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  • 1980-1984  (5,217)
  • Inorganic Chemistry  (3,506)
  • Biochemistry and Biotechnology  (1,710)
  • Nuclear reactions
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 121-127 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A kinetic model was devised for the hydrolysis and synthesis of maltose and isomaltose by two glucoamylases from Rhizopus niveus and Aspergillus niger, and the validity of the model was verified experimentally at 313 K and pH 5.0. For both enzymes, the formations of maltose and isomaltose from glucose were parallel reversible reactions, and glucosyl transfer between maltose and isomaltose was not observed. The enzymes catalyzed rapid hydrolysis and synthesis of maltose. Isomaltose was hydrolyzed and synthesized more slowly, but the level produced from glucose was much higher than that of maltose. These hydrolysis and condensation reactions were expressed well by the model.
    Additional Material: 11 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 128-133 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pichia polymorpha has inulinase activity and could be used for the production of fructose syrup from inulin. The application of immobilized P. polymorpha whole cells for the continuous hydrolysis of inulin is, however, limited since the biosynthesis of this enzyme system is repressed by the reaction products, dextrose and fructose. A derepressed mutant hyperproducer of inulinase was isolated after treatment with EMS followed by a selection step with deoxyglucose.
    Additional Material: 2 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 134-141 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The technique of cell immobilization using porous support particles (biomass support particles) has been successfully applied to yeast cells. Two reactor configurations exploiting the use of these particles have been developed and assessed for use in aseptic yeast fermentations. A liquid-fluidized bed fermenter has been devised for use with particles denser than the fermentation liquor whilst a gas-stirred circulating bed fermenter proved suitable for particles of essentially neutral buoyancy. Both systems have been operated successfully for extended periods of continuous operation. The utilization of biomass support particle technology in such reactors provides a practical and robust system for immobilized cell reactors. This technology offers significant opportunities for further development.
    Additional Material: 6 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 142-147 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Biomass autoflocculation in outdoor algal cultures was found to be associated with increases of culture pH levels, due to CO2 consumption by the algal photosynthetic activity. Under these alkaline conditions, some medium chemical ions precipitated together with the algal biomass. The chemical substances involved with the process and its dependence on pH value were studied by simulation of autoflocculation in laboratory experiments. Proper concentrations of calcium and orthophosphate ions in the medium are important for autoflocculation and, in order to attain it within the pH range 8.5-9.0, the culture should contain 0.1mM-0.2mM orthophosphate and 1.5mM-2.5mM calcium prior to raising the pH level. Calcium phosphate precipitates are considered as the flocculating agent which reacts with the negatively charged surface of the algae and promotes aggregation and flocculation.
    Additional Material: 7 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 156-166 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experimental investigation is by far the most effective approach for studying the behavior of physical systems. However, an enzymatic solubilization of vegetable protein is a complex combination of intrinsic problems, of which many are not easily adaptable to experimental investigation. Experimental designs to study enzyme vegetable protein reactions yield data which describe the extramembraneous activity of the immobilized enzyme. In a continuous recycle immobilized enzyme reactor, the microenvironment concentration of the substrate or product in the membrane phase, or the concentrations along the reactor axial length in the bulk phase are not discernible to the experimenter. However, the knowledge of such concentration profiles is important in weighing the significance of such factors as intermembrane diffusion, enzyme loading, wet membrane size, and the mode of operation of the reactor. The simulation of mathematical models, which describe the physical system within the constraints imposed, yields information which is vital to the understanding of the process occurring in the reactor. The kinetics and diffusion of an immobilized thermophilic Penicillium duponti enzyme at pH 3.4-3.7 and 50°C was modeled mathematically. The kinetic parameters were evaluated by fitting a model to experimental data using nonlinear regression analysis. Simulation profiles of the effects of reactor geometry, substrate concentration, membrane thickness, and enzyme leading on the hydrolysis rate are presented. From the profiles generated by the mathematical model, the best operational reactor strategy is recommended.
    Additional Material: 11 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 188-190 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Tab.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 257-264 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Bioconversion of acetic acid to methane by a crude culture of methanogens in a continuous multireactor system was investigated. Culture of methanogens was drawn from an active cow-dung digester (12 days) and was grown in a semisynthetic medium (pH 6.3, 37°C) with acetic acid as the sole carbon source. The solubilities of CO2, HCO3-, and CO32- increased with the rise in pH and exercised considerable influence on the gas composition. Various mechanisms for methanogenesis of acetic acid based on the available pathways were considered. Experimental data were compared with these mechanisms, the best fit was determined, and the corresponding rate expression was identified. This mechanism predicted that, of the total methane produced, 72%;comes from acetic acid directly and 28%;via the CO2 reduction route.
    Additional Material: 4 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 340-346 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The rate of celluose degradation, limited due to the inhibition by cellobiose, can be increased by the hydrolysis of cellobiose to glucose using immobilized β-glucosidase. Production of β-glucosidase in four yeasts was studied and a maximum activity of 1.22 IU/mg cells was obtained in cells of Pichia etchellsii when grown on 3% cellobiose as the sole carbon source. A study of the immobilization of β-glucosidase containing cells of Pichia etchellsii on various solid supports was conducted and immobilization by entrapment in calcium alginate gel beads was found to be the most simple and efficient method. A retention of 96.5% of initial activity after ten sequential batch uses of the immobilized preparation was observed. The pH and temperature optima for free and immobilized cells were the same, i.e., 6.5 (0.05M Maleate buffer) and 50°C, respectively. Even though the temperature optimum was found to be 50°C, the enzyme exhibits a better thermal stability at 45°C. Beads stored at 4°C for six months retain 80% of their activity. Kinetic studies performed on free and immobilized cells shown that glucose is a noncompetitive product inhibitor.The immobilized preparation was found to be limited by pore diffusion but exhibited no film-diffusion resistance during packed bed column indicated by a low dispersion number of 0.1348. A model for reaction with pore diffusion for a noncompetitive type of inhibited system was developed and applied to the cellobiose hydrolysis system. The rate of reaction with diffusional limitations was determined by using the model and effectiveness factors were calculated for different particle sizes. An effectiveness factor of 0.49 was obtained for a particle diameter of 2.5 mm. The modified rate expression using the effectiveness factor represented batch and packed bed reactor operation satisfactorily. The productivity in the packed bed column was found to fall rapidly with increase in conversion rate indicating that the operating conditions of the column would have to be a compromise between high conversion rates and reasonable productivity. A half-life of over seven days was obtained at the operating temperature of 45°C in continuous operation of the packed bed reactor. However, the half-life in the column was found to be greatly affected by temperature, increasing to over seventeen days at a temperature of 40°C and decreasing to less than two days at 50°C.
    Additional Material: 7 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 347-351 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Invertase immobilized onto corn grits was utilized in the hydrolysis of highly concentrated sucrose solutions producting liquid sugar solutions containing glucose and fructose. Comparisons of conversion efficiencies of this immobilized invertase in a continuous stirredtank reactor and a plug-flow reactor indicated that the plug-flow reactor has an higher efficiency. Continuous sucrose hydrolysis was then performed in 0.1- and 1-L tubular reactors. This tenforld scaling-up was achieved without any noticeable loss in efficiency. This process thus was scaled-up to a 17.6-L pilot reactor set in a cane sugar refinery. This reactor was fed with highly concentrated sucrose solutions [71% (w/w)] to produce invert sugar syrup with the desired inversion degree. It allows a productivity equal to 9.1 kg sucrose hydrolyzed/h in the case of a 69% (w/w) sucrose initial concentration with a 72% conversion rate.
    Additional Material: 5 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 352-361 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model has been developed which describes organics removal, oxygen utilization, ammonianitrogen removal, ortho-phosphate removal, and biomass production in an aggregated microbial suspension containing a uniform floc size and the organics as a soluble biodegradable material. It is applicable to both steady-state and transient conditions, as well as to systems experiencing only carbon oxidation or to systems experiencing both carbon oxidation and nitrification. The model, consisting of five partial differential equations and four ordinary differential equations, takes into account the flow pattern in the reactor, intraparticle mass transport of oxygen, organics, ammonia-nitrogen and ortho-phosphate, and biochemical reactions by the individual cells embedded in the floc.
    Additional Material: 8 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 390-391 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 392-393 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 412-418 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pyridoxaminephosphate oxidase (EC 1.4.3.5, deaminating) that was partially purified about 40-fold from dry baker's yeast was immobilized to iodo- and bromoacetyl polysaccharides. The most effective carrier was an iodoacetyl cellulose, to which almost complete activity of pyridoxine 5′-phosphate oxidase was immobilized in 0.02M potassium phosphate buffer (pH 8.5) containing 2M ammonium sulfate at 4°C. The immobilized enzyme was more stable than the purified, soluble enzyme against heat and pH change. It was confirmed that N-(5′-phosphopyridoxyl)-L-serine was degradedly oxidized to pyridoxal 5′-phosphate and L-serine by the immobilized enzyme as comparable rate as pyridoxine 5′-phosphate, whereas N-(5′-phosphopyridoxyl)-D-serine did not serve as substrate, as in the purified, soluble enzyme.
    Additional Material: 4 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 814-819 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 820-823 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 844-847 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This article presents several characteristics of a state-of-the-art fermentation air filter. The filter medium is composed solely of PTFE and has an absolute pore size rating of 0.2 μm. Quantitative bacteria and bacteriophage retention is shown based on live organism challenge tests. A nondestructive filter test, correlated to the microorganism challenge tests and called the Forward Flow Integrity Test, is described. This test has a sensitivity of one part in 1012 and can be performed in situ.
