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  • Inorganic Chemistry  (668)
  • Biochemistry and Biotechnology  (472)
  • 1985-1989  (1,140)
  • 1950-1954
  • 1986  (1,140)
Collection
Keywords
Publisher
Years
  • 1985-1989  (1,140)
  • 1950-1954
Year
  • 1
    Electronic Resource
    Electronic Resource
    Masthead (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986) 
    Details
    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
    URL: http://dx.doi.org/10.1002/bit.260280101
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  • 2
    Electronic Resource
    Electronic Resource
    Monitoring of protein product formation during fermentation with fast protein liquid chromatography (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 16-20 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method is described using fast protein liquid chromatography (FPLC) for the monitoring of protein formation during fermentation. The procedure consists of centrifugation to recover the cells, sonication of the cells, centrifugation to remove cell debris, and analysis of supernatant on a column of Mono Q (a strong anion exchanger). Analysis of peak areas provides quantitative determination of product concentration. Maintenance and life of the Mono Q column is discussed. We find that FPLC is a convenient method for measuring products in cell homogenates because it gives rapid, highly resolved separations.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280104
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  • 3
    Electronic Resource
    Electronic Resource
    Biosorption of uranium and lead by Streptomyces longwoodensis (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 21-28 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Biosorption of uranium and lead by lyophilized cells of Streptomyces longwoodensis was examined as a function of metal concentration, pH, cell concentration, and culture age. Cells harvested from the stationary growth phase exhibited an exceptionally high capacity for uranium (0.44 g U/g dry weight) at pH 5. Calculated values of the distribution coefficient and separation factor indicated a strong preference of the cell mass for uranyl ions over lead ions. The specific uranium uptake was similar for the cell wall and the cytoplasmic fraction. Uranium uptake was associated with an increase in hydrogen ion concentration, and phosphorus analysis of whole cells indicated a simple stoichiometric ratio between uranium uptake and phosphorus content. It is proposed that metal ions are bound to phosphodiester residues present both in the cell wall and cytoplasmic fractions. Based on this model, it was shown that uranium accumulation exhibits a maximum at pH 4.6 that is supported by experimental data from previous investigations.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280105
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  • 4
    Electronic Resource
    Electronic Resource
    The production of cellulase in a spouted bed fermentor using cells immobilized in biomass support particles (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 41-50 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Continuous cellulase production by Trichoderma viride QM 9123, immobilized in 6 mm diameter, spherical, stainless steel biomass support particles, has been achieved using a medium containing glucose as the main carbon source. Experiments were carried out in a 10-L spouted bed fermentor. In this type of reactor-recycled broth is used to create a jet at the base of a bed of particles, causing the particles to spout and circulate. During the circulation, particles pass through a region of high shear near the jet inlet. This effectively prevents a buildup of excess biomass and thus enables steady-state conditions to be achieved during continuous operation. Continuous production of cellulase was achieved at significantly higher yield and productivity than in conventional systems. At a dilution rate of 0.15 h-1 (nominal washout rate for freely suspended cells is 0.012 h-1), the yield of cellulase on glucose was 31% higher than that measured during batch operation, while the volumetric productivity (31.5 FPA U/L· h) was 53% greater than in the batch system. The specific cellulase productivity of the immobilized cells was more than 3 times that of freely suspended cells, showing that diffusional limitations can be beneficial. This offers significant opportunity for the further development of biomass support particles and associated bioreactors.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280107
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  • 5
    Electronic Resource
    Electronic Resource
    Parameters affecting optimum activity and stability of urokinase-bound fibrocollagenous tubes (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 64-72 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Urokinase was immobilized by entrapment to fibrocollagenous tubes in order to develop a small-caliber fibrinolytic vascular prosthesis. Several parameters associated with the immobilization process were studied in order to optimize bound urokinase activity and stability. A total of 37% of the absorbing enzyme was attached to the collagen tube and 38% of the attached enzyme retained esterolytic activity, under optimal conditions. In the crosslink step of the entrapment process, the glutaraldehyde concentration was varied from 0.01 to 5.00% (i.e., 0.01, 0.1, 1.0, 3.0, and 5.0%). Urokinase activity was optimized at a 1.0% glutaraldehyde crosslink concentration. Urokinase-bound fibrocollagenous tubes (UK-FCT) prepared at the above glutaraldehyde concentrations were tested for their activity with time. The UK-FCT's with 0.1, 1.0, and 3.0% glutaraldehyde retained constant activity for at least 75 h operation time. The UK-FCT's with 0.1, 1.0, and 3.0% glutaraldehyde retained constant activity for at least 75 h operation time. The UK-FCT's with 5.0 and 0.01% glutaraldehyde remained stable for the first 50 h operation time, but begandeactivating beyond 50 h. UK-FCT'S Crosslinked with 0.01, 0.1, 1.0, and 5.0% glutaraldehyde were recrosslinked with 0.02% glutaraldehyde for 24 h, after they have been operating for 50 h, and the effect of reexposing the crosslink agent on the stability of the UK-FCT's was studied. The results showed that 0.02% glutaraldehyde reexposure had no effect on 0.1, 1.0, and 5.0% glutaraldehyde crosslinked UK-FCT's but exerted an inhibitory effect on a 0.01% crosslink density UK-FCT. Several fibrocollagenous tubes were exposed to various glutaraldehyde concentrations prior to immobilizing urokinase. The subsequent immobilization process occurred under optimal conditions. The effect of the precrosslink step on the activity of the UK-FCT was studied. Results indicated that UK-FCT activity decreases as the precrosslink density increases. The UK-FCT's made under optimal conditions remained stable for at least 75 h operation time, corresponding to ca.1 year of storage time. Ex vivo exposure of UK-FCT's to whole canine blood did not affect catalytic activity. Implantation of a UK-FCT by carotid arterial interposition via an end-to-end anastomosis and subsequent excision after 60 days resulted in an enhanced esterolytic activity which decreased with time to a level close to preoperative levels.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280110
