω-diphenoxydodecane with terephthaloyl dihydrazide (TDH) in order to prepare polyhydrazide/poly-amide 6 (PEHZ12/PA6) blends. The thermal analysis of the blends by DSC seems to indicate that the two polymers are not interacting. Nevertheless, when the blends are subjected to an extraction process with formic acid in order to remove the PA6, the characterization of the residual PEHZ12 reveales that some interactions do occur between the constituent polymers, at least for selected compositions. Model experiments permit to hypothesize that the polymerization of PEHZ12 proceeds with a chemical interaction between amino end groups of PA6 and growing PEHZ12 chains.
    Additional Material: 7 Ill.
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  • 46
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 179-196 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The crystallization behavior of PBT as well as PC is changed in the controlled-processed blend due to intermolecular interactions between the different macromolecules in molten state.If the kinetics of the crystallization process prevents a crystallization-induced separation, the partial miscibility of the amorphous phases, measured by the glass transition temperatures, will lead to a decrease of the crystallinity of PBT. The crystallinity, normalized to the concentration of PBT in the blend, is independent from the concentration of PC at low coolling rates.At high cooling rates, PBT is crystallizing stepwise in the blend PBT/PC 40/60 wt.-%. The crystallization temperature in the anisothermic crystallization process is increased at low contents of PC due to a changed nucleation mechanism. The half-time of crystallization is increasing in blends with an increasing PC-content in isothermic crystallization experiments.The normally amorphous PC crystallizes considerably fast in presence of PBT in PC-rich blends. The crystallization or change in the state of order of PC was measured in situ by X-ray diffraction. Calorimetric experiments confirm this result and allow a quantitative estimation of the PC-crystallinity, which amounts to some 20% in the blend PBT/PC 5/95 wt.-%.
    Notes: Das Kristallisationsverhalten sowohl von PBT als auch von PC ist im definiert verarbeiteten Blend infolge intermolekularer Wechselwirkungen zwischen den unterschiedlichen Molekülen in der Schmelze verändert.Die über die Glasübergangstemperaturen gemessene teilweise Mischbarkeit der amorphen Phasen führt bei PBT zu einer Erniedrigung des Kristallinitätsgrades, wenn die kinetischen Bedingungen des Kristallisationsprozesses keine kristallisationsbedingte Entmischung zulassen. Der auf den PBT-Anteil normierte Kristallinitätsgrad ist bei kleinen Abkühlgeschwindigkeiten vom PC-Anteil unabhängüg.In der Mischung PBT/PC 40/60 Gew.-% kommt es bei hohen Kühlraten zu einer fraktionierten Kristallisation. Die Kristallisationstemperatur bei anisothermer Kristallisation ist bei geringen PC-Gehalten durch Änderung des Keimbildungsmechanismus erhöht. Bei isothermer Kristallisation steigt mit zunehmendem PC-Anteil die Kristallisationshalbwertszeit des PBT an.Das normalerweise amorphe PC kann in Gegenwart von PBT in den PC-reichen Mischungen besonders schnell kristallisieren, wobei der Kristallisations- bzw. Ordnungsprozeß des PC in situ mittels der Röntgenbeugung gemessen wurde. Kalorimetrische Untersuchungen bestätigen dieses Ergebnis und erlauben eine quantitative Abschätzung des PC-Kristallinitätsgrades zu ca. 20% im Blend PBT/PC 5/95 Gew.-%.
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  • 47
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 197-210 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Elementaranalytische sowie NMR-, IR- und UV-spektroskopische Untersuchungen zeigen, daß die Photolyse von Halogenphenolnovolaken zur Substitution der Halogenatome durch Wasserstoff, der Bildung chinoider Gruppen und intermolekularen Vernetzung führt. Die Geschwindigkeit der Halogeneliminierung hängt von der Art des Halogens ab. Sie steigt in der Reihenfolge F 〈 Cl 〈 Br 〈 I. Die Chloreliminierung aus der 4-Position ist gegenüber der aus der 2- und 3-Position begünstigt. Außerdem verläuft die Abspaltung para-ständiger Chloratome aus Dimeren schneller als aus Trioder Tetrameren. ESR-Messungen bei 77 K sowie die Laserblitzphotolyse bei 296 K deuten auf die intermediäre Bildung von Phenoxyl- und Arylradikalen. Lithographische Tests belegen die hohe UV-Empfindlichkeit von Resisten auf der Basis von Halogenphenolnovolaken. Im Vergleich zu nichthalogenhaltigen Novolakresisten wird eine 6 - 10fache (System: 4-Chlorphenolnovolak/4,4′-Bisazidobiphenyl (5%)) bzw. eine ca. 25fache (System: 4-Chlorphenol-/m-Cresolnovolak/Hexamethoxymethylmelamin (5%)) Steigerung der Empfindlichkeit erreicht. Zur Interpretation wird ein Mechanismus postuliert, demzufolge die durch Halogenabspaltung hervorgerufene Sekundärradikalbildung zu einer zusätzlichen Vernetzung beiträgt. In den melaminhaltigen Resisten katalysiert der gebildete Halogenwasserstoff (Hal· + RH → H-Hal + R·) außerdem die Reaktion der Melaminverbindung mit der Novolakmatrix.
    Notes: The photolysis of halogenophenol novolacs is determined by the substitution of halogens by hydrogen and the formation of quinoid groups and intermolecular crosslinks. This is concluded from elemental analysis, NMR, IR and optical absorption measurements. The rate of halogen release depends on the chemical nature of the halogen. It increases in the order F 〈 Cl 〈 Br 〈 I. Chlorine elimination from 4-position is favored over that from 2- and 3-position. Moreover, dimers release chlorine from 4-position much more readily than trimers and tetramers. ESR measurements at 77 K and flash photolysis studies at 296 K yielded evidence for the intermediate existence of phenoxyl and aryl radicals. Lithographic tests demonstrated the high UV-sensitivity of resist formulations based on halogen-containing novolacs. The increase in sensitivity relative to that of formulations based on nonhalogenated novolacs is 6 to 10fold system: 4-chlorophenol novolac/4,4′-bisazidobiphenyl (5%) and ca. 25fold system: 4-chlorophenol/m-cresol novolac/hexamethoxymethylmelamine (5%). A postulated reactions mechanism concerning the sensitivity increase takes into account that halogen elimination results in the formation of additional radicals that accelerate the rate of crosslinking. Moreover, hydrogen halide generated by hydrogen abstraction of halogen radicals (Hal· + RH → H-Hal + R·) provides for the acid required to catalyze the reaction of the melamine compound with the novolac matrix.
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  • 48
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 11-24 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Calciumcarbonate unterschiedlicher Teilchenform (sphäarisch, kubisch und nadelfäormig) wurden mit Polypropylen (PP) in einer Zwei-Walzen-Mäuhle gemischt und anschließend zu Platten gepreßt. Der Einflußder Teilchenform auf das Kristallisationsverhalten der PP/CaCO3-Composite, d.h. Kristallisationspeaktemperatur (Tmax), Kristallisationsverlauf usw., wurde mittels Differentialkalorimetrie untersucht. Der Wert von Tmax häangt von der Größe der Gesamtoberfläache der CaCO3-Teilchen ab; Tmax ist bei nadelfäormigen Teilchen gräoßer als bei kubischen oder sphäarischen und hauangt in allen Fäallen der nicht-isothermen Kristallisation von der Abkäuhlgeschwindigkeit und der vorher erreichten maximalen Temperatur ab.
    Notes: Calcium carbonate of various particle shape (spheric, cubic, needle-shaped type) and polypropylene (PP) were mixed on a two roll mill and the mixture was pressed into plates. The effect of particle shape on the crystallization behavior of PP/CaCO3 composites, such as crystallization peak temperature (TMAX), crystallized pattern, etc., was investigated with differential scanning calorimetry measurements. The value of TMAX is explained by the total surface area of added CaCO3 particles; TMAX of needle-shaped series is larger than that of cubic or spheric ones. TMAX of various shaped CaCO3-filled PP totally depends on the cooling rate and maximum temperature in the non-isothermal crystallization, respectively.
    Additional Material: 9 Ill.
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  • 49
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 107-119 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Polyaddition von Polyethylenglykol (PEG) Oligoglycidylethern (Mn (PEG): 396,587, 1437 und 3554) mit asymmetrischen Diaminen, wie N,N-Dimethylund N,N-Diethyl-1,3-diaminopropan, wurden wasserläosliche kationische Polymere erhalten. Die Eigenschaften der kationischen Polymeren sind vom urspräunglichen PEG-Molekulargewicht und der Diaminreaktivitäat abhäangig. PEG mit Mn = 396 zeigt das beste Verhalten. In verdäunnten wäassrigen Läosungen und in wäassrigen 2M NaCl-Läosungen der Polymeren wurde das Polyelektrolytverhalten veranschaulicht. Die Gegenwart der PEG Kette bestimmt das Polyelektrolytverhalten in den 2M NaCl Läosungen.