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 848-856 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The continuous slow feed of animal and vegetable oils is frequently found to be an economically attractive method for maintaining antibiotic fermentations at a highly productive rate. The sterilization of oil feeds can present a major problem in the production plant. In this article, we present data and methodology on the kinetics of the thermal sterilization of No. 2 lard oil and soybean oil. It was also determined that dry heat sterilization condition could occur if dry spores were added to dry oil. This condition could only be partially alleviated by the addition of water to the oil. The theory and design of a small tubular coil continuous sterilizer for sterilizing oils at the point of use is also presented. This type of sterilizer is economical and versatile and simplifies control and instrument requirements. It provides a realistic alternative to the use of sterile feed tanks and sterile headers.
    Additional Material: 11 Ill.
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  • 18
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Proper design of fermentation facilities and equipment modification can control the risks associated with largescale production and purification of microbially produced cytotoxic agents and oncogenic viruses. The primary biohazard risks to operators and the environment are generation of aerosols and accidental spills. Fermentation and recovery facilities can be constructed to contain these agents by installing fermentation equipment within a HEPA-filter-exhausted biological barrier. Within this barrier system, large-scale processing that generates potentially hazaradous areosols (filtration, centrifugation of transformed cells or crystal slurries, and banding of viruses) should be isolated from other operations. Isolation of equipment is often required, with provision for both chemical and biological decontamination of process wastes. Failsafe fermentor over-pressure sensors, parallel exhaust gas filtration, welded transfer lines, and modified sampling systems for elimination of aerosols can be installed on most fermentation equipment. Aerosol and spill containment by proper equipment design, coupled with appropriate personnel protective equipment and medical monitoring, make possible safe production of experimental growth factors and viruses from large-scale culture of transformed mammalian cells and production of cytotoxic antitumor antibiotics.
    Additional Material: 22 Ill.
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  • 19
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effects of pretreatment process variables [straw concentration between 20 and 90 kg volatile solids (VS)/m3, temperature between 30 and 85°C, and alkaline dosage between 0 and 80 g NaOH/kg VS] on acidogenesis and methanogenesis were investigated. Rates of acidogenesis and methanogenesis were determined using firstorder kinetics, and ultimate acid and methane yields were measured. The acid yield was not affected by pretreatment concentration or temperature, but increased as alkaline dosage increased. The acidogenesis rate was not affected by pretreatment temperature or alkaline dosage, but decreased as the substrate concentration increased. This decrease in the acidogenesis rate was attributed to a decrease in the inoculum: substrate ratio as the substrate concentration increased. The methane yield and methanogenesis rate were not affected by pretreatment substrate concentration or temperature, and both increased with alkaline dosage up to about 40 g NaOH/kg VS, then remained relatively constant above 40 g NaOH/kg VS.
    Additional Material: 6 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 892-900 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Proteins have been immobilized in porous support particles held in a fixed-bed reactor through which protein solution is continuously circulated. Changing the recirculation flow rate alters the observed immobilization kinetics and the maximum enzyme loading which can be achieved for glucose oxidase and glucoamylase on carbodiimide-treated activated carbon and for glucoamylase immobilized on CNBr-Sepharose 4B. Direct microscopic examination of FITC-labelled protein in sectioned Sepharose particles and indirect activity-loading studies with activated carbon-enzyme conjugates all indicate that immobilized enzyme is increasingly localized near the outer surface of the support particles at larger recirculation flow rates. Restricted diffusion of enzymes may be implicated in this phenomenon. These contacting effects may be significant considerations in the scaleup of processes for protein impregnation in porous supports, since apparent activity and stability of the final preparation depend on internal protein distribution.
    Additional Material: 6 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 901-904 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Immobilized β-galactosidase was obtained by crosslinking the enzyme with hen egg white using 2% glutaraldehyde. The gel obtained could be lyophilized to give a dry enzyme powder. The pH optimum of both the soluble and immobilized enzyme was found to be 6.8. The immobilized enzyme showed a higher Km for the substrates. The extent of enzyme inhibition by galactose was reduced upon immobilization. The stability towards inactivation by heat, urea, gamma irradiation, and protease treatment were enhanced. The bound enzyme as tested in a batch reactor could be used repeatedly for the hydrolysis of milk lactose. The possible application of this system for small-scale domestic use has been suggested.
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  • 22
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 905-910 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Inulin, a polyfruction, is found as the reserve carbohydrate in the roots and tubers of various plants (i.e. Jerusalem artichoke, chicory, and dahlia tubers). The β-fructofuranosidase (inulase) from the yeast Kluyveromyces fragilis is of interest because of its industrial potential in fructose syrup and alcohol production from inulin containing plants. We have found that the inulase of K. fragilis can be immobilized in the yeast cells by glutaraldehyde treatment. These cells are resistant to physical and enzymatic destruction. Although the exact nature of the immobilization is not fully understood, the kinetic parameters of the immobilized enzyme are similar to those of the soluble enzyme. No reduction of enzyme activity was observed after glutaraldehyde treatment and glutaraldehyde concentration did not affect enzyme activity. A 96% hydrolysis of dahlia inulin was achieved in 10.5 h with a 9.5% (w/v) fixed enzyme suspension. A Jerusalem artichoke extract containing 16.8%polyfructan was completely hydrolyzed in 3.5 h with a 0.24% (w/v)fixed enzyme suspension. This is a time frame feasible for industrial consideration.
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  • 23
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 911-915 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An enzymatic method for the preparative resolution of racemic carnitine (whose L-isomer and its acyl-derivatives have numerous therapeutical applications) has been developed. It is based on our finding that electriceel acetylcholinesterase hydrolyzes the D- but not the L-isomer of acetylcarnitine. (Another cholinesterase tested, horse serum butyrylcholinesterase, is also stereospecific and hydrolyzes only the L-isomer of butyrylcarnitine.) Acetylcholinesterase, covalently attached to alumina, was employed for the resolution of D,L-carnitine; the latter was first chemically acetylated, then stereoselectively hydrolyzed with the immobilized enzyme, and finally the acetyl-L-carnitine and D-carnitine produced were separated by ion-exchange chromatography. Gram quantities of D,L-carnitine were thereby resolved.
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  • 24
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 916-925 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Based on the material balance principle applied to microbial reactions in continuous bioprocesses, the concept of reaction rate control has been developed theoretically. This concept provides a more direct way of controlling biological activities than the control of physical or chemical parameters in practice today. From an analysis of dynamic and steady-state experiments, two control systems for carbon dioxide production rate control during the continuous culture of baker's yeast have been designed and evaluated experimentally. In these control methods, intracellular NADH concentration is used as an immediate indication of the onset of glucose repression. A more sophisticated master controller based on the respiratory quotient can be combined with these control methods. The resulting control system provides a means to indirectly optimize biomass production while preventing ethanol formation in the continuous culture of baker's yeast.
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  • 25
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    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 926-935 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Methods are presented for examining the consistency of experimental data for microbial growth where light energy is converted to chemical energy through photosynthesis. True growth yield and maintenance parameters are estimated for several sets of available experimental data. Methods of parameter estimation are presented which allow all of the measured variables to be used simultaneously for parameter estimation. The results show that a wide range of values have been found for the true growth yield and maintenance parameters. Values of the true growth yield range from 0.04 to values above those predicted by the Z-scheme model for photosynthesis.
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  • 26
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    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 936-941 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two empirical models for the enzymatic hydrolysis of cellulose are used to analyze the same set of experimental data to determine if one model is superior to the other. Both models adequately describe the data. The parameters in both models may be correlated to the hydrolysis conditions of enzyme, substrate, and product inhibitor concentrations. Both empirical models have features which are consistent with theoretical models of cellulose hydrolysis.
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  • 27
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    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 942-947 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A simple operational strategy is shown to offer a viable means of enhancing plasmid stability in chemostat systems where plasmid loss is a common problem. Feedback control can be used to stabilize coexistence states, which are naturally unstable in the system investigated, and thus gurantee retention of the plasmid-carrying strain. The strategy exploits the normally undesirable characteristics of substrate inhibited growth kinetics, and is illustrated with specific reference to methanolutilizing organisms. Since the methodology may be easily implemented in practice, it offers an alternative to costly environmental methods such as antibiotic addition.
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  • 28
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    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 26 (1984), S. 583-589 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Enzymatic properties of Alcaligenes faecalis cells immobilized in polyacrylamide were characterized and compared with those reported for the extracted enzyme, and with those measured for free cells. Many of the properties reflected those of the extracted enzyme rather than those measured in the free whole cells prior to immobilization, suggesting cell disruption during immobilization. These properties included the pH activity profile, a slightly broader pH stability profile, and the activation energy. Electron micrographs showed evidence of cell debris among the polymer matrix. The immobilized cells were not viable, and did not consume glucose. Thermal stability was less after immobilization with a half-life of 16 h at 45°C, and 3.5 h at 50°C. The immobilized preparation was more stable when stored lyophilized rather than in buffer, losing 23 and 52% activity, respectively, after six months. The enzyme was irreversibly inhibited by both acetate and citrate buffers. If the immobilized enzyme is to be used in conjunction with cellulases from Trichoderma reesei for cellulase saccharification, the optimal conditions would be pH 5.5 and 45°C in a buffer containing no carboxylic acid groups.
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  • 29
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    Biotechnology and Bioengineering 26 (1984), S. 599-603 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new enzymatic method for the removal of phenols from industrial aqueous effluents has been developed. The method uses the enzyme polyphenol oxidase which oxidizes phenols to the corresponding o-quinones; the latter then undergo a nonenzymatic polymerization to form water-insoluble aggregates. Therefore, the enzyme in effect precipitates phenols from water. Polyphenol oxidase has been found to nearly completely dephenolize solutions of phenol in the concentration range from 0.01 to 1.0 g/L. The enzymatic treatment is effective over a wide range of pH and temperature; a crude preparation of polyphenol oxidase (mushroom extract) is as effective as a purified, commercially obtained version. In addition to phenol itself, polyphenol oxidase is capable of precipitating from water a number of substituted phenols (cresols, chlorophenols, naphthol, etc.). Also, even pollutants which are unreactive towards polyphenol oxidase can be enzymatically coprecipitated with phenol. The polyphenol oxidase treatment has been successfully used to dephenolize two different real industrial waste-water samples, from a plant producing triarylphosphates and from a coke plant. The advantage of the polyphenol oxidase dephenolization over the peroxidase-catalyzed one previously elaborated by the authors is that the former enzyme uses molecular oxygen instead of costly hydrogen peroxide (used by peroxidase) as an oxidant.
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  • 30
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    Biotechnology and Bioengineering 26 (1984), S. 604-612 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A dynamic mathematical model has been developed to describe microbial desulfurization of coal by Thiobacillus ferrooxidans. The model considers adsorption and desorption of cells on coal particles and microbial oxidation of pyritic sulfur on particle surfaces. The influence of certain parameters, such as microbial growth rate constants, adsorption-descrption constants, pulp density, coal particle size, initial cell and solid phase substrate concentration on the maximum rate of pyritic sulfur removal, have been elucidated. The maximum rate of pyritic sulfur removal was strongly dependent upon the number of attached cells per coal particle. At sufficiently high initial cell concentrations, the surfaces of coal particles are nearly saturated by the cells and the maximum leaching rate is limited either by total external surface area of coal particles or by the concentration of pyritic sulfur in the coal phase. The maximum volumetric rate of pyritic sulfur removal (mg S/h cm3 mixture) increases with the pulp density of coal and reaches a saturation level at high pulp densities (e.g. 45%). The maximum rate also increases with decreasing particle diameter in a hyperbolic form. Increases in adsorption coefficient or decreases in the desorption coefficient also result in considerable improvements in this rate. The model can be applied to other systems consisting of suspended solid substrate particles in liquid medium with microbial oxidation occurring on the particle surfaces (e.g., bacterial ore leaching). The results obtained from this model are in good agreement with published experimental data on microbial desulfurization of coal and bacterial ore leaching.
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  • 31
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    Biotechnology and Bioengineering 26 (1984), S. 613-619 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Batch growth tests were performed under both replicating and nonproliferating (no nitrogen source in medium) conditions with acclimated heterogenous populations that utilized phenol as a sole source of carbon and energy. It was shown that the acclimated populations could efficiently remove the toxic waste component phenol under nonproliferating conditions by utilizing an oxidative assimilation mechanism. The phenol was assimilated and converted into nonnitrogenous storage products. During the assimilation process, the cells had a tendency to excrete some product (nonsubstrate) chemical oxygen demand (COD). Bench-scale oxidative assimilation units were operated by sequentially feeding a carbon source (phenol) and nitrogen source (ammonium sulfate) to heterogeneous populations. This demonstrated that, subsequent to the addition of the nitrogen source to the medium, the cells utilized the stored carbon for replication. Four of these units were operated at different phenol COD-to-ammonia-nitrogen ratios of 10:1, 20:1, 40:1, and 50:1. All of these units demonstrated excellent removal of phenol using an oxidative assimilation mechanism. These results suggested the feasibility of utilizing a continuous flow oxidative assimilation process for the treatment of nitrogen-deficient phenolic wastes. This process would be advantageous over conventional treatment processes in that it would realize a savings in chemical costs (ammonia as nitrogen source) and prevent leakage of excess ammonia from the system.
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  • 32
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    Biotechnology and Bioengineering 26 (1984), S. 623-626 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 33
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 34
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    Biotechnology and Bioengineering 26 (1984), S. 1306-1312 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Frog epidermis tyrosinase has been immobilized on Enzacryl-AA (a polyacrylamide-based support) and CPGzirclad-Arylamine (a controlled pore glass support) in order to stabilize the tyrosine hydroxylase activity of the enzyme; in this way, the immobilized enzyme could be used to synthesize L-dopa from L-tyrosine. The activity immobilization yield YIMEact (higher than 86%), coupling efficiency (up to 90%), storage stability (no loss in 120 days), and reaction stability (t1/2 was higher than 20 h in column reactors) were measured for tyrosinase after its immobilization. The results showed a noticeable improvement (in immobilization yield, coupling efficiency, and storage and operational stabilities) over previous reports in which tyrosinase was immobilized for L-dopa production. The activity and stability of immobilized enzyme preparations working in three different reactor types have been compared when used in equivalent conditions with respect to a new proposed parameter of the reactor (Rp), which allows different reactor configurations to be related to the productivity of the reactor during its useful life time. The characteristic reaction inactivation which soluble tyrosinase shows after a short reaction time has been avoided by immobilization, and the stabilization was enhanced by the presence of ascorbate. However, another inactivation process appeared after a prolonged use of the immobilized enzyme. The effects of reactor type and operating conditions on immobilized enzyme activity and stability are discussed.
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  • 35
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    Biotechnology and Bioengineering 26 (1984), S. 1066-1070 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effectiveness of attaching flavin adenine dinucleotide (FAD) via a C bridge to Teflon-bonded carbon black (CB), and the subsequent immobilization of glucose oxidase on the FAD-modified electrodes has been studied by cyclic voltammetry. When FAD alone is bound to the electrode, it undergoes reduction and oxidation at -0.62 and -0.5 V, respectively - values similar to those obtained with free FAD. Compared to the free enzyme, the reduction of FAD as part of the immobilized enzyme is 200 mV more cathodic, while the oxidation potential remains the same in both cases.
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  • 36
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The massive conversion of δ-aminolevulinic acid (ALA) to protochlorophyllide (Pchlide) and the massive conversion of chlorophyllide a (Chlide a) to chlorophyll a (Chl a) are two essential conditions for the ALA-dependent assembly of photosynthetic membranes in vitro. In this work, we describe the development of a cell-free system capable of the forementioned biosynthetic activities at rates higher than in vivo, for the first 2 h of dark-incubation. The cell-free system consisted of (1) etiochloroplasts prepared from kinetin and gibberellic-acid-pretreated cucumber cotyledons, and (2) cofactors and additives described elsewhere and which are needed for the massive conversion of ALA to Pchlide, (3) high concentrations of ATP, MgCl2, and an isoprenol alcohol such as phytol, were required for the massive conversion of Chlide a to Chl a. An absolute and novel requirement of Mg2+ for the conversion of Chlide a to Chl a was also demonstrated. In addition to the role of phytol as a substrate for the conversion of Chlide a to Chl a, the data suggested that this alcohol may also be involved in the regulation of the reactions between ALA and Pchlide. It is proposed that during greening, the conversion of Chlide a to Chl a may follow different biosynthetic rates, having different substrate and cofactor requirements, depending on the stage of plastid development.
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  • 37
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    Biotechnology and Bioengineering 26 (1984), S. 1352-1363 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The growth dynamics of a methanol utilizing bacterium, L3, in batch bioreactors were experimentally investigated. Formaldehyde, a key intermediate of methanol oxidation, is indicated to have a significant role in the complex batch growth behavior of L3. The intricate batch growth dynamics of many microorganisms can be elegantly characterized by examining the specific rates of exchange of nutrients and products between the cells and the cellular environment. Following such an analysis, the batch growth of L3 on methanol was characterized by the presence of unbalanced and balanced growth phases. The nature and significance of nutrient and product concentration profiles or semilog-arithmic profiles of nutrient and product exchange rates during balanced and unbalanced growth phases are also outlined.
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  • 38
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    Biotechnology and Bioengineering 26 (1984), S. 508-512 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Addition of microcarrier beads to a matrix perfusion cell culture system allowed growth of anchorage dependent human foreskin fibroblasts which would not grow in the culture units alone. The utility of the system for collection of cellular products was demonstrated by the induction and harvesting of human (β) interferon. Interferon production was highest in perfusion cultures when medium was circulated throughout the induction and when inducer containing 100 μg/mL polyriboinosinic: polyribocytidylic acid was placed directly in contact with cells in the extracapillary space. These conditions provided 4-to-10-fold greater interferon yields per cell, and approximately 12-fold increases per vessel, than monolayer cultures. Perfusion grown cells produced interferon at a maximal level for 20 h postinduction compared to approximately 2 h for monolayer grown cells, thus giving a higher total yield of interferon. Other procedures increasing the efficiency of the system included priming with 50 U/mL interferon standard, reinduction of cells, use of antibiotic free medium, reduced serum concentrations, and in vitro aging of the cells.
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  • 39
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    Biotechnology and Bioengineering 26 (1984), S. 544-545 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 40
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    Biotechnology and Bioengineering 26 (1984), S. 1390-1392 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 41
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    Biotechnology and Bioengineering 26 (1984), S. 1395-1397 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 42
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    Biotechnology and Bioengineering 26 (1984), S. 1393-1394 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 43
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    Biotechnology and Bioengineering 26 (1984), S. 1398-1401 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 44
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    Biotechnology and Bioengineering 26 (1984), S. 1425-1429 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two-phase anaerobic digestion of liquid swine manure has been developed with options for single-cell protein (SCP) or methane production. In the acidogenic phase at two to four days retention time, and 2.5-7.0% dry matter (DM) concentration, 8-46% of the volatile solids was solubilized. Maximum reactor capacity was 3.86 g/L at 7.0% DM concentration, but optimal operation was achieved at 4.5% DM concentration at four days retention time. The second methanogenic phase was operated continuously and had a maximum specific methane production rate of 0.70 L/L day at 12 days retention time. With recirculation, the rate was 1.16 L/L day at 8.5 days retention time with 52.7% conversion of organic matter. Maximum digestibility was 66% of the lignin free organic matter.