    Notes: Water-soluble cationic polymers were obtained by polyaddition of poly(ethylene glycol) (PEG) diglycidylethers (M̄n of PEG were 396, 587, 1437 and 3554, resp.) with asymmetrical diamines such as N,N-dimethyl-1,3-diaminopropane and N,N-diethyl-1,3-diaminopropane. The cationic polymer properties depend on the PEG initial molecular weight and on the diamine reactivity too. PEG with M̄n = 396 had the best behaviour in these reactions. The polyelectrolyte feature of cationic polymers was emphasized both in dilute aqueous solutions and in 2M aqueous NaCl solutions. The polyelectrolyte behaviour in 2M aqueous NaCl solution is determined by the PEG chain presence.
    Additional Material: 4 Ill.
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  • 50
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 139-145 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Reaktion von o-Kresol mit Formaldehyd wurde unter Verwendung verschiedener tertiäarer Amine als Katalysatoren untersucht. Der Einfluß der Reaktionsparameter Basizitäat, Temperatur, Reaktionszeit und Formaldehydkonzentration wird diskutiert. Für die bevorzugte Bildung von 2,4-Bis(hydroxymethyl)-6-methylphenol wurden optimierte Synthesebedingungen erarbeitet. Die Bildung von Zwei-bzw. Mehrkernprodukten konnte nicht ausgeschlossen werden.
    Notes: The reaction between o-cresol and formaldehyde was investigated using various tertiary amines as catalysts. The influence of the reaction parameters basicity, temperature, reaction time and concentration of formaldehyde was discussed. To yield preferentially 2,4-bis(hydroxymethyl)-6-methylphenol the conditions of synthesis were optimized. The formation of bi- and polynuclear products cannot be avoided.
    Additional Material: 4 Ill.
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  • 51
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 189-200 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Scherviskositäat fläussigkristalliner Ethylcellulose, die mit Cellulosepulver unterschiedlicher Partikelgräoße gefäullt war, wurde bei konstantem Schergefäalle mit einem Kegel-Platte-Viskosimeter bestimmt. Der Einfluß des Cellulosepulvergehalts, des Läange/Breite-Verhäaltnisses der Pulverteilchen und der Temperatur auf das viskose Verhalten und die Phasenäubergäange wird diskutiert. Der Zusatz von Cellulosepulver erhäoht die Viskositäat und verringert die Aktivierungsenergie des Fließens(Ea), ohne jedoch die Phasenäubergäange zu beeinflussen. Die Viskositäat und die Aktivierungsenergie sind abhäangig vom Läange/Breite-Verhäaltnis der Pulverteilchen; mit zunehmender Gräoße dieses Verhäaltnisses wird die Viskositäatszunahme beschleunigt und die Aktivierungsenergie des Fließens erhäoht, wäahrend die Aktivierungsenergie mit steigendem Pulvergehalt abnimmt. Die Phasenumwandlungen sind unabhäangig von der Partikelform. Der Einfluß des Pulvergehalts auf Viskositäat und Aktivierungsenergie ist abhäangig von der Art der fläussigen Phase; in der anisotropen Phase ist der Einfluß geringer als in der isotropen Phase. Dies scheint von der Ausrichtung der Pulverteilchen und der stäabchenfäormigen Molekäule herzuräuhren.
    Notes: Steady-state shear viscosity for the liquid crystalline ethyl cellulose solution filled with cellulose powders was determined using a cone-plate-type viscometer and the effects of cellulose powder content, powder aspect ratio and temperature on the viscometric behavior and phase transformation were discussed. The addition of powder increased the viscosity and decreased the activation energy (Ea) for flow, but did not affect the phase transformation. The viscosity and Ea depended on the aspect ratio; with greater aspect ratio, the viscosity enhancement was accelerated and Ea as well as the decrease in Ea with powder content increased. The phase transformation did not depend on the aspect ratio, the dependences of viscosity and of Ea on powder content depended on the solution phase; the dependences for the anisotropic phase were smaller than those for the isotropic one. The findings appeared to originate from the alignments of powders and rod-like molecules.
    Additional Material: 4 Ill.
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  • 52
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The UV-degradation of an unstabilized and two HALS stabilized polyethylene (PE) films is described. The degradations are characterized by measuring the oxygen uptake, the formation of CO and CO2, the FT-IR spectra, the mechanical properties, the stabilizer concentration and the oxygen content of the film.The oxygen uptake of the unstabilized PE film led to the expected changes in the IR spectra and embrittlement of the film, while the oxygen uptake by the HALS stabilized films caused only minor changes. The differences between the results for the unstabilized and the HALS stabilized polymers are explained assuming that the initiation of the photodegradation of PE is due to charge transfer complexes.
    Additional Material: 6 Ill.
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  • 53
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Principal chemical pathways characteristic of active participation of radical scavenging polymer stabilizers (phenols, aromatic, hydroaromatic and hindered aliphatic amines) are outlined. Pathways resulting in a partial depletion or distortion of activity of stabilizers, in formation of polymer discolouring products, or in interactions in bifunctional stabilizers are involved.
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  • 54
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Irradiations (λ≥300 nm) of poly(butyleneterphtalate) films were carried out in both vacum and air. Photoproducts were investigated by FTIR spectroscopy, chemical derivatization reactions and physical treatments. The repartition of photoproducts in the polymer was shown to be heterogeneous. A scheme accounting for the main routes of PBT photolysis was found on the basis of photoproducts identification. Most of oxidation products were analogous to vacum photolysis species; the mechanism of photooxidation proposed implied both pure photolytical processes and a photo-induced oxidation route.
    Additional Material: 8 Ill.
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  • 55
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of polymer density, processing conditions (quenching of annealing), degree of crystallinity, size of crystallite and mobility of polymer chains on the photo-and radiation-induced degradation and the polymer stability have been studied by UV, FTIR spectroscopic, viscosity and mechanical property measurements. Four kinds of annealed or quenched polyethylene (PE) films varying densities were used to the studies. Polystyrene (PSt) films were used to investigate the effect of chain mobility on polymer degradation. The following results were obtained. 1.In linear low density (LLD) PE, greater amounts of crosslinking (irradiated in vacuum) and chain scission (irradiated in air) were noticed than in mediun density (MD) PE and high density (HD) PE samples.2.Polyene formation is favored in the case of the irradiation in vacuum for LLDPE.3.Polymer stability evaluated by mechanical property such as elongation at break (%) is superior in LLDPE to MDPE and HDPE for annealed and quenched samples.4.Segmental motion of polymer chain also affects the polymer stability
    Additional Material: 19 Ill.
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  • 56
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 217 (1994), S. 43-49 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The study is on two component blends of high density polyethylenes, having normal and ultra-high molecular weight. The polyethylenes were homogenized by two routes: in powder state or by rolling in melt, then pressed at temperatures in the range from 140°C to 220°C. Comparative studies showed that the way of homogenizing of the components does practically not affect the main mechanical properties of the blends when pressed at temperatures ≥ 160°C. Of special interest are the characteristics of those systems where ultra-high molecular weight polyethylene is the matrix component.
    Notes: Untersucht wurden binäre Mischungen von Polyethylenen hoher Dichte rnit normaler und ultrahochmolekularer Molmasse, die auf zweierlei Weise - in Pulverform oder durch Walzen im Schmelzezustand - homogenisiert und bei Temperaturen zwischen 140 und 220°C gepreßt waren.Es wurde festgestellt, daß die Art der Homogenisierung der Komponenten praktisch keinen Einfluß auf die Eigenschaften bei Preßtemperaturen ≥ 160°C hat. Von besonderem Interesse sind die Eigenschaften der Systeme, in welchen das ultrahochmolekulare Polyethylen die Rolle der Matrixkomponente spielt.
    Additional Material: 4 Ill.
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  • 57
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 218 (1994), S. 81-109 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Verhalten eines neuartigen photoinitiierenden Systems, das die Polymerisation von pigmenthaltigen Schichten großer Dicke in einem Reaktionsschritt gestattet, wird dargestellt. Die verschiedenen Wechselwirkungen, die in einem pigmenthaltigen System auftreten, werden qualitativ beschrieben, und der Anteil der von einem Photoinitiator absorbierten Lichtintensität wird berechnet. Neben dem Absorptions- und Reflexionsverhalten von verschiedenen Pigmentklassen werden die optischen Eigenschaften verschiedener Strahlungsquellen untersucht, um die Strahlungsbereiche zu finden, die am besten mit den optischen Parametern der Pigmente korrespondieren. Weiterhin wird die Beschleunigung von Polymerisationen durch die photokatalytische Wirkung einiger Pigmente behandelt.
    Notes: Ce travail sur le rôe des pigments définit le comportement d'un nouveau systeme photosensible qui permet de polymériser des milieux épais et pigmentés selon un procédé en une seule étape. Les différentes interactions présentes en milieu pigmenté sont décrites de façon qualitative, et la part de l'intensité lumineuse absorbée par un photo-amorceur dans un systéme pigmenté est evaluée. Les propriétés optiques telles que l'absorption et la réflectance des différentes familles chimiques de pigments sont déterminées, et, en paralléle, les propriétés optiques des différentes sources d'irradiation sont étudiées de manière à répondre au mieux aux fenêtres de transmission des pigments. L'effet photocatalytique de certains pigments est mentionné, ceci afin d'amkliorer la réaction de polymérisation.
    Additional Material: 18 Ill.