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  • 45
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    Biotechnology and Bioengineering 26 (1984), S. 1430-1435 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This article presents a clear experimental determination of the behavior of nutrient uptake rate, mean cell nutrient content, and specific growth rate following the injection of pulses of additional limiting nutrient into a chemostat culture of Chlamydomonas reinhardii. The uptake rate per cell is a hyperbolic function of external nutrient concentration. The specific growth rate is related to the mean cell nutrient content by a hysteresis loop. The data obtained is used to test the performance of the Caperon-Droop mean cell quota model. It is demonstrated that this model cannot be used under severe transient conditions, even when modified by the introduction of a discrete time delay, a simple memory function, or time-dependent intracellular nutrient processing.
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  • 46
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    Biotechnology and Bioengineering 26 (1984), S. 1436-1444 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In many anaerobic fermentation processes, high energy bonds in adenosine triphosphate (ATP) are produced when available electrons are converted from organic substrate into extracellular organic products such as ethanol. The true growth yield and maintenance parameters are directly related to the product formation kinetic parameters for these anaerobic processes. Methods are presented which allow all of the experimental measurements to be used simultaneously to estimate these parameters. Results are presented for several different anaerobic fermentations.
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  • 47
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Lipase from Candida cylindracea has been found to be a highly stereospecific catalyst suitable for preparative resolution of racemic acids and alcohols. Using (R, S)-2-(p-chlorophenoxy) propionic acid (whose R isomer is a herbicide) and (R, S)-sec-butanol (a versatile synthon) as model compounds, three alternative approaches to lipase-catalyzed resolutions - asymmetric hydrolysis, esterification, and transesterification - have been compared. Enzymatic esterification in biphasic systems has been ruled out for preparative resolutions because addition of the acids lowers the pH of the aqueous phase thereby greatly reducing the efficiency of the procedure. Both enzymatic hydrolysis and biphasic transesterification afforded resolution of the racemates on a gram scale. From the standpoint of productivity, ease of product separation, and the amount of steps required, lipasecatalyzed asymmetric hydrolysis has been judged to be superior for the practical resolution of racemic acids, and lipase-catalyzed asymmetric transesterification to be the method of choice for the practical resolution of racemic alcohols.
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  • 48
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    Biotechnology and Bioengineering 26 (1984), S. 1475-1484 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Enzymatic corn starch liquefaction with α-amylase was carried out. Molecular weight distributions of the resulting hydrolysates are presented using aqueous size exclusion chromatographic techniques. It is demonstrated that despite the fact that the enzyme employed reacts in a random endoacting manner, the product distributions are nonrandom. The results are explained in part by a multimerization process whereby the polymeric substrate molecules preferentially associate, forming intermolecular aggregates. These aggregates are either a consequence of the manner in which the material is deposited into the native granular structure of starch or due to intrinsic physical chemical properties of the polysaccharide. In the latter case, the results are shown to correspond to known multimerized amylose, although complete characterization of the polysaccharide is currently not available. The results presented are used to develop a simplified kinetic model of starch liquefaction and shown to simulate the product distributions accurately.
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  • 49
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The design and operation of an industrial penicillin-V deacylation reactor is simulated, using a kinetic expression and mass transport parameters for the immobilized enzyme particles which were determined experimentally in a previous study. It is desirable to use a series of equalsized plug flow reactors with pH control at the entrance to each reactor, and with a possibility of recycling reactant in each reactor. These measures are necessary to avoid a steep pH profile through the reactor; the deacylation reaction is accompanied by an increase of acidity of the reaction medium, and H+ is a strong inhibitor and may deactivate the enzyme. The optimization study which is carried out at a fixed penicillin conversion of x = 0.99 shows that it is uneconomical to use penicillin feed concentrations above 150mM-175mM, and that the buffer concentration in the reaction medium should not be less than 50mM-75mM. Increasing the number of reactors from 4 to 8 or 10 leads to higher productivity of 6-APA, and a moderate recycle in the first couple of reactors diminishes the sharp decrease in pH which will be found in a straight plug flow reactor operation of the equipment. Higher pumping costs and lower productivity are unavoidable drawbacks of an operation mode where the separation costs for the product mixture are desired to be low.
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  • 50
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    Biotechnology and Bioengineering 26 (1984), S. 1498-1505 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Removal of hemicellulose by acid pretreatment in a flow reactor followed by enzymatic hydrolysis of the neutralized slurry has resulted in glucose yields as high as 95% for mixed hardwood. For white pine, however, the maximum glucose yield is 65%. Although pine has a higher extractives content, removal of the extractives prior to enzymatic hydrolysis does not increases the glucose yield. Pore size measurements reveal that the increase in pore volume, in the size range of the cellulase molecule, following pretreatment for pine is only about one-half the value obtained with mixed hardwood. This suggests that pore volume is an important determinant of substrate-enzyme reactivity.
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  • 51
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    Biotechnology and Bioengineering 26 (1984), S. 1140-1140 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 52
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    Biotechnology and Bioengineering 26 (1984), S. 670-676 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The use of alcohol/water/catalyst mixtures to delignify wood allows the lignin to be recovered in a usable form while leaving the carbohydrate fraction relatively intact. The effects of temperature, reaction time, and the type of solvent and catalyst on the delignification of milled poplar wood were investigated. The lignin, cellulose, and hemicellulose composition of the pretreated material was measured for each treatment condition. In addition, the pretreated samples were subjected to enzymatic hydrolysis using the cellulases produced by the thermophilic bacterium Thermomonospora sp. YX. The extent of enzymatic hydrolysis was characterized using an empirical model, and the results were used to examine the effectiveness of the pretreatment.
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  • 53
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    Biotechnology and Bioengineering 26 (1984), S. 682-686 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This article derives a number of equations which can be used in both continuous and the semicontinuous cultures of microorganism populations in chemostat systems. Using these equations, some phenomena which have been known for many years can be explained reasonably in terms of chemical kinetics, and a number of analytical solutions can be obtained instead of numerical solutions previously published.
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  • 54
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    Biotechnology and Bioengineering 26 (1984), S. 687-690 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The refractory organic sulfur compound dibenzothiophene (DBT) has been oxidized by the thermophilic, sulfur oxidizing organism Sulfolobus acidocaldarius. Sulfate ions were released into the medium as the oxidation product. The kinetics of this oxidation have been investigated on the basis of sulfate released as a result of oxidation. Dibenzothiophene was found to be inhibitory to the organisms for initial concentrations over 500 mg/L. The organism may prove to be capable of oxidizing thiophene compounds present in oil refinery wastewater, coal, and crude oil.
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  • 55
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    Biotechnology and Bioengineering 26 (1984), S. 677-681 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Chlorella sp. strain VJ79 was isolated from a total heterotrophic count of a wastewater collector. It grows autotrophically, heterotrophically, and mixotrophically on a variety of organic substrates. Glucose and serine promote a mixotrophic growth from which the yield is higher than the sum of autotrophic and heterotrophic yields, but serine assimilation requires light. The interaction of glucose and light was studied in proliferating and nonproliferating cells by respirometry (IRGA and Warburg) and growth experiments. Glucose inhibits the photosynthetic CO2 fixation ten-fold and modifies the pigmentary system as it does in heterotrophic cultures. Light inhibits glucose uptake and assimilation, but under mixotrophic conditions maximal utilization of glucose is obtained. Mutants defective in autotrophic growth were isolated by mutagenesis with nitrosoguanidine. They show a degenerated pigmentary system and a mixotrophic growth yield equal to that of the heterotrophic growth. The analysis of the mixotrophic system shows that light energy, dissipated during autotrophic growth, is used under mixotrophic conditions. From the increase in growth, the increase in photosynthetic efficiency can be calculated as ca. sixfold.
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  • 56
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    Biotechnology and Bioengineering 26 (1984), S. 691-698 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A theoretical description of a low-frequency, dual-source acoustic treatment of protein precipitates is presented. Two mechanisms for the potential improvement of the centrifugal separation of precipitates are proposed. They are acoustic aggregation, which causes an increase in particle size, and aggregate deformation, which results in an increase in aggregate density. Experiments with isoelectric soya protein precipitate indicated that the extent of ageing prior to acoustic conditioning is important. Support for both aggregation and dewatering was found and a maximum increases in the particle settling velocity of 20% was observed.
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  • 57
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    Biotechnology and Bioengineering 26 (1984), S. 699-701 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Wood waste powder from Tectona grandis containing melanin was less susceptible to enzymatic hydrolysis than powder without melanin. About a 53% increase in saccharification was noted when melanin was removed. Melanin caused inhibition to all cellulolytic enzymes, but in different degrees. Endo-β-1,4-glucanase and β-glucosidase were markedly inhibited when melanin was preincubated with enzyme, while exo-β-1,4-glucanase was severely inhibited when melanin was preincubated with substrate. The latter was found to be dependent on the contact time. The activities of endo-β-1,4-glucanase and β-glucosidase were noncompetitively inhibited by melanin.
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  • 58
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    Biotechnology and Bioengineering 26 (1984), S. 714-718 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Culture filtrates of Talaromyces emersonii UCG 208 grown on beet pulp can convert the polysaccharide components of this agricultural waste to soluble sugars. The saccharification process is facilitated if the pulp is milled or incubated with alkali or peracetic acid before addition of enzyme. However, treatment of unmilled pulp with commercial pectinase prior to incubation with Talaromyces filtrate is also very effective; under suitable conditions, complete hydrolysis of total polysaccharides has been achieved.
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  • 59
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    Biotechnology and Bioengineering 26 (1984), S. 702-713 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This study was performed to evaluate the effects of the air sparge rate, working liquid volume, liquid feed rate onto the disk, and disk diameter on the foam-breaking performance of foam-breaking apparatus with a rotating disk (FARD) installed in the bubble column. Experimental results showed that the smaller the air sparge rate and working liquid volume were, and the larger the liquid feed rate and disk diameter, the lower the critical disk rotational speed required for reduced foam-breaking. The presence of the effective ranges of the disk diameter and liquid feed rate for foam breaking was also confirmed. Furthermore, the quantitative predictions of the upper limits of the liquid feed rate, foam-breaking regions, and the required foam-breaking power were carried out, based on the results obtained above. Comparison of the FARD with two conventional mechanical foam-breaking spray-type apparati also demonstrated the highest level of the FARD in respect not only to foam-breaking performance but also to power requirements.
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  • 60
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    Biotechnology and Bioengineering 26 (1984), S. 719-726 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The influence of methanol dispersion and fluid mixing upon respiratory patterns observed during unlimited fedbatch growth of the methylotrophic bacterium Methylophilus methylotrophus has been investigated. A concentric tube air-lift fermenter was employed for which the mixing and fluid circulation patterns have been well characterized. Respiratory quotients showed a marked dependence upon the position in the vessel at which methanol was injected, the volumetric rate of such methanol addition, the fluid circulation time, and the local mixing behavior; the latter two factors of which are both determined by the air throughput. Such variations are discussed on the basis of simple mixing concepts and observations of fluid dispersion.
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  • 61
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    Biotechnology and Bioengineering 26 (1984), S. 727-736 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nonuniform enzyme distributions can be obtained by kinetic control of the immobilization process. Such heterogeneous biocatalysts exhibit higher effectiveness compared to conventional immobilization procedures, when the mass transfer of substrates or products is limiting. Model calculations provide some insight into the relative weight of the immobilization parameters with respect to optimal control of the enzyme distribution. Experimental results and model calculations show that considerably improved effectiveness of biocatalysts can be obtained. The role of external mass transfer is emphasized.
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  • 62
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    Biotechnology and Bioengineering 26 (1984), S. 737-741 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A catalase has been purified from aerobically grown Escherichia coli K12. The enzyme exhibits unorthodox properties compared with catalyse from bovine liver and seems to be identical to hydroperoxidase II from E. coli. A mathematical model is presented which makes it possible to calculate the steady-state concentration of hydrogen peroxide in an open system. The model has been verified experimentally. It has been shown that the catalase from E. coli is better suited than the bovine liver enzyme for oxygen supply to cell suspensions using hydrogen peroxide.
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  • 63
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    Biotechnology and Bioengineering 26 (1984), S. 742-747 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mutant of Saccharomyces cerevisiae, which forms large, multicellular flocs in liquid culture, rapidly fermented media containing high concentrations of glucose (100-180 g/L) in a continuous nonaerated tower fermentor at 30°C. The fermentor operated continuously for seven months. Batch and tower fermentor data were fitted to a kinetic model incorporating linear ethanol inhibition and Monod dependence on glucose. Conversion, ethanol yield, and ethanol productivity were related to the apparent fermentation time for initial glucose concentrations of 130 and 180 g/L. Productivities of 8-12 g ethanol/L h were achieved through the yeast bed giving conversions exceeding 90% of the theoretical yield.
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  • 64
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    Biotechnology and Bioengineering 26 (1984), S. 748-752 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Candida utilis was grown on a pineapple cannery effluent as the sole carbon and energy source in a chemostat at dilution rates between 0.10 and 0.62 h-1 to determine the growth kinetics. The principal sugars in the effluent were sucrose, glucose, and fructose. The cell yield coefficient on carbohydrate varied with dilution rate and a maximum value of 0.63 was observed at a dilution rate of 0.33 h-1. The steady-state concentrations of carbohydrate, reducing sugar, and chemical oxygen demand (COD) appeared to follow Monod saturation kinetics with increasing dilution rate, although none of the measured parameters represented a pure substrate. The maximum specific growth rate and reducing sugar saturation constant were 0.64 h-1 and 0.060 g/L, respectively. A maximum cell mass productivity of 2.3 g/L h was observed at a dilution rate of 0.51 h-1. At this dilution rate, only 68% of the COD was removed. A 95% COD removal was attained at a dilution rate of 0.10 h-1. Optimal yeast productivity and COD reduction occurred at a dilution rate of 0.33 h-1.
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  • 65
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    Biotechnology and Bioengineering 26 (1984), S. 788-796 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A washed carrot substrate, prepared with high yields and easy handling properties, was found to be a suitable substrate for studying cellulolytic and pectinolytic degradation processes. A cellulase from Trichoderma reesei, and Rohament P, a macerating enzyme from Aspergillus alleaceǔs in endopolygalacturonase, degraded the washed carrot substrate to an extent of 60%. With the combined action of both enzymes, degradation was more than 80%. Simultaneous action of both enzymes was more efficient than their sequential use. The effect of temperature, pH, incubation time, enzyme concentration, and substrate concentration on the degradation by the single enzymes and their mixture were studied. Gas chromatographic sugar analysis revealed that Rohament P liberated glucose, arabinose, and galactose in the low-molecular-weight fraction obtained by ultrafiltration, in addition to high amounts of galacturonic acid. These carbohydrates were also found in the high-molecular-weight fraction (retentate) together with rhamnose and mannose. Cellulase BC released mainly glucose, although galacturonic acid, arabinose, xylose, and mannose were also detected both in the ultrafiltrate and retentate. Morphologically, during Rohament P degradation of the washed carrot substrate, damaged tissues and disintegrated cells were seen, whereas on cellulase BC action mainly disintegrated cell walls were observed.
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  • 66
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    Biotechnology and Bioengineering 26 (1984), S. 797-799 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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    Biotechnology and Bioengineering 26 (1984), S. 800-802 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 68
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    Biotechnology and Bioengineering 26 (1984), S. 803-804 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 69
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    Biotechnology and Bioengineering 26 (1984), S. 805-806 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 70
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    Biotechnology and Bioengineering 26 (1984), S. 807-810 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 71
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    Biotechnology and Bioengineering 26 (1984), S. 811-813 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 72
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    Biotechnology and Bioengineering 26 (1984), S. 1233-1238 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A kinetic study of the enzymatic hydrolysis of two celluloses with different structural features was performed at various temperatures (26-50°C). The enzymatic system consisted of three types of enzymes: E1 - β-1,4-glucan glucanohydrolase; E2 - β-1,4-glucan cellobiohydrolase; and E3 - β-glucosidase. A mathematical model for the mechanism of the hydrolysis of cellulosic materials catalyzed by a multienzymatic system was checked and a good rationalization of the experimental results was achieved. Uncompetitive and competitive glucose inhibition on E1 and E2, respectively, appeared to occur for both substrates. Inhibition by cellobiose was checked at 34°C on one substrate. The Vmax, Km, and glucose inhibition constants were optimized and their dependence on temperature determined.
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  • 73
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    Biotechnology and Bioengineering 26 (1984), S. 1239-1244 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A novel algorithm for predicting BOD5 from the dissolved oxygen (DO) concentration after a relatively short incubation period is presented and evaluated experimentally. Test runs on synthetic and experimentally derived raw data suggest that BOD5 can be predicted to within 15% ca. 36 h. The method can be improved by filtering out, via a digital filter, noise from the raw data. The suggested algorithm does not require elaborate computations or large data storage and can therefore be implemented on a low-cost microcomputer for fast on-line determination of BOD5.
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  • 74
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    Biotechnology and Bioengineering 26 (1984), S. 1227-1232 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dihydrofolate reductase, purified to homogeneity from amethopterin-resistant Lactobacillus casei, was immobilized by coupling to cyanogen bromide-activated Sepharose or carbodiimide-activated CH-Sepharose. Coupling yields were determined by amino acid analysis following the hydrolysis of the gel. Enzyme activity was measured by the conventional spectrophotometric procedure, thus permitting the facile characterization of the immobilized enzyme. The pH optimum of the immobilized enzyme was shifted to 5.8 compared with pH 5.5 for the soluble enzyme. The immobilized enzyme retained greater than 90%of the initial activity over a six-month period and could be reused as many as ten times without loss of activity. As observed with the soluble enzyme, the activity of immobilized enzyme, which was lost on denaturation with 4M guanidine hydrochloride, was recovered rapidly and completely by washing the gel with buffer. The Kmapp values for dihydrofolate and NADPH for the immobilized enzyme were increased 15-164-fold over the Km values measured for soluble dihydrofolate reductase. Scatchard analysis of the interaction of amethopterin with the immobilized enzyme yielded linear plots and a Kdapp value of 0.56 ×10-8M, and revealed that all of the immobilized enzyme molecules were capable of binding the ligand.
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  • 75
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    Biotechnology and Bioengineering 26 (1984), S. 1245-1251 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The forces required to remove living, fully attached barnacles from the surface of a number of polymeric solids were measured. The forces were related to the surface energy components of the materials. The results indicate a positive correlation between polymer surface energy and force required for barnacle removal. The nonpolar component of the surface energy was more closely related to the removal force than the polar component, although the polar component is significant. Adherence to some composite materials was greater than was consistent with the correlation for noncomposites.
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  • 76
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    Biotechnology and Bioengineering 26 (1984), S. 1258-1260 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 77
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    Biotechnology and Bioengineering 26 (1984), S. 1261-1264 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 78
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    Biotechnology and Bioengineering 26 (1984) 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 79
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    Biotechnology and Bioengineering 26 (1984), S. 1313-1322 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The photosynthetic growth action spectrum of a green alga at three bands of visible light (blue, orange, and red) at fixed quanta input and under light-limiting conditions was measured in a batch cultivation system. Quantum efficiencies (biomass dry weight increment per quanta absorbed) were better in the yellow-red region than in the blue region. Results served as a basis for the design and optimization of a dye system that would shift the energy of solar radiation to the required wavelength range by absorbing ultraviolet to blue radiation and emitting in the yellow-red, thus enhancing algae growth. Direct incorporation of dyes into the growth medium, although theoretically expected to enhance growth, in fact resulted in dye decomposition, toxicity to algae and consequently in growth inhibition. Indirect application of dyes in a double tubular reactor (algae inside and dye solution outside) demonstrated growth enhancement for certain dyes with high quantum yields and stability, which had suitable absorption/emission spectra for artificial light sources used. The maximum indirect growth enhancement was obtained using rhodamine 6G at a concentration of 3×10-5M with tungsten filament lamp sources.