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  • 58
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 218 (1994), S. 153-162 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Herstellung von cis-1,4-Polybutadien erfolgte mittels Polymerisation von 1,3-Butadien mit einem Katalysatorsystem, das in einer zweistufigen Reaktion gebildet wird: (1) BF3 · O(C2H5)2 und Al(C2H5)3, (2) Ni(OOC8H15)2 und Al(C2H5)3, genannt in-situ-Katalysatorsystem.Die Molmassenverteilungen (MMD) der erhaltenen Polymeren sind mit der Größenausschlußchromatographie (SEC) untersucht worden. Sie lassen sich mit Summen aus Schulz-Flory-Funktionen (SFF) beschreiben. Veränderte Katalysatorformierungs- und Polymerisationsbedingungen beeinflussen die Parameter der SFF. Veränderte Peakflächen und Molmassenmittelwerte der Einzelpeaks zeigen, daß die Polymerisation über mehrere Arten aktiver Zentren verläuft.
    Notes: Cis-1,4-polybutadiene was produced by polymerization of 1,3-butadiene using a catalyst system formed by a two-step formation, Namely (1) BF3 . O(C2H5)2 and Al(C2H5)3, (2) Ni(OOC8H15)2 and Al(C2H5)3 named in-situ-catalyst.The molar mass distributions (MMD) of the polybutadienes are investigated by means of size exclusion chromatography (SEC). The MMD's were fitted by a sum of Schulz-Flory-Functions (SFF). Changed catalyst formation and polymerization conditions influenced the parameters of the SFF. Changed areas and changed molar mass averages indicate a polymerization with more than one peak maximum and kind of active species and lead to a better understanding of the polymerization.
    Additional Material: 9 Ill.
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  • 59
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 1-10 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Umsetzung von Chromacrylat mit Bisphenol A und einem Überschuß Epichlorhydrin wurden neuartige Epoxid-Harze hergestellt. Epoxy-Äquivalentgewicht, Gehalt an Hydroxygruppen und hydrolysierbarem Chlor sowie die Viskosität wurden bestimmt, und die Harze wurden mittels IR- und 1H-NMR-Spektroskopie charakterisiert. Die thermischen Eigenschaften der bei 30°C für 24 h mit Ciba Geigy HY 850 (aliphatisches Amin) gehärteten Harze wurden gemessen. Die Harze besitzen eine gute thermische und chemische Stabilität und eine gute elektrische Leitfähigkeit. Die Reaktion verläuft nach erster Ordnung; die Aktivierungsenergie beträgt 47 kJ mol-1 bzw. 34 kJ mol-1 mit bzw. ohne Chromacrylat. Aus spektroskopischen Untersuchungen wird geschlossen, daß das Chrom mit Bisphenol A einen Komplex bildet, der die Epoxidierung beschleunigt.
    Notes: Novel epoxy resins containing chromium acrylate have been synthesized by reacting chromium acrylate with bisphenol-A and excess epichlorohydrin. The quantities such as epoxy equivalent weight, hydroxy content, hydrolyzable chlorine content and viscosity have been determined. The resins have been characterized by IR and 1H NMR spectroscopy. The cured resins were evaluated for thermal properties. The curing of resins was carried out with Ciba Geigy HY 850 (aliphatic amine adduct) at 30°C for 24 h. The cured resins have excellent thermal and chemical resistance, in addition to an excellent electrical conductivity. The reaction follows first order kinetics with an activation energy of 47 kJ mol-1 and 34 kJ mol-1 in the presence and absence of chromium acrylate, respectively. The chromium forms a complex with bisphenol-A, as indicated by spectroscopic studies, which increases epoxidation.
    Additional Material: 6 Ill.
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  • 60
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 67-76 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Interpenetrierende Polymernetzwerke (IPNs) aus Polystyrol und Polyurethan auf der Basis von hydroxyterminiertem Naturkautschuk mit unterschiedlichen NCO/OH-Verhältnissen wurden unter verschiedenen Reaktionsbedingungen hergestellt und zu widerstandsfähigen Filmen verarbeitet. Die IPNs wurden durch ihre physikalischen, mechanischen und morphologischen Eigenschaften wie Dichte, Shore-A-Härte, Vernetzungsdichte, Zugfestigkeit und Reißdehnung charakterisiert. Mit steigendem Polystyrolgehalt erhöhen sich auch Dichte, Shore-A-Härte und Zugfestigkeit, während die Reißdehnung abnimmt. Die Untersuchungen der Vernetzungsdichte lassen eine Phasenumkehr vermuten.
    Notes: Interpenetrating polymer networks (IPNs) of polyurethane based on hydroxyterminated natural rubber with varying NCO/OH ratios and polystyrene were synthesized under different experimental conditions. These IPNs were found to make tough films. The IPNs were characterized by their physical, mechanical and morphological properties like density, Shore-A hardness, crosslink density, tensile strength and elongation at break. The IPNs exhibited an increasing trend in density, Shore-A hardness and tensile strength with increasing polystyrene content, while elongation at break decreased with similar variation in polystyrene content. The crosslink density measurements indicated a possible phase inversion process.
    Additional Material: 7 Ill.
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  • 61
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 117-124 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß einer Plasmabehandlung von Ultrafiltrationsmembranen aus Polyethylen auf die Fouling- und Reinigungseigenschaften bei der Filtration von Rinderserumalbumin werden diskutiert. Bei 2,45 GHz erzeugtes Luft-Plasma steigert die Hydrophilie der Membranoberfläche von 0 auf 60%. Der Durchfluß bleibt bei 90 bis 99%. Mit Plasma behandelte Membranen sind leichter zu reinigen als unbehandelte; dennoch sind sie anfälliger für die Ablagerung von Rinderserumalbumin.
    Notes: The effect of plasma treatment of polyethylene ultrafiltration membranes on fouling and cleaning phenomena during filtration of bovine serum albumin solutions is discussed. Air-plasma of 2.45 GHz raises the membrane surface hydrophilicity from 0 up to 60%. The flux is maintained at 90-99%. Plasma-treated membranes are easier to clean than untreated polyethylene membranes. Despite that, the plasma-modified membranes are susceptible to more intensive deposition of albumin.
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  • 62
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 101-115 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Immobilisierung von Glucose-Oxidase in einer Poly(vinylalkohol) (PVAL)-Membran in Gegenwart von UV-Photoinitiatoren wurde untersucht. Enzym-Membranen wurden aus PVAL-Diazoharz- und PVAL-Photoinitiator-Systemen durch Vernetzung mit UV-Licht hergestellt. Mit diesen immobilisierten Glucose-Oxidase-Membranen wurde eine wirkungsvolle Enzymelektrode entwickelt, deren Eigenschaften untersucht wurden. Der Einfluß der Photoinitiatorkonzentration in Poly(vinylalkohol) und der UV-Bestrahlungsdauer auf den Grad der Unlöslichkeit sowie die Aktivitätsausbeute der Membran wurden mit Glucose als Substrat untersucht. Temperatur- und pH-Abhängigkeit der relativen Aktivität, Stabilität bei mehrmaligem Gebrauch, Lagerstabilität und Kalibrierungsdiagramme der Enzym-Membranen wurden ermittelt. Eine beim Erstgebrauch auftretende Instabilitätserscheinung der Membranen wurde ebenfalls untersucht.
    Notes: A study of the immobilization of glucose oxidase on a poly(vinyl alcohol) (PVAL) membrane in the presence of UV sensitizers was carried out. Enzyme membranes were prepared from PVAL-diazoresin and PVAL-sensitizer systems, crosslinked by means of UV irradiation. An effective enzyme electrode was developed by using the immobilized glucose oxidase membrane, and its characteristics were investigated. The effects of the concentration of sensitizers in poly(vinyl alcohol) and UV irradiation time on the degree of insolubility as well as the activity yield of the membrane were examined for the immobilized glucose oxidase using glucose as a substrate. Temperature and pH dependences of the relative activity, stability in repeated use, storage stability and calibration plots of the enzyme membranes were evaluated. The unstability phenomenon, found in the initial use of the immobilized glucose oxidase membrane, which was prepared from PVAL-sensitizer system, was also investigated.
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  • 63
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 11-26 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Biopol, Biocellat and Mater-Bi, three biologically decomposable plastics have been tested for their use in medical industries. Biopol did not loose its stress and stiffness under sterilisation, and was also resistant against temperature and alcohol. Mater-Bi and Biocellat, the two other materials, did not satisfy the test applications. Water vapor sterilisation, temperature up to 60°C, at higher temperatures this material will embrittle.
    Notes: Für den Einsatz biologisch abbaubarer Kunststoffe in der pharmazeutischen Industrie und Medizintechnik wurden Produkte verschiedener Hersteller, wie Biopol, Biocellat und Mater-Bi untersucht. Dabei zeigte vor allem Biopol das notwendige Anforderungsprofil, d.h. die Anwendbarkeit aller Sterilisationsverfahren ohne Festigkeitsbzw. Steifigkeitsverluste sowie Temperatur- und Alkoholbeständigkeit. Dagegen wiesen die Werkstoffe Mater-Bi und Biocellat einige Schwachstellen auf. Bei Mater-Bi lagen diese bei der Wasserdampfsterilisation sowie bei der geringen thermischen und Medienbeständigkeit. Biocellat versprödet dagegen durch die erhöhte Temperatur bei der Dampfsterilisation, d.h. daß ein Einsatz über 60°C nicht möglich wäre.