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  • 80
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    Biotechnology and Bioengineering 26 (1984), S. 1343-1351 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The immobilization of pullulanase and β-amylase on soluble polysaccharides (dextrans and amylose) has been carried out. The method used for coupling the enzymes to the carbohydrate support involves limited periodate oxidation of the polysaccharide followed by reductive alkylation with sodium cyanoborohydride or borohydride. The influence of the degree of functionalization of the carbohydrate, the incubation time, the nature of the reducing agent and, for the dextrans studied, their molecular weight, on the properties of the conjugate were studied. We have observed an apparent correlation between the molecular weight of the glycoprotein conjugates formed and their thermal stability, resistance to urea denaturation and their kinetic parameters. By selecting the proper experimental conditions leading to conjugates with maximum thermal stabilities, it has also been shown that β-amylase conjugates can hydrolyze starch at a temperature 20°C higher than the corresponding value for the native enzyme. This result demonstrates that conjugation may result in modified enzymes leaving a high operational stability at elevated temperatures. We suggest that the immobilization method presented in this article represents an approach to the stabilization of enzymes employed at an industrial level, which may be of general application.
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  • 81
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    Biotechnology and Bioengineering 26 (1984) 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 82
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2337-2350 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hetero-π-Systems, 7. SilabenzeneFlash pyrolysis of silacyclohexadiene derivatives 5k, 5m, and 7b yields silabenzene (1), which can be isolated in an argon matrix at 10 K. 1 exhibits characteristic IR and UV spectra. By photoexcitation a mutual interconversion between silabenzene (1) and dewarsilabenzene (2) can be achieved.
    Notes: Durch Kurzzeitpyrolyse der drei Silacyclohexadien-Derivate 5k, 5m und 7b läßt sich Silabenzol (1) erzeugen und in einer Argonmatrix bei 10 K isolieren. 1 zeichnet sich durch charakteristische IR- und UV-Spektren aus. Mittels photochemischer Anregung ist eine gegenseitige Umwandlung zwischen Silabenzol (1) und Dewarsilabenzol (2) zu erreichen.
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  • 83
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2452-2463 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photochemistry of 1,3,5-TristyrylbenzeneDepending on the reaction conditions the irradiation of the title compound 1 yields the cyclophane 5, the pyrene derivative 6, or the polycondensed aromatic system 9. An X-ray analysis was performed for 5, representing a new type of cyclophane in which two benzene rings are bridged again by rings.
    Notes: In Abhängigkeit von den Reaktionsbedingungen erhält man bei der Belichtung der Titelverbindung 1 das Cyclophan 5, das Pyrenderivat 6 oder das polykondensierte aromatische System 9. Für den neuen Cyclophantyp 5, bei dem zwei Benzolringe selbst wieder durch Ringe verbrückt sind, wurde eine Röntgenstrukturanalyse durchgeführt.
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  • 84
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2469-2478 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cyclopropenes as Complex Ligands: η4-Vinylketene Complexes of Manganese, Vanadium, and Cobalt; Preparative and X-ray Crystallographic ResultsThe reaction of 1,2,3-triphenylcyclopropene with (η5-C5H5)Mn(CO)3, (η5-C5H5)V(CO)4, (η5-C5H5)Co(CO)2 and Co2(CO)8 yields via ring opening and carbonylation the new compounds LMn(C5H5)CO (1), LV(C5H5)(CO)2 (2), LCo(C5H5) (3, 4) and L2Co2(CO)4 (6) (L = η4-C3Ph3HCO), respectively. In the reaction with (η5-C5H5)Co(CO)2 additionally the formation of 2,3-diphenylindenone (5) is observed. The X-ray structures of 1, 3 and 5 have been determined.
    Notes: Die Umsetzung von 1,2,3-Triphenylcyclopropen mit (η5-C5H5)Mn(CO)3, (η5-C5H5)V(CO)4, (η5-C5H5)Co(CO)2 und Co2(CO)8 ergibt unter Ringöffnung und Carbonylierung die neuen Verbindungen LMn(C5H5)CO (1), LV(C5H5)(CO)2 (2), LCo(C5H5) (3, 4) bzw. L2CO2(CO)4 (6) (L = η4-C3Ph3HCO). Bei der Reaktion mit (η5-C5H5)Co(CO)2 wird außerdem die Bildung von 2,3-Diphenylindenon (5) beobachtet. Die Röntgenstrukturen von 1, 3 und 5 wurden bestimmt.
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2495-2503 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 1401). Boron, Aluminium, and Gallium Halide Adducts of a Tetraaminodiboron CompoundThe tetraamino diboron compound 1 adds trihalides EX3 (E = B, Al, Ga, X = Cl, Br, I) to yield 1:1- and 1:2-coordination compounds. The BBr3 adduct 1b is thermally stable and shows nonfluxional behaviour in solution in contrast to the AlCl3 and GaCl3 adducts. The 1:2 adducts are nonfluxional and, according to NMR spectra, only the meso-form is present. The structure of the 1:1-adducts was ascertained by an X-ray structure determination of 1g. The single crystal contained R configurated molecules. A change from planar to the envelope conformation of the diazaborolidine ring occurs on adduct formation.
    Notes: Die Tetraaminodibor-Verbindung 1 lagert die Trihalogenide EX3 (E = B, Al, Ga; X = Cl, Br, I) zu 1:1- bzw. 1:2-Koordinationsverbindungen an. Von diesen zeigt nur das thermisch stabilere BBr3-Addukt 1b in Lösung im Gegensatz zu den AlCl3- und GaCl3-Addukten kein fluktuierendes Verhalten. Die 1:2-Addukte sind starr, und nach NMR-Spektren bildet sich nur die meso-Form. Die Struktur der 1:1-Addukte wurde durch Röntgenstrukturanalyse von 1g gesichert; die Einkristalle enthielten ein R-konfiguriertes Molekül. Durch die Addition nimmt der sonst planare Diazaborolidin-Ring Briefumschlag-Konformation an.
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  • 86
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2504-2509 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 1411). Unexpected Formation of a Bis(amino)borane: Synthesis and Structure of Bis(benzyl-tert-butylamino)boraneThe reaction of BCl3 with 3 molar equivalents of lithium benzyl-tert-butylamide produces the bis(amino)borane 2 in 29% yield. According to an X-ray structure determination the compound crystallizes in the monoclinic system, space group C2/c, and the molecule possesses almost C2 symmetry. The mean BN bond lenght is 142 pm, and the C2N planes are twisted by an average of 23.8° versus the HBN2 plane.
    Notes: Die Umsetzung von BCl3 mit 3 mol Lithium-benzyl-tert-butylamid liefert mit 29% Ausbeute das Bis(amino)boran 2. Nach Röntgenstrukturanalyse der monoklin in der Raumgruppe C2/c kristallisierenden Verbindung besitzt das Molekül nahezu C2-Symmetrie. Der durchschnittliche BN-Abstand beträgt 142 pm, und die C2N-Ebenen sind gegen die HBN2-Ebenen um durchschnittlich 23.8° verdrillt.
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  • 87
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2479-2494 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 139. Addition Compounds of Alkylhalogenoboranes with 1,3,2-Diazaborolidines: Structure, Stability, and Exchange ReactionsReactions of alkylhalogenoboranes RnBX3 - n (n = 0 - 2) with the 1,3-dimethyl-1,3,2-diazaborolidines 1 - 4 yield stable 1:1 addition compounds 1a - e, 2a, 3a - d, 4a irrespective of the boron substituents. Coordination of the borane moiety occurs at a ring N atom. An X-ray structure determination of the BCl3-adduct 3a shows two enantiomers in the asymmetric unit, envelope ring conformation, and strong π-bonding between the non-coordinated B an N atoms. - Equilibria of the 1:1 adducts with their ring cleavage products and their behaviour towards a second mol of BX3 was studied. In this case, replacement of the ring-BR group occurs. In contrast, haloboranes react with the 2-(dimethylamino)diazaborolidine 5 with R2N-substituent exchange while diborane yields in the first instance the (dimethylamino)borane adduct 5a.
    Notes: Umsetzungen von Alkylhalogenboranen RnBX3 - n (n = 0 - 2) mit den 1,3-Dimethyl-1,3,2-diazaborolidinen 1 - 4 führen unabhängig vom Bor-Substituenten zu stabilen 1:1-Additionsverbindungen 1a - e, 2a, 3a - d, 4a, wobei die Koordination über ein N-Atom des Fünfrings erfolgt. Die Röntgenstrukturanalyse des BCl3-Addukts 3a zeigt zwei enantiomere Formen in der asymmetrischen Einheit, “envelope”-Ringkonformation und eine starke π-Rückbindung des Ringbors zum nicht koordinierten Stickstoff. - Gleichgewichte der 1:1-Additionsverbindungen mit ihrem Ringöffnugsprodukt sowie ihr Verhalten gegenüber einem zweiten mol Lewis-Säure wurden untersucht. Hierbei wird die Ring-BR-Gruppe verdrängt. Im Gegensatz dazu tauscht das 2-(Dimethylamino)diazaborolidin 5 mit Halogenboranen den R2N-Substituenten aus, während die Umsetzung mit Diboran zunächst ein wenig stabiles (Dimethylamino)boran-Addukt 5a liefert.