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  • 64
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Alkylierung von Poly(5-vinyltetrazol) mit Dimethylsulfat und tert-Butylalkohol sowie Alkylhalogeniden RHal (R=CH3, C2H5, CH2—CH=CH2, n-C4H9 und t-C4H9) und die Kinetik dieser Reaktion wurden untersucht, um eine neue Herstellungsmethode für tetrazolhaltige Polymere mit wertvollen Eigenschaften zu entwickeln. Die vergleichenden Untersuchungen über die isomere Zusammensetzung und die spektroskopischen Daten von Poly(N-alkyl-5-vinyltetrazol)en, die durch die Alkylierung von Poly(5-vinyltetrazol) sowie durch die Copolymerisation der entsprechenden Monomeren hergestellt wurden, wurden mit IR-, 1H-NMR- und 13C-NMR-Spektroskopie durchgeführt. Der Alkylierungsumsatz beträgt bis zu 99,8%; dadurch können polymere Produkte erhalten werden, deren Zusammensetzung, Struktur und Eigenschaften denen der Homo- und Copolymeren sehr ähnlich sind.
    Notes: Alkylation of poly(5-vinyl tetrazole) with dimethyl sulfate and tert-butyl alcohol as well as with alkyl halides RHal (R=CH3, C2H5, CH2—CH=CH2, n-C4H9, t-C4H9) has been studied under various conditions in order to develop a new method of synthesis of tetrazole-containing polymers having a complex of valuable properties. The kinetic study of the process and comparison of isomeric compositions and spectroscopic characteristics (IR, 1H NMR and 13C NMR) of poly(N-alkyl-5-vinyl tetrazole)s synthesized by alkylation of poly(5-vinyl tetrazole) and of those prepared by (co)polymerization of the corresponding vinyl tetrazoles have been carried out. The alkylation is found to proceed to high conversion extents (up to 99.8%) and enables to obtain a wide variety of polymeric products having the composition, structure and properties very similar to those of homo- and copolymers.
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  • 65
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Farbstoffe mit nichtlinearen optischen Eigenschaften wurden in einer zweistufigen Synthese aus 2-Hydroxyethylmethacrylat (HEMA), 4-Carboxybenzaldehyd und verschiedenen Anilinderivaten hergestellt. Die Farbstoffe (aromatische Iminester von HEMA) wurden mit Styrol copolymerisiert, die erhaltenen Copolymere wurden mit DSC sowie IR-, 1H NMR- und UV-VIS-Spektroskopie charakterisiert, und ihre nichtlinearen Eigenschaften wurden untersucht. Es zeigte sich, daß die nichtlinearen Koeffizienten d31 und d33 vom Farbstoffgehalt der Copolymeren und der Art der elektronenspendenden Gruppen abhängig sind.
    Notes: Dyes for nonlinear optics have been synthesized in two steps from 2-hydroxyethyl methacrylate (HEMA), 4-carboxybenzaldehyde and various substituted anilines. The obtained dyes (aromatic imine esters of HEMA) have been copolymerized with styrene, the copolymers characterized by DSC as well as IR, 1H NMR and UV-VIS spectroscopy, and studied for their nonlinear properties. The d31 and d33 nonlinear coefficients proved to be dependent on the dye content of the copolymers and on the nature of electrondonating groups.
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  • 66
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    Angewandte Makromolekulare Chemie 220 (1994), S. 123-132 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß von Ca2+-bzw. Al3+-Ionen auf das Viskositätsverhalten (Salzverträglichkeit) wäßriger Lösungen von Natriumcarboxymethylcellulose (CMC) sowohl mit unterschiedlichem Polymerisationsgrad (DP) als auch mit unterschiedlichem Substitutionsgrad (DS) und verschiedenartiger Substitutentenverteilung wurde untersucht. Aus Viskositätsmessungen mit einem Rotationsviskosimeter bei einer Scherrate von 500 s-1 geht hervor, daß die relative Abnahme der Viskosität im Ergebnis des Zusatzes der mehrwertigen Metallkationen unabhängig vom DP (im Bereich von 160 bis 900) der CMC ist. Homogen hergestellte CMC-Proben 2 mit einem größeren Gehalt an 2,3,6-Tri-O-carboxymethylglucose-Einheiten in der Polymerkette weisen im Vergleich zu heterogen hergestellten CMCs 1 bei gleichem Gesamt-DS eine höhere Salzverträglichkeit auf.
    Notes: The influence of Ca2+-and Al3+-ions, respectively, upon the viscosity behaviour (so-called salt tolerance) of aqueous solutions of sodium carboxymethyl cellulose (CMC) with different degree of polymerization (DP) and, on the other hand, with both different degree of substitution (DS) and distribution of substituents, was investigated. Viscosimetry by means of a rotational rheometer at a shear rate of 500 s-1 shows that the relative drop in viscosity as a result of addition of the multivalent metal cations is independent of DP (ranging from 160 to 900) of the CMC samples. Homogeneously synthesized CMCs (2) with a higher content of 2,3,6-tri-O-carboxymethyl glucose units in the polymer chain possess a significantly higher salt tolerance than those (1) prepared under heterogeneous reaction conditions at comparable total DS values.
    Additional Material: 4 Ill.
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  • 67
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    Angewandte Makromolekulare Chemie 222 (1994), S. 61-87 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Melamin-Formaldehyd-Harz-Formmassen (MF) wurden durch mechanisches Mischen mit Ethylen-Vinylacetat-Copolymeren (EVA) und teilverseiftem EVA modifiziert, wobei Etherbindungen zwischen dem hydrolysierten EVA und dem MF-Harz nachgewiesen werden konnten, die die mechanischen Eigenschaften von spritzgepreßten Formteilen im Vergleich zur Modifizierung mit EVA verbessern. Der Zusatz solcher Modifikatoren erhöht die Duktilität und verringert im Falle von EVA die Nachschwindung der überaus steifen MF-Matrix, solange der Modifikatoranteil gering bleibt. Dagegen werden die Steifigkeit und die Wärmeformbeständigkeit verschlechtert. Die durch solche unvernetzten Polymeren erreichbare Steigerung der Schlagzähigkeit bleibt allerdings unzureichend.
    Notes: Melamine-formaldehyde moulding compounds (MF) were modified by mechanical mixing with ethylene/vinyl acetate copolymers (EVA) and with partially hydrolysed EVA. Ether linkages between the hydrolysed material and the MF resin improve the mechanical properties of the transfer moulded parts containing the hydrolysed material compared to those made with EVA. The use of both modifying polymers improves the ductility and, in case of the partially hydrolysed material, the postshrinkage of the extremely rigid MF matrix, as long as the modification polymer content is kept low. On the contrary, Young's modulus and the heat deflection temperature are deteriorated. The improvement in impact strength by use of those uncrosslinked polymers is still insufficient.
    Additional Material: 17 Ill.
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  • 68
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    Angewandte Makromolekulare Chemie 222 (1994), S. 111-123 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine Reihe von Copolyesteramiden mit Molekulargewichten zwischen 1000 und 7000 (GPC, NMR) wurden aus Adipinsäure/1,6-Hexandiamin/∊-Caprolacton bzw. Nylon 6,6-Salz/∊-Caprolacton hergestellt. Die thermischen Eigenschaften der synthetisierten Polymeren (Glasübergangs-, Schmelz-, und Zersetzungstemperaturen, Schmelzenthalpien) wurden durch DSC- und TGA-Messungen bestimmt und in Bezug auf das Comonomerverhältnis in der Ausgangsmischung diskutiert. Die Übereinstimmung der Copolymerzusammensetzung mit dem Ausgangscomonomerverhältnis wurde mit FT-IR- und NMR-Spektroskopie untersucht. Die Bioabbaubarkeit der Copolyesteramide wurde durch enzymatische Hydrolyse geprüft.
    Notes: A series of copolyesteramides based on adipic acid/1,6-hexane diamine/∊-caprolactone and Nylon 6,6 salt/∊-caprolactone were synthesized. Their molecular weights, determined by gel permeation chromatography and NMR spectroscopy, were found to lie within the range from 1000 up to 7000. Their thermal properties (glass transitions, melting points and heats of melting, and decomposition temperatures) were recorded with diferential scanning calorimetry and thermogravimetry, respectively, and correlated to the comonomer feed composition. The FT-IR and NMR spectra were also recorded in order to confirm the composition of the copolyesteramides and to compare them with that of the comonomer feed. The biodegradability of the synthesized copolymers was tested by enzymatic hydrolysis.
    Additional Material: 4 Ill.
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  • 69
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    Angewandte Makromolekulare Chemie 222 (1994), S. 165-174 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch sulfonsäurekatalysierte Umsetzung von Abietinsäure und Paraformaldehyd bei hohen Temperaturen wurden neuartige Kondensationsprodukte erhalten. Als Nebenprodukte der Polykondensation werden eine Ketoverbindung sowie Wasser und Kohlendioxid gebildet. Die Carboxygruppen der Abietinsäure sind an der Kondensationsreaktion beteiligt. In Abwesenheit von Paraformaldehyd wurde das Abietinsäure/Sulfonsäurekatalysator-System untersucht, um zusätzliche Informationen über die Reaktion zu erhalten. Der Reaktionsverlauf hängt von der Temperatur und der chemischen Struktur des Katalysators ab. Ein möglicher Reaktionsmechanismus der Kondensation wird diskutiert.