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  • 88
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2527-2530 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition Metal Ketene Compounds, XXII. Anionic η2-Ketenyl Complexes of Molybdenum and TungstenAnionic η2-ketenyl complexes [NR4′]{η5-C5H5(CO) (CN)M[η2-O=C=C—R]} [M = molybdenum: 3a, b; M = tungsten: 4a - c] are formed by ligand substitution on neutral η2-ketenyl compounds as well as by reaction of dicarbonyl(η5-cyclopentadienyl)carbyne complexes with tetraalkylammonium cyanides.
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  • 89
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aminyl Oxides (Nitroxides), XXXV. The Tricyclic Dimer of a Vinyl Aminyl Oxide (Vinyl Nitroxide) and its Isomerization to give a 2,4,7,9-Tetraoxa-5,10-diazatetracyclo[4.4.2.03,12.08,11]dodecaneVinyl aminyl oxide 6 is formed by oxidation of hydroxylamine 3 via the intermediates 4 and 5. Dimerization of 6 yields the tricyclic compound 8. In solution dissoziation of 8 occurs at approximately 40°C, four bonds being cleaved to afford radical 6. By prolonged heating in various solvents as well as by proton catalysis at room temperature 8 is rearranged to give the tetracyclic isomer 9, the structure of which has been confirmed by X-ray analysis.
    Notes: Das Vinylaminyloxid 6 entsteht bei der Oxidation des Hydroxylamins 3 über die Zwischenstufen 4 und 5. 6 dimerisiert unter Bildung der tricyclischen Verbindung 8. 8 dissoziiert in Lösung bereits bei etwa 40°C unter Spaltung von vier Bindungen in das Radikal 6. Durch längeres Erhitzen in verschiedenen Lösungsmitteln, aber auch unter Protonenkatalyse bei Raumtemperatur, wird 8 in ein tetracyclisches Isomeres 9 umgewandelt. Die Struktur von 9 wurde durch Röntgenstrukturanalyse ermittelt.
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  • 90
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 91
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1-22 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 3-Metalated Enamines, X. Formation and Reactivity of 1-(Diethoxyphosphoryl)-1-(dimethylamino)allyl Anions1-Phosphorylenamines 8 and 10 react regio- and stereoselectively after deprotonation as anions 8A and 10A with silylating and alkylating reagents to give homologous (E)-1-phosphorylenamines 13, 15, 19 - 32. These can be hydrolyzed to give the corresponding carboxylic acids alkylated at C-3. Deprotonation of 10 occurs always on the methyl group cis to the phosphoryl group. The primarily formed anion isomerizes rapidly about the C-1 - C-2 bond. The highly regio- and stereoselective deprotonation allows the controlled introduction of up to three different alkyl groups. The results of NMR spectroscopic investigations of 8A and 10A are discussed.
    Notes: Die 1-Phosphorylenamine 8 und 10 reagieren nach Deprotonierung als Anion 8A und 10A regio-und stereoselektiv mit Silylierungs- und Alkylierungsmitteln zu homologen (E)-1-Phosphorylenaminen 13, 15, 19 - 32. Diese lassen sich zu den entsprechenden in 3-Stellung alkylierten Carbonsäuren hydrolysieren. Bei 10 erfolgt die Deprotonierung stets an der zur Phosphorylgruppe cis-ständigen Methylgruppe. Anschließend isomerisiert das primär gebildete Allyl-Anion rasch um die C-1 - C-2-Bindung. Diese hohe Regio- und Stereoselektivität der Deprotonierung gestattet die gezielte Einführung von bis zu drei verschiedenen Alkylgruppen. Die Ergebnisse der NMR-spektroskopischen Untersuchung von 8A und 10A werden diskutiert.
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  • 92
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2839-2849 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chromoionophores, 51). Chromoionophores with Azulene Units as Chromophores and π-Donor ComponentsThe synthesis and spectroscopic investigation of a series of new chromoionophores with azulene as chromophore and of suitable reference compounds are described. Cations complexed by the ionophore influence the chromophore, causing downfield shifts in the 1H NMR spectra and ion-selective changes in the absorption spectra. It is concluded that the chromophore can interact with the cations via carboxylic oxygen atoms or directly via the π-electrons of the azulene unit. Crystalline complexes of the azulene ligands 6 and 7 with alkali and alkaline-earth metal salts are synthesized. The geometry of the 7 · KSCN complex is examined by X-ray structure analysis.
    Notes: Synthese und spektroskopische Untersuchung einer Reihe von neuen Chromoionophoren mit Azulen als Farbträger und von geeigneten Vergleichsverbindungen werden beschrieben. Die Beeinflussung des Chromophors durch im Ionophorteil komplexierte Kationen verursacht in Lösung 1H-NMR-Tieffeldverschiebungen und ionenselektive Veränderungen in den Elektronenspektren. Daraus wird gefolgert, daß der Chromophor über Carboxyl-Sauerstoffatome oder direkt über die π-Elektronen des Azulens mit den Kationen in Wechselwirkung treten. Kristalline Komplexe der Azulen-Liganden mit Alkali- und Erdalkalimetallsalzen werden hergestellt. Die Geometrie des 7 · KSCN-Komplexes wird durch Röntgenstrukturanalyse ermittelt.
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  • 93
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2875-2885 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Unsaturated Aldehyde Dimethylhydrazones with Electrophilic ReagentsCrotonaldehyde dimethylhydrazone (1) is substituted at C-3 by electrophiles such as chlorine, bromine, iodine, arylsulfenyl chloride, phenylsulfinyl chloride, and nitronium tetrafluoroborate to form the products 10a  -  c, 18a, b, 25, and 26. In contrast, from 1 and p-nitrobenzoyl chloride the dienehydrazide 3 is obtained. Acrolein dimethylhydrazone reacts with diazoacetic ester to give the cyclopropane derivative 29. Isoxazole 32 is obtained from 28 and p-chlorobenzonitrile oxide.
    Notes: Crotonaldehyd-dimethylhydrazon (1) wird durch elektrophile Reagenzien wie Chlor, Brom, Iod, N-Chlorsuccinimid, Arylsulfenylchlorid, Phenylsulfinylchlorid oder Nitryl-tetrafluoroborat and C-3 unter Bildung der Produkte 10a  -  c, 18a, b, 25 und 26 substituiert. Bei Einwirkung von p-Nitrobenzoylchlorid auf 1 erhält man dagegen das Dienhydrazid 3. Acrolein-dimethylhydrazon (28) reagiert mit Diazoessigester zum Cyclopropanderivat 29, mit p-Chlorbenzonitriloxid zum Isoxazolin 32.
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  • 94
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2886-2899 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Partially Substituted Tetrazenes (Me3E)nN4H4 - n (E = Si, Ge, Sn): Preparation, Characterization, and Thermolysis1)Partially substituted tetrazenes (Me3E)nN4H4 - n (E = Si, Ge, Sn) can be prepared by protolysis of higher substituted tetrazenes (Me3E)oN4H4 - o (O 〉 n) or by silylation, germylation, or stannylation of lower substituted tetrazenes (Me3E)mN4H4 - m (m 〈 n). The obtained tetrazenes (Tab. 1) are colorless compounds; they have 2-tetrazene constitution, and trans-tetrazene configuration. The tetrazene (Me3Si)2N  -  N = N  -  NHX (X = H or GeMe3) isomerize by heating in dilute solution into (Me3Si)XN  -  N = N  -  NH(SiMe3). The thermolysis of (Me3Si)2N  -  N = N  -  NH(SiMe3) leads mainly to Me3SiN3 and (Me3Si)2NH (t140°C1/2140°C = 3/4 h), of (Me3Si)2N  -  N = NH2 to Me3SiN3 and Me3SiNH2 (concentrated solution; t140°C1/240°C ca. 1/4 h), and of (Me3Si)HN  -  N = N  -  NH(SiMe3) to N2 and (Me3Si)2N  -  NH2 (dilute solution; t140°C1/2140°C 〉 1 h) or to NH3 and (Me3Si)2NH (concentrated solution; t140°C1/2 〈 1 h).
    Notes: Teilsubstituierte Tetrazene (Me3E)nN4H4 - n (E = Si, Ge, Sn) können durch Protolyse höher substituierter Tetrazene (Me3E)oN4H4 - o (O 〉 n) oder durch Silylierung, Germylierung bzw. Stannylierung niedriger substituierter Tetrazene (Me3E)mN4H4 - m (m 〈 n) dargestellt werden. Die gewonnenen Tetrazene (Tab 1) sind farblose Verbindungen: sie haben 2-Tetrazen-Konstitution und trans-Tetrazen-Konfiguration. Die Tetrazene (Me3Si)2N  -  N = N  -  NHX (X = H oder GeMe3) isomerisieren sich in verdünnter Lösung beim Erhitzen in (Me3Si)XN  -  N = N  -  NH(SiMe3). Die Haupttermolyse von (Me3Si)2N  -  N = N  -  NH(SiMe3) führt zu Me3SiN3 und (Me3Si)2NH (t140°C1/2140°C = 3/4 h), von (Me3Si)2 (Me3Si)2N  -  N = NH2 zu Me3SiN3 und Me3SiNH2 (konzentrierte Lösung; t140°C1/240°C ca. 1/4 h) und von (Me3Si)HN  -  N = N  -  NH(SiMe3) zu N2 und (Me3Si)2N  -  NH2 (verdünnte Lösung; t140°C1/2140°C 〉 1 h) oder zu NH3t140°C und (Me3Si)2NH (Konzentrierte Lösung; t140°C1/2140°C 〈 1 h).
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  • 95
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2900-2909 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Assignment of Configuration of Larger Bicyclo[n.1.0]alkyl Amines: The Hexahydro-1-azepinyl Residue as „Stereo Indicator“The temperature dependency of the 1H NMR spectra of the hexahydro-1-azepinylbicyclo[9.1.0]-dodecanes 3a  -  f is investigated. The ΔG≠-values of the hexahydroazepine dynamics permit an easy assignment of the endo-amino configuration in 3a  -  f. Starting from 3a, which is synthesized via the enaminosulfonium salt 7, the derivatives 3b  -  f are obtained by nucleophilic substitutions. Normally the cis-configuration of the bicyclo system is not changed during these reactions. However, reaction of the cis-compound 3a with hexahydroazepine leads either to a cis-aminal 3e or to a trans-aminal 4e depending on the conditions of the reaction.
    Notes: Die aus der Temperaturabhängigkeit der 1H-NMR-Spektren der Hexahydro-1-azepinylbicyclo [9.1.0]dodecan-Derivate 3a  -  f ermittelten ΔG≠-Werte der Hexahydroazepinyl-Dynamik ermöglichen eine einfache Festlegung der endo-Amino-Konfiguration. Die Verbindungen 3b  -  f werden aus 3a über eine Folge nucleophiler Substitutionen erhalten; 3a ist über das Enaminsulfonium-Salz 7 zugänglich. Normalerweise bleibt die cis-Konfiguration des Bicyclosystems bei den Substitutionen erhalten. Jedoch führt die Umsetzung der cis-Verbindung 3a mit Hexahydroazepin  -  abhängig von den Reaktionsbedingungen  -  zu einem cis-Aminal 3e oder einem trans-Aminal 4e.
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  • 96
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2910-2927 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions with Aminobicyclo[n.1.0]alkanes, I Thermolysis of Aminobicyclo[n.1.0]alkanes with a Dimedone MoietyFrom the bicyclic aminals 4 and dimedone (5) derivatives 6 are obtained, which give different types of products upon thermolysis depending on the ring size of the bicyclus. The bicycloheptane and -octane compounds 6b, c lead to diacylated enamines 8b, c by protonation of the cyclo-propane ring. Contrarily, an elimination of morpholine takes place in 6a, d, e containing a bicyclohexane, -undecane, or -dodecane ring. There are formed derivatives with an exo-methylenefuran unit, which has a Z-configuration in 17a and an E-configuration in 16d, e. 16e the product of a kinetically controlled reaction, rearranges via the Z-isomer 17e to give the furan 18e by heating in morpholine. A methylenebicyclo[n.1.0]alkane 14 is discussed to be an intermediate in the formation of 16d, e and 17a, respectively.
    Notes: Aus den bicyclischen Aminalen 4, und Dimedon (5) werden Derivate 6 erhalten, die in Abhängigkeit von der Ringgröße des Bicyclus unterschiedliche Thermolyseprodukte ergeben. Die Bicycloheptan- und -octanverbindungen 6b, c, führen unter Protonierung des Cyclopropanrings zu Diacylenaminen 8b, c. Eine Eliminierung von Morpholin wird dagegen bei 6a, d, e mit einem Bicyclohexan-, -undecan- bzw. -dodecan-Ring beobachtet. Dabei entstehen Verbindungen mit einem exo-Methylenfuran-Strukturelement, das bei 17a in der Z- und bei 16d, e in der E-Konfiguration vorliegt. 16e, das kinetisch kontrollierte Reaktionsprodukt, kann durch Erhitzen in Morpholin über das Z-Isomere 17e zum Furan 18e umgelagert werden. Die Beteiligung einer Methylenbicyclo-[n.1.0]alkan-Zwischenstufe 14 beim Entstehen von 16d, e bzw. 17a wird diskutiert.
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  • 97
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 172-186 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Radical Ions, 55. The One-Electron Oxidation of Tetrahedrane to Cyclobutadiene Radical CationTetra-tert-butyltetrahedrane, on one-electron oxidation using AlCl3 in CH2Cl2, opens to form tetra-tert-butylcyclobutadiene radical cation, which can also be generated under identical reaction conditions from tetra-tert-butylcyclobutadiene itself. The assignments of the ESR and ENDOR spectra are supported by deutero substitution of one tert-butyl group and by MNDO hypersurfaces for the thermal and for the oxidative structural changes of both C4 skeletons. The feasible formation of a valence isomeric tert-butyl(tri-tert-butylcyclopropenyl)carbene radical cation is discussed.
    Notes: Tetra-tert-butyltetrahedran öffnet sich bei Einelektronen-Oxidation mit AlCl3 in CH2Cl2 zum Tetra-tert-butylcyclobutadien-Radikalkation, das unter gleichen Reaktionsbedingungen auch aus Tetra-tert-butylcyclobutadien erzeugt werden kann. Die Zuordnungen der ESR- und ENDOR-Spektren werden durch Deutero-Substitution einer tert-Butyl-Gruppe sowie durch MNDO-Hyperflächen für die thermischen und oxidativen Strukturänderungen der beiden C4-Gerüste gestützt. Die mögliche Bildung eines valenzisomeren tert-Butyl(tri-tert-butylcyclopropenyl)carben-Radikalkations wird diskutiert.
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  • 98
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    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 222-233 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Dynamic Behaviour of PentamethylcyclopentadienylphosphanesBy reaction of pentamethylcyclopentadienyl(Me5cp)-lithium with halogenophosphanes the Me5cp-phosphanes 1 - 5, 7, 8, 11, 12, 14, 15, and 19 - 24 are synthesized. Substitution reactions with the Me5cp-halogenophosphanes 7 and 14 lead to the Me5cp-phosphanes 6, 9, 10, 13, and 16 - 18. These molecules posses a fluxional structure owing to 1,5-sigmatropic rearrangements of the particular phosphorus group. It is demonstrated by 1H dnmr investigations and lineshape analyses, that the ligands at phosphorus influence drastically the speed of these rearrangements (activation energies between 5 and 31 kcal/mol).
    Notes: Durch Umsetzung von Pentamethylcyclopentadienyl(Me5cp)-lithium mit Halogenphosphanen werden die Me5cp-Phosphane 1 - 5, 7, 8, 11, 12, 14, 15 und 19 - 24 hergestellt. Substitutionsreaktionen an den Me5cp-Halogenphosphanen 7 und 14 führen zu den Me5cp-Phosphanen 6, 9, 10, 13 und 16 - 18. Diese Moleküle besitzen eine fluktuierende Struktur aufgrund von 1,5-sigmatropen Umlagerungen der jeweiligen Phosphorgruppierung. Durch 1H-NMR-Untersuchungen und Linienformanalysen wird gezeigt, daß die phosphorständigen Liganden die Geschwindigkeit dieser Umlagerungen drastisch beeinflussen (Aktivierungsenergien zwischen 5 und 31 kcal/mol).
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  • 99
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polyspiranes, 7. Cascade Rearrangements, 2: From Polyspiranes to Polycycles - Sixfold 1,2-Shifts in Functionalized Pentaspiro[2.0.2.0.2.0.2.0.2.1]hexadecanesThe pentaspirohexadecanes 3a, b may be rearranged to 8a, b via 7a, b, which are potential precursors of the [6.4]coronane 1. 7a and 8a were benzoylated to give 7d and 8e, respectively, the molecular structures of which were determined by X-ray analysis. 7a, b and 8a, b adopt the all-cis-configuration. 7a and 7b contain axial hydroxyl groups. The overall rearrangements of 3a, b may thus be described in terms of sixfold 1,2-shifts with inversion at both the migration origins and termini.
    Notes: Die Pentaspirohexadecane 3a, b können über 7a, b in 8a, b umgelagert werden. 7a, b sind potentielle Vorläufer des [6.4]Coronans 1. 7a und 8a wurden zu 7d bzw. 8e benzoyliert, die Molekülstrukturen von 7d und 8e röntgenographisch bestimmt. 7a, b und 8a, b sind all-cis-konfiguriert, 7a und 7b enthalten die Hydroxylgruppe axial gebunden. Die Gesamtumlagerungen von 3a, b können demnach als sechsfache 1,2-Verschiebungen unter Inversion am jeweiligen Ausgangs- und Endpunkt der Umlagerung beschrieben werden.
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  • 100
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 187-202 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Gas Phase Reactions, 40. Selenoformaldehyde: Highly Correlated Wave Function and Photoelectron Spectroscopic EvidenceA systematic search for the unknown molecule selenoformaldehyde, H2C = Se, starts with the precalculation of its ionization pattern from ab-initio-PNO-CI and CEPA wave functions. The selenium precursors H3CSeSeCH3, H3CSeCN, H3CSeCl, and (H2CSe)3 are pyrolyzed in a flow system under PE spectroscopic real-time analysis: Applying “computerized spectra stripping” to the PE spectra of the pyrolysis mixtures, an ionization pattern can be extracted which correlates satisfactorily with the quantum chemical prediction for H2C = Se. To further support the assignment, selenoacetaldehyde, CH3CH = Se, and selenocarbonyl difluoride, F2C = Se, are prepared by thermal monomerization of ((H3C)HCSe)3 and (F2CSe)2, respectively.
    Notes: Nach dem unbekannten Molekül Selenoformaldehyd, H2C = Se, wird systematisch gesucht, beginnend mit der Vorausberechnung seines Ionisationsmusters aus ab-initio-PNO-CI-und CEPA-Wellenfunktionen. Als Selen-Ausgangsverbindungen werden H3CSeSeCH3, H3CSeCN, H3CSeCl und (H2CSe)3 im Gasstrom unter PE-spektroskopischer Echtzeit-Analytik pyrolysiert: Aus den Pyrolysegemisch-Spektren läßt sich durch Spektren-Subtraktion mit Hilfe eines Rechners ein Ionisationsmuster herausschälen, das mit der quantenchemischen Voraussage für H2C = Se zufriedenstellend korreliert. Zur weiteren Stützung der Spektrenzuordnung werden Selenoacetaldehyd, CH3CH = Se, und Selenocarbonyldifluorid, F2C = Se, durch thermische Monomerisierung von ((H3C)HCSe)3 und (F2CSe)2 dargestellt.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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