    Notes: New condensation products have been synthesized by heating abietic acid and formaldehyde at high temperatures in the presence of sulfonic-type acid catalysts. The main polycondensation reaction is associated with a secondary one which leads to a ketonic compound, carbon dioxide and water. The carboxylic groups of abietic acid participate in this condensation reaction. The behaviour of the abietic acid-sulfonic acid catalyst system was studied in absence of formaldehyde to acquire additional information about the reaction. The process is defined by the reaction temperature and chemical nature of the catalyst. A possible mechanism of the condensation reaction is discussed on the basis of the obtained results.
    Additional Material: 2 Ill.
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  • 70
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    Angewandte Makromolekulare Chemie 223 (1994), S. 1-11 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: After a general classification of the cationic ring-opening polymerizations (CROP's) according to their polymerization mechanism, a number of examples of tailored polymers based on CROP are presented. The monomers used for the synthesis of these tailored structures are tetrahydrofuran (THF), N-tert-butyl aziridine (TBA), 2-methyl-1,3-oxazoline (MeOX) and 1,3-dioxolane (DXL).The polymer structures include different block and graft copolymers, macromonomers, star-shaped polymers, polymer networks and interpenetrating polymer networks (IPNs).
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  • 71
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In diesem Beitrag wird ein überblick über neuere Entwicklungen auf dem Gebiet der Synthese von Telechelen, Makromonomeren, Block- und Pfropfcopolymeren gegeben. Synthesestrategien aus den Bereichen der Polykondensation, der radikalischen, anionischen und kationischen Polymerisation, der Kettenspaltung sowie der Criss-Cross-Cycloaddition werden diskutiert.
    Notes: New developments in the synthesis of telechelics, macromonomers, block- and graftcopolymers are presented. Synthetic strategies for them are demonstrated with examples from different fields such as polycondensation, radical, anionic, and cationic polymerization, chain cleavage and criss-cross-cycloaddition.
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  • 72
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    Angewandte Makromolekulare Chemie 223 (1994), S. 69-79 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Alkanes with highly substituted carbon-carbon bonds can be cleaved in free radicals by homolytic dissociation under the influence of thermal energy. The energy of dissociation is mainly determined by the type and size of the respective substituents. For tetraarylbutane dinitriles the temperatures of decomposition are in the range of other technically used initiators. But nevertheless, these compounds are up to now rather seldom used to initiate free radical polymerizations. This is connected with the special mechanism of initiation: the formed highly substituted alkyl radicals are relatively stable and show only a rather low reactivity against the usually used monomers. Therefore, in the beginning of the polymerization the radical concentration is rather high which leads not only to addition to monomers but also to a pronounced primary radical termination. In some cases this termination process is reversible which results in an unusual polymerization kinetics. Depending on the type of monomer and the degree of reversibility of the primary radical termination, either a period of “dead-end” polymerization follows or the cleavage of the oligomers at the chain end results in a re-initiation process with a “normal” polymerization with increased rate. The reaction mechanism, kinetics and some possible applications of such initiating alkanes are reported.
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  • 73
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    Angewandte Makromolekulare Chemie 223 (1994), S. 121-133 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Untersuchungen wesentlicher Aspekte der Polymerisation und der Eigenschaftsmodifikation auf Metallocen-Katalyse basierender Cycloolefin-Copolymere (COC) zeigen, daß mit dieser Monomer-Katalysator-Kombination eine neue Klasse transparenter Thermoplasten zugänglich gemacht wird. COC können mit Metallocenen in beliebiger zusammensetzung und mit kontrollierter Mikrostruktur hergestellt werden. Die somit erreichte und durch zusätzliche Modifikationen noch erweiterbare Breite des Eigenschaftsspektrums ermöglicht vielfältige Anwendungen dieser neuen Polymerklasse. Die wichtigsten Schlüsselfaktoren im rohstofflich-technologischen Bereich, die diese Struktur- und Eigenschaftsvielfalt ergeben, werden beispielhaft beschrieben.
    Notes: Investigation of the polymerization process and property modification of metallocene-based cycloolefin copolymers (COC) shows that this monomer-catalyst combination enables synthesis of a new class of transparent thermoplastic polymers. Metallocene catalysis offers much opportunity to vary the composition and microstructure of the copolymers. The breadth of the polymer spectrum which can be further widened by polymer modification enables many applications for this new class of thermoplastics. The key parameters that control structure and properties in the COC family are discussed in this paper.
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  • 74
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    Angewandte Makromolekulare Chemie 223 (1994), S. 165-175 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The present paper deals with the synthesis and modification of functionalized polymers characterized by a special molecular architecture. The reactivity of a functionalized polymer with comb-like structure can be controlled in a significant manner by the crystalline order of the side chains. In contrast, photocrosslinking of comblike polymers containing cinnamic components in the side chains influences the crystallization process. The air drying process of a modified polybutadiene system with comb-like structure was shown to depend sensitively on the side chain order. Enzymatic synthesis of new monomers and polymers is briefly reviewed. The complexing capability of cyclodextrines were used to synthesize polyrotaxanes. Finally, the synthesis of a chiral polymerizable dendrimer containing eight estergroups in the monomer unit is presented.
    Additional Material: 8 Ill.
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  • 75
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    Angewandte Makromolekulare Chemie 223 (1994), S. 203-216 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Intramolecularly crosslinked poly(organosiloxane) particles are prepared by means of emulsion polycondensation or emulsion polymerization of alkoxysilanes or cyclic organic siloxanes. Starting from these intramolecularly crosslinked poly(organosiloxane) particles, graft copolymers are obtained by free-radical emulsion polymerization of unsaturated olefinic monomers (e.g. acrylates, styrene) in the presence of (functionalized) organosiloxanes. Intramolecularly crosslinked poly(siloxane) particles and their graft copolymers are characterized by means of light scattering (in dispersion), electron microscopy and thermal analyses (DSC, DMTA).
    Additional Material: 4 Ill.
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  • 76
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    Angewandte Makromolekulare Chemie 214 (1994), S. 153-167 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Zusammenhang zwischen der Mischbarkeit und den physikalischen Eigenschaften von Polymerblends aus Poly(2,6-dimethyl-1,4-phenylenoxid) (PPO), die in unterschiedlichen Zusammensetzungen in einem Doppelschneckenextruder mit Polystyrol, schlagzähem Polystyrol oder Styrol-Butadien-Copolymeren hergestellt wurden, wird diskutiert. Die Verträglichkeit der Komponenten wurde mittels DSC und DMA, die Morphologie der Blends mittels SEM untersucht. Mit abnehmendem Polystyrolanteil wurde eine schlechtere Mischbarkeit bei den Blends beobachtet, deren Kerbschlagempfindlichkeit sich erhöhte. Die Untersuchungsergebnisse werden mit dem Micellmodell interpretiert.
    Notes: The relationship between the miscibility and the physical properties of polymer blends of poly(2,6-dimethyl-1,4-phenylene oxide) and polystyrene (PS), high-impact polystyrene (IPS) and poly(styrene-block-butadiene-block-styrene) (SBS), which are blended in different compositions by a twin-screw extruder is discussed. The three types of SBS that were used are SBS1, SBS2 and SBS3 having different styrene/butadiene ratios. Dynamic mechanical analysis and differential scanning calorimetry were used to study the miscibility. The morphology was examined by SEM. The miscibility of the blends decreases with decreasing PS content. The notch sensitivity is improved by blending. Finally, the micelle model was used to explain the testing phenomena.
    Additional Material: 8 Ill.
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  • 77
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Aliphatische Polyamide mit Poly(ethylenoxid)-Kettensegmenten unterschiedlicher Länge wurden durch Grenzflächenpolymerisation aus Succinylchlorid und Jeffamine ED-900 (O,O'-Bis(2-aminopropyl)poly(ethylenglykol) 800) bzw. Jeffamine ED-2001 (O,O'-Bis(2-aminopropyl)poly(ethylenglykol) 1900) zur Verwendung als Trägersubstanzen für Medikamente synthetisiert. Copolyamide mit kurzkettigen Diamin- und Jeffamine-Segmenten sowie Polyamide aus Cystin und Diamineinheiten wurden auf die gleiche Weise hergestellt. Die Polymerisationen wurden im zweiphasigen System Dichlormethan/Wasser bei Temperaturen um 0°C durchgeführt. Die Polymerprodukte wurden durch stufenweise Dialyse in wäßriger Phase bis zu einem Molekulargewicht von 25000 fraktioniert, nach Gefriertrocknung als wasserlösliche Harze oder Feststoffe erhalten und durch Mikroanalyse sowie 1H NMR-Spektroskopie charakterisiert. Die inhärenten Viskositäten liegen im Bereich von 10-20 ml/g. Die Eignung eines repräsentativen Zielmoleküls zur Bindung von Medikamenten wurde durch eine kovalente Verankerung einer als Medikamentmodell fungierenden Ferrocen-Verbindung untersucht. Dabei wurde ein wasserlösliches Polymer-Ferrocen-Konjugat erhalten.
    Notes: Aliphatic polyamides comprising poly(ethylene oxide) chain segments of various lengths, designed for use as drug carriers, are synthesized by interfacial polymerization of succinyl chloride with the two Jeffamine types ED-900 and ED-2001, formally described by the supplier as O,O'-bis(2-aminopropyl)poly(ethylene glycol) 800 and O,O'-bis(2-aminopropyl)poly(ethylene glycol) 1900. Copolyamides comprising both short-chain diamine and Jeffamine segments are similarly prepared, as are polyamides made up of cystine and diamine segments. The polymerizations are performed in a two-phase methylene chloride-water system at temperatures near or below 0°C. The product polymers, crudely fractionated by staged aqueous-phase dialysis at an ultimate molecular-mass cut-off of 25000, are collected after freeze-drying as water-soluble resins or solids and are characterized microanalytically and by 1H NMR spectroscopy. Inherent viscosities are in the range of 10-20 ml g-1. The drug-binding potential of a representative target polymer is probed by the covalent anchoring of a ferrocene compound used as a drug model, giving a water-soluble polymer-ferrocene conjugate.
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  • 78
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    Angewandte Makromolekulare Chemie 214 (1994), S. 211-216 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Über die Anwendung von Vinylesterharzen aus dem Diglycidylether von Bisphenol A sowie dessen Urethanderivat als Beschichtungsmaterial wird berichtet. Die mit den Harzen beschichteten Flußstahlplatten wurden auf Oberflächenglanz, Kratzfestigkeit und Chemikalienbeständigkeit untersucht. Harze mit Styrolanteil zeigen deutlich verbesserte Beschichtungseigenschaften.
    Notes: The present paper is concerned with the coating applications of a vinyl ester resin derived from diglycidyl ether of bisphenol-A and its urethane derivative. The mild steel panels coated with the synthesized resins were evaluated for their gloss on the surface, scratch hardness and chemical resistance. The incorporation of styrene in the resin systems improves the properties of coatings remarkably.
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  • 79
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Katalysatorsystem Zirkonocendichlorid/Methylalumoxan wurde auf Siliciumdioxid aufgebracht, um Katalysatoren fur die Suspensions- order Gasphasenpolymerisation von Ethylen herzustellen. Die häochste Aktivitäat wurde für eine sandwichartige, dreilagige Verankerung von Zirkonzentren auf der Träageroberfläache gefunden. Dieneuen Katalysatorsysteme besitzen eine im Vergleich zu den entsprechenden homogenen Katalysatoren geringere Aktivitäat. Die Immobilisierung der aktiven Katalysatorzentren führt zu einer deutlichen Erhäohung der Polymermolmassen. Dabei bleibt die enge Molekulargewichtsverteilung der Polymerprodukte nahezu erhalten. Solche auf Träager aufgebrachte Metallocen-Katalysatoren käonnten für die Herstellung von Polyethylenen mit kontrollierter Rheologie Anwendung finden.
    Notes: The system zirconocene dichloride/methylalumoxane was supported on silica in order to provide ethylene polymerization catalysts for suspension or gas phase processes. Highest activity was found for a sandwich-like, three layer anchoring of the zirconium centers on the support surface. The new catalyst systems show a decrease of activity compared to polymerization experiments in homogeneous phase. However, the molecular weights are increased and the weight distributions remain narrow by immobilization of the active catalyst sites. Those supported metallocene catalysts could find application for the synthesis of polyethylene materials with controlled rheology.
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  • 80
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    Angewandte Makromolekulare Chemie 215 (1994), S. 129-138 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Vernetzte Copolmere aus Butylacrylat (BA) und Ethylenglycol-dimethacrylat (EGDMA) wurden auf ihre Eignung als stationäare Phase für die Chromatographie untersucht. Es wurde festgestellt, daß gering vernetzte Copolymere (〈 30 Gew.-% EGDMA) nicht poräos sind, wäahrend Matrices mit mehr als 40 Gew.-% EGDMA eine konstante Porositäat aufweisen. Eine Erhäohung des Vernetzergehaltes beeinflußt hauptsäachlich die Hydrophobie der Oberfläache. Zwei Meßmethoden für diese Eigenschaft werden diskutiert: Die Absorption von Alkylalkoholen und von Aminosäauren. Für letztere wurde aus der Steigung der Beziehung zwischen der Sälenkapazitäat und dem Hydrophobie-Parameter der Aminosäauren ein Matrix-Hydrophobie-Index berechnet und dieser mit den bekannten Energien der Wechselwirkung von Alkylalkohol—CH2 Gruppen mit der Polymermatrix verglichen. Die Vorteile der Verwendung des Hydrophobie-Indexes bei der Bewertung von polymeren Sorbentien werden aufgezeigt.
    Notes: Copolymers of butyl acrylate (BA) crosslinked with ethylene glycol dimethacrylate (EGDMA) were evaluated as potential chromatographic packings. It was found that slightly crosslinked copolymers (up to 30 wt.-% EGDMA) did not provide porous material, while for matrices which exceeded 40 wt.-% of EGDMA the porous structure remained unchangeable. The increase of crosslinker content mostly affected the surface hydrophobicity. Two methods of measurement of this property were discussed: Sorption of alkyl alcohols and amino acids. Taking the latter for testing, a polymer matrix hydrophobicity index was calculated as the slope of dependence of column capacity vs. amino acid hydrophobicity parameter. The indices were verified against well-established interaction energies of —CH2— groups of alkyl alcohols and polymer surfaces. Some benefits of the use of the hydrophobicity index in evaluation of polymer sorbents were demonstrated.
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  • 81
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Kondensation von 3-Glycidyloxypropyltrimethoxysilan I mit Diphenylsilandiol II wurde untersucht. Abhängig von Lösungsmittel, Temperatur und Katalysator werden unterschiedliche Primärprodukte erhalten. Die Reaktion in Masse bei 120°C mit Titan(IV)-isopropylat als Katalysator liefert ein transparentes Harz A. Das eduktfreie Produkt wurde IR-, 1H- und 13C-NMR-spektroskopisch charakterisiert und chromatographisch mit GPC und HPLC untersucht. Die trimeren und tetrameren Siloxane bestehen aus Diphenylsilan- und 3-Glycidyloxypropylmethoxysilaneinheiten. Das Verhältnis von cyclischen zu linearen Molekülen beträgt 2:1. Höhermolekulare Verbindungen entstehen nur in geringen Mengen. Das Epoxysiloxangemisch löst sich in unterschiedlichen organischen Lösungsmitteln und ist mit kommerziell verfügbaren Epoxiden mischbar. Die Zeitabhs̈ngigkeit von Viskosität und Epoxidwert bei der Lagerung unter Normalbedingungen wurden gemessen und mit HPLC verfolgt . Die Lagerstabilität wurde durch eine zusätzliche thermische Behandlung verbessert.
    Notes: Condensation of 3-glycidyloxypropyltrimethoxysilane I with diphenylsilanediol II was investigated. Depending on solvent, temperature and catalyst, different products were obtained. Bulk reaction at 120°C using titanium(IV)-isopropylate as a catalyst provided the transparent resin A. A was characterised by IR, 1H- and 13C-NMR spectroscopy and contained no reactants. GPC and HPLC studies revealed that A consists of trimer and tetramer siloxanes of pertinent diphenylsilane and 3-glycidyloxypropylmethoxysilane moieties. The proportion of cyclic to linear molecules was evaluated 2:1. Only small amounts of high-molecular-weight compounds were observed. The epoxysiloxane product proved to be miscible with various organic solvents and with commercial epoxy resins. Time dependence of viscosity and epoxy content were recorded during ambient storage and monitored by HPLC. Pot-life was improved by a subsequent thermal procedure.
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  • 82
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    Angewandte Makromolekulare Chemie 218 (1994), S. 163-170 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Cis-1,4-Polybutadien wurde durch Polymerisation von 1,3-Butadien mit Katalysatorsystemen hergestellt, die Ni(OOC8H15)2 und Al(C2H5)3 sowie die Lewissäuren BF3 · O(C2H5)2 oder TiCl4 enthalten. Die Molmassenverteilungen (MMD) der erhaltenen Polybutadiene wurden mit der Größenausschlußchromatographie (SEC) untersucht. Sie lassen sich mit Summen aus Schulz-Flory-Funktionen (SFF) beschreiben. Da eine Art aktiver Zentren eine SFF ergibt, die durch Molmassenmittelwerte definiert ist, lassen sich verschiedene Molmassenverteilungen nach Bandentrennung auf gleiche und verschiedene Arten aktiver Zentren untersuchen. In den untersuchten Systemen lassen sich zwei vergleichbare und eine unterscheidbare Art aktiver Zentren zuordnen. Auf diese Weise wurde das Kettenwachstum in Abhängigkeit von den Komponenten und Katalysatorformierungsbedingungen untersucht.
    Notes: Cis-1,4-polybutadiene was produced by polymerization of 1,3-butadiene using a catalyst system containing Ni(OOC8H15)2 and Al(C2H5)3 and the Lewis acids BF3 · O(C2H5)2 or TiCl4. The molar mass distributions (MMD) of the polybutadienes are investigated by means of size exclusion chromatography (SEC). The MMD's were fitted by a sum of Schulz-Flory-Functions (SFF). Taking into account that one kind of active species gives one SFF defined by molar mass averages, one comparable active species in both systems and one different were found. This way it was tried to find a relationship between the grown up of the active species depending on components and reactions conditions.
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  • 83
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    Biopolymers 34 (1994), S. 11-20 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: αD-N-acetyl neuraminic acid (Neu5Ac, sialic acid) is a commonly occurring carbohydrate residue in various cell surface glycolipids and glycoproteins. This residue is linked terminally or internally to Gal residues via an α(2 → 3) or α(2 → 6) linkage. In the cell surface receptor, sialyl-LewisX, a terminal α(2 → 3) linkage is present. Previous studies from our laboratory have shown that in solution LewisX adopts a relatively rigid structure. In order to model the Neu5Ac residue, vacuum molecular dynamics of this monosaccharide were compared with simulations that explicitly include solvent water. The dynamical average of the monosaccharide conformation obtained from the two simulations was similar. Vacuum calculations for the disaccharide Neu5Ac α(2 → 3) Gal β-O-methyl show that a number of low energy minima are accessible to this disaccharide. Molecular dynamics simulations starting from the low energy minima show conformational transitions with a time scale of 10-50 ps among several of the minima while large barriers between other minima prevent transitions on the time scale studied. Simulations of this disaccharide in the presence of solvent show fewer conformational transitions, illustrating a dampening effect of the solvent that has been observed in some other studies. Our results are most consistent with an equilibrium among multiple conformations for the Neu5Ac α(2 → 3) Gal β linkage. © 1994 John Wiley & Sons, Inc.
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  • 84
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The properties of collagen are affected by the replacement of Pro by imino acid analogues. The structural effect of the low-level local substitution of L-azetidine-2-carboxylic acid (Aze) has been analyzed by computing the energy of CH3CO-(Gly-Pro-Pro)4-NHCH3 triple helices in which a single residue of one strand has been replaced by Aze. When Aze is in position Y of a (Gly-X-Y) unit, low-energy local deformations are introduced in the triple helix, i.e., it becomes more flexible. On the other hand, the flexibility of the triple helix is not increased with Aze in position X. The energy of the triple helix to coil transition is not changed significantly by this amount of substitution. In an earlier study, we have demonstrated that the regular substitution of Aze in every tripeptide distorts or destabilizes the triple helix to a large extent [A. Zagari, G. Némethy, & H. A. Scheraga (1990) Biopolymers, Vol. 30, pp. 967-974 ]. Thus, it appears that a high level of substitution is required to cause the observed chemical and biological effects of Aze on collagen. © 1994 John Wiley & Sons, Inc.
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  • 85
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    Biopolymers 34 (1994), S. 357-364 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A dielectric relaxation peak due to bound water of globule proteins in aqueous solution was observed at first by the use of a time domain reflectometry. This peak locates around 100 MHz as well as that of the aqueous DNA solution and the moist collagen, and has a relaxation strength in proportion to surface of the globule protein except for trypsin and pepsin of hydrolase. It is suggested that this peak is caused by orientation of bound water molecules on the protein surface. The number of bound water molecules estimated is in good agreement with that obtained by other method such as x-ray analysis. The solution exhibits another peak below 100 MHz, which is caused by the rotation of globule protein supplemented by migration of the counterion. Its relaxation time is completely proportional to the molecular weight of the protein. © 1994 John Wiley & Sons, Inc.
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  • 86
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    Biopolymers 34 (1994), S. 393-401 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enthalpies of interactions of porcine arterial elastin with alkali metal and alkali earth halides and sulphates were investigated by means of flow microcalorimetry and the stoichiometry measured using radiotracer techniques. In aqueous solutions, all alkali earth halides interacted exothermically at concentrations ranging from 0.01 to 2.5M. All the alkali metal halides, particularly NaCl, exhibited complex concentration-dependent interactions, exothermic at low concentrations and endothermic at high concentrations. Both the anion and cation contributed to the response, although the anion seemed to dominate. SO42- interacted most strongly of the anions tested. All interactions were reversible in the sense that repeat experiments gave identical results, but the enthalpy of “adsorption” was generally different from that of “desorption.” The enthalpy of interaction depended on the conformation of the elastin in a salt-specific manner. For example, CaCl2 and MgCl2 interacted similarly in water but very differently in 1 : 1 water : methanol. © 1994 John Wiley & Sons, Inc.
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  • 87
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    Biopolymers 34 (1994), S. 435-442 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photophysical behavior of protoporphyrin IX (P) and 1-naphthylacetic acid (N), covalently bound to ε-amino groups of poly (L-lysine) (PL), was investigated by steady-state and time-resolved fluorescence as a function of pH. Within the whole range of pH explored, i.e., 7-11, exciplex emission is minor and nearly pH independent. Fluorescence quantum yields, decay time measurements, and transient absorption spectra suggest that quenching of the excited naphthyl chromophore chiefly occurs by interconversion to the triplet state when the sample is randomly coiled and by intramolecular electron transfer (ET) from ground-state porphyrin when the polypeptide is in α-helical conformation. The kinetic law, based on a two-state model for the polymeric matrix, is presented. The specific rate constant of photoinduced ET is 3.1 · 107 s-1 (25°C), in excellent agreement with that obtained by taking simply into account the lifetimes of naphthalene fluorescence in α-helical PNPL and NPL (pH 11). The relaxation time of the helix-coil transition was found to be definitely shorter than 20 ns. © 1994 John Wiley & Sons, Inc.
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  • 88
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aggregation of filipin in aqueous medium and filipin-induced changes in cholesterol micelles have been studied using intensity and dynamic light scattering. The dependencies of filipin aggregate dimensions on concentration, solvent, and temperature were studied, and revealed that the aggregates do not have a well-defined geometry, i.e., a critical micelle concentration cannot be detected and stable structures are not formed. The aggregates are of size Rg ≈ 110 nm and Rh ≈ 63 nm, referring to the radius of gyration and hydrodynamic radius, respectively. In the concentration range studied (1 μM 〈 C 〈 30 μM), a low molecular weight species (monomer/dimer) is always present together with the aggregates. In ethanol/ water mixtures, large (Rg ≈ 500 nm), narrow distribution aggregates are formed in the water volume fraction range 0.45 〈 ΦH2O 〈 0.65. Aggregation also occurs on changing the temperature; In the range 7-37°C, smaller aggregates (10-30 nm) form and the process is only partially reversible.No pronounced effect of filipin on the structure of the cholesterol micelles was observed (a small increase in Rg and Rh is noted). These results rule out any “specificity” for the filipin interactions with cholesterol, which has been considered a key event in the filipin biochemical mode of action. A reevaluatiori Of this question is suggested and some alternatives are advanced. © 1994 John Wiley & Sons, Inc.
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  • 89
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    Biopolymers 34 (1994), S. 489-505 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polypeptide α-carbon backbones were modeled as freely rotating chains made up of spherical monomers. The monomers were assigned an abstract binary “hydrophobicity” property that could be either present or absent. Under the assumption that “hydrophobic” residues tend to cluster together, away from the polar solvent, three-dimensional conformations of random copolymers of “hydrophobic” and “hydrophilic” monomers were calculated by a novel algorithm based on distance geometry techniques. The simulated molecules were globular and compact, in shape, and possessed distinct hydrophobic cores, indicating that our method was capable of reproducing some of the important global features of real polypeptides. © 1994 John Wiley & Sons, Inc.
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  • 90
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    Biopolymers 34 (1994), S. 559-563 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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  • 91
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The linear nonapeptide hormone bradykinin (Arg1-Pro2-Pro3-Gly4-Phe5-Ser6-Pro7-Phe8-Arg9) is involved, either directly or indirectly, in a wide variety of physiological processes, particularly pain and hyperanalgesia. Additional evidence suggests that bradykinin also plays a major role in inflammatory response, asthma, sepsis, and symptoms associated with the rhinoviral infection. It has long been speculated that a β-turn at the C-terminus of bradykinin plays a major role in the biological activity of the neuropeptide. The β-turn forming potential of bradykinin in three vastly different local chemical environments, DMSO, 9 : 1 dioxane/water, and in the presence of 7.4 mM lyso phosphatidylcholine micelles, was investigated using two-dimensional homonuclear nmr experiments coupled with simulated annealing calculations. The results of these investigations show that in all three systems residues 6-9 of the C-terminus adopt very similar β-turn like structures. These results suggest that the β-turn at the C-terminus of bradykinin is an important secondary structural feature for receptor recognition and binding. © 1994 John Wiley & Sons, Inc.
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  • 92
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using dynamic light scattering (DLS), we have measured the diffusion coefficient and internal motions of narrow topoisomer distributions of pUCl8 DNA (2687 base pairs) as a function of linking number. The topoisomer distributions were prepared by C-18 reversed phase high performance liquid chromatography separation of topoisomerase I/ethidium-generated topoisomer families. The measured diffusion coefficients agree well with those predicted by a Monte Carlo model for the generation of equilibrium ensembles of DNA topoisomers of defined linking number. The only parameters used in the model were the bending persistence length, torsional rigidity, and hydrodynamic radius of DNA known independently from other techniques. Two different values for the torsional rigidity, α = 4 · 10-12 and 8.8 · 10-12 dyn cm, were used. Intrachain interactions in the DNA were taken into account by using an “effective DNA radius,” which was varied between rDNA = 1-8 nm. The best agreement between the measured and calculated values was obtained for α = 4 · 10-12 dyn cm, rDNA = 4 nm. The internal motions of the DNA topoisomers were characterized by the amplitude of the fast relaxation of the DLS autocorrelation function. Our earlier result that supercoiling leads to a decrease in the amplitude of internal motion was confirmed. In addition, we see a characteristic maximum of the internal motion amplitude at a superhelix density of σ = -0.03. The maximum occurs in the same range as a structural transition in pUC8 dimers previously described by L. Song et al. (1990 J. Mol. Biol. 214, 307-326). © 1994 John Wiley & Sons, Inc.
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  • 93
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of a series of 2-phenylquinoline derivatives with RNA was investigated by means of viscometric, pKa, spectroscopic, binding, Tm, and kinetic methods. Compounds 1,2, and 3 have a piperazyl substituent at the para, meta, or ortho position, respectively, while 4 has an unsubstituted phenyl ring. The pKa results suggest that 1 has three charges, 2 and 3 have more than two charges, and 4 has two charges at pH 6.2. Spectroscopic and Tm results indicate that 1 binds more strongly to RNA than 2-4. Kinetic and modeling results indicate that 1 is a threading intercalator while 2 and 4 are classical intercalators. All experimental results indicate that 3, which has a large twist between the phenyl and quinoline rings, binds weakly with RNA. © 1994 John Wiley & Sons, Inc.
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  • 94
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Urethane bonds, derived from the hydroxyl group of the tyrosine side chain, have been investigated as a new type of amide bond mimetic in the design of pseudopeptides. The structure of a representative cyclic pseudotetrapeptide that consists of an  -  Ala  -  Tyr(urethane) Ala  -  Tyr (urethane) sequence fused into a rigid ring has been studied in the solid state by x-ray crystallography and in solution by two-dimensional nmr techniques. The cyclic pseudotetrapeptide has an oblong shape. The backbone urethane bonds assume a trans-trans conformation. The carbonyl groups in the ring have an alternating pattern of down, up, down, up with respect to the average ring plane. Solution nmr studies give observed nuclear Overhauser effects and coupling constants largely in agreement with the crystal structure. However, in solution the observed structure is likely to be conformationally averaged, and in the averaged structure, the urethane bond is perpendicular to the plane of the aromatic ring of the tyrosine, while in the crystal it is close to this plane. These differences may be explained by intermolecular hydrogen-bonding interactions. Four aspects of the conformation of the cyclic pseudotetrapeptide were investigated in detail: the tyrosine residue with the attached side-chain urethane bond (the tyrosine-urethane unit), the conformation of the two urethane backbone linkages, the conformation of the two conventional peptide bonds within this unusual ring structure, and the tight turns within the cyclic pseudotetrapeptide. The conformation of the tight turns present in the cyclic pseudotetrapeptide is very similar to that of a β-bend of type II. Intermolecular hydrogen bonding, joining adjacent layers of the cyclic pseudotetrapeptide in the solid state, resemble a parallel β-pleated sheet. The presence of these structural motifs in the cyclic pseudotetrapeptide indicates that the tyrosine urethane unit may find applications in peptide and protein engineering. © 1994 John Wiley & Sons, Inc.
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  • 95
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    Biopolymers 34 (1994), S. 415-433 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have developed a model for the simulation of the structure and dynamics of covalently closed circular DNA. It is based on the generalization of the original Brownian dynamics algorithm [D. L. Ermak & J. A. McCammon (1978) Journal of Chemical Physics, Vol. 69, pp. 1352-1359; M. Fixman (1978) Journal of Chemical Physics, Vol. 69, pp. 1527-1537] developed for bead-chain models of linear DNA to a second order numerical integration [ A. Iniesta & J. Garcia de la Torre (1990) Journal of Chemical Physics.Vol. 92, pp. 2015-2018], which we extended here to accommodate the torsional potential. The topological constraints and torsional-bending coupling in superhelical DNA are explicitly taken into account in this work by adapting a model for torsional-bending motion of linear DNA developed by Allison et al. [S. A. Allison, R. Austin, & M. Hogan (1989) Journal of Chemical Physics, Vol. 90, pp. 3843-3854].The dynamics of closed DNAs of 1124 base pairs (380 nm in length) were simulated up to ≅ 40 μs for linking number differences ΔLk between 0 and -6. Each bead in the model corresponded to 37 base pairs.For -2 ≅ ΔLk -6, the writhing number appears to decay to a limiting negative value with a single exponential law, and the relaxation time of this decay, starting from a planar closed molecule, is 3-6 μs. For the trajectories studied here, the formation of the superhelix proceeds through an initial phase of 1-2 μs where a toroidal-like structure is formed, which then converts into an interwound structure starting from a random nucleation site. For one simulation at ΔLk = -6, a branched structure was observed that did not convert into the linear interwound form for the time course of the simulation (31 μs).A verification of the simulation was performed by computing the diffusion coefficient of the 1124 base pair circle through known hydrodynamic formulas or through the center of mass displacement, and comparing these theoretical values with diffusion coefficients previously measured by dynamic light scattering. © 1994 John Wiley & Sons, Inc.
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  • 96
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    Biopolymers 34 (1994), S. 443-445 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 97
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    Biopolymers 34 (1994), S. 337-346 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present a new method for measuring the widths and depths of the grooves formed within DNA helices. This method overcomes the limitations of simply measuring interstrand phosphate-phosphate distances and has the advantage of yielding continuous values for groove geometry along a DNA fragment. In the case of oligonucleotides, it also clearly indicates the zones in which grooves exist, bounded by two phosphodiester backbones. The methodology has been developed within the Curves algorithm for studying irregular DNA geometries and is based on the optimal, and generally curved, helical axis obtained by this analysis. © 1994 John Wiley & Sons, Inc.
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  • 98
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the component synthesis method (CSM) for analyzing the normal mode dynamics of macromolecules is reported. The procedure involves a reduction of the dimensions of the normal mode problems for large molecular systems and the accurate extraction of the low-frequency modes. A macromolecule is divided into small components based on a hierarchical clustering of the residues in the structure. Interactions between coupled components are treated by the method of static correlation. The normal modes of the components are obtained first, and a fraction of the low-frequency normal modes of the components under mutual correlations are then used as a reduced basis for solving for the normal modes of the whole molecule. Multiple components are introduced for large macromolecules so that the dimensions of the eigenvalue problems at the component level are small. The method is applied to the protein crambin. In test calculations in which the dimensions of the eigenvalue equations are reduced to 1/6 of their natural size, the errors in the normal mode frequencies calculated by the CSM procedure are only about 1-2% when compared with the exact values. The rms fluctuations of all atoms in crambin calculated by the CSM procedure are basically identical to the exact results. The CSM procedure is shown to be accurate for calculating the normal modes of large macromolecules with a significant reduction of the size of the problem. © 1994 John Wiley & Sons, Inc.
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  • 99
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    Biopolymers 34 (1994), S. 365-370 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water loss during lyophilization of a 49.4 mg/mL solution of lysozyme in D2O was studied with ir spectroscopy using a low-temperature, single reflection, horizontal, attenuated, total reflectance accessory. Four regions of water loss were identified and assignable to different forms of bound water. The amide I band begins to shift to higher frequency while the amide II concurrently shifts to lower frequency and broadens after the first stage of water loss (sublimation) at -10°C. Additionally, the carboxylate band (at 1584 cm-1) shifts slightly to lower frequency. A second stage at 17°C is characterized by continued shifts in the carboxylate and amide II bands to low frequency, further broadening in the amide II and greater shift to high frequency in the amide I (ascribed to the removal of periphery water around the protein). At the third stage of water loss, the carboxylate band decreases substantially in relative absorbance (consistent with the removal of water from the carbonyl backbone). In the fourth and last stage, the carboxylate band nearly disappears and water loss is very slow. Based upon a final level of hydration of 0.037 h, the last stage corresponds to 25% completion of the removal of water associated with ionizable side chains. From start to finish, the amide I shifts 9 cm-1 to higher frequency. © 1994 John Wiley & Sons, Inc.
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  • 100
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using internal conformational degrees of freedom for biopolymers as natural variables, and introducing a Lagrangian dynamics approach, one can simulate time-dependent processes over a much longer time scale than in classical Newtonian molecular dynamics (MD) techniques. Two factors contribute to this: a substantial reduction in the number of degrees of freedom and a very large increase in the size of the time step. We present the Lagrangian equations of motion for repuckering transitions in model furanose (F), ribose (R), and 2′-deoxyribose (dR) ring systems using the pseudorotation phase angle as the single dynamic variable. As in most Lagrangian analyses, the effective masses for the R and dRmodels are dependent on conformation, and we test the behavior of this variable mass (VM) model. Since the variation in effective mass is small, the VM model is compared with a simplified constant mass (CM) model, which is shown to be an excellent approximation. The equations of motion for the CM and VM models are integrated with the leapfrog and the iterative leapfrog algorithms, respectively. The Lagrangian dynamics approach reduces the number of degrees of freedom from about 40 to 1, and allows the use of time steps on the order of 20 fs, about an order of magnitude greater than is used in conventional MD simulations. © 1994 John Wiley & Sons, Inc.
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