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  • 6
    Electronic Resource
    Electronic Resource
    Iron availability in mixed cultures of sulfate-reducing bacteria (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 101-106 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280114
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  • 7
    Electronic Resource
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    The polymeric p- and o-quinones as the reactive supports for the enzymes immobilization (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 110-111 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280116
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  • 8
    Electronic Resource
    Electronic Resource
    Simultaneous saccharification/fermentation with zymomonas mobilis (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 115-118 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280118
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  • 9
    Electronic Resource
    Electronic Resource
    An automatic and sterilizable sampler for laboratory fermentors: Application to the on-line control of glucose concentration (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 119-121 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: No Absract.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280119
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  • 10
    Electronic Resource
    Electronic Resource
    Release of cellulases from penicillium janthinellumNCL Communication No. 3517. (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 129-132 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280122
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  • 11
    Electronic Resource
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    Role of water activity in ethanol fermentations (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 29-40 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A separate role for water activity in the conversion of sugars to ethanol by two strains of yeast is identified. During fermentation of both single and mixed sugar substrates, the water activity was shown to remain constant during the logarithmic growth phase. This is despite the changes in concentration of substrates and product, the constancy reflecting the fact that the greater influence of ethanol on the solution activity is counterbalanced, in the early stages of the fermentation, by its low yield. The end of the log phase of growth coincides with the start of a period of gradually decreasing water activity. For the more ethanol-tolerant strain UQM66Y, growth was found to cease at a constant value of water activity while that for the less tolerant strain UQM70Y depended on both ethanol concentration and water activity. It is argued that water activity is a more appropriate variable than ethanol concentration for describing some of the nonspecific inhibitory effects apparent in ethanol fermentations. A straightforward method for the calculation of water activity during such fermentations based on the use of solution osmolality is presented.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/bit.260280106
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  • 12
    Electronic Resource
    Electronic Resource
    Immobilization of BSA, enzymes and cells of Bacillus stearothermophilus onto cellulose, polygalacturonic acid and starch based graft copolymers containing maleic anhydride (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 51-57 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Poly(maleic anhydride styrene) graft copolymers of cellulose, pectin polygalacturonic acid salt, calcium polygalacturonate, and starch were prepared and used to immobilize proteins. The cellulose grafts coupled quite appreciable quantities of acid phosphatase, glucose oxidase, and trypsin. However, the general retention of activity was somewhat disappointing. Further investigation with acid phosphatase showed that the amount of enzyme immobilized increased as the amount of anhydride in the graft copolymer increased but no such relationship existed for the enzymic activity. The cellulose graft copolymers were hydrolyzed and it appeared that the carboxyl group aided adsorption of the enzyme. Attempts to couple acid phosphatase using CMC through the free carboxyl groups, created by hydrolysis, gave only a small increase in the extent of protein coupling. However, the unhydrolyzed system gave a useful degree of immobilization of cells of Bacillus stearothermophilus, as did a poly(maleic anhydride/styrene)-cocellulose system. Attempts to improve the activity by using grafts based on other polysaccharide supports met with mixed success. Pectin products were soluble. Polygalacturonic acid products were partially soluble and extremely high levels of enzymic activity were obtained. This was probably due in part to the hydrophilic nature of the system, which also encouraged absorption of the enzyme. Attempts were made to reduce the solubility by using the calcium pectinate salt. Immobilization of acid phosphatase and trypsin resulted in inceased protein coupling but relatively poor activities were attained. A starch based system gave similar results. Calcium polygalacturonate was used to prepare an insoluble graft copolymeric system containing acrylonitrile-comaleic anhydride. The resulting gels gave excellent coupling with acid phosphatase which had a very good retention of activity.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280108
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  • 13
    Electronic Resource
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    A method for the determinations of the activity and optimal pH of glucose oxidase in an unbuffered solution (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 107-109 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280115
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  • 14
    Electronic Resource
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    A simple device for leaf luice coagulation (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 603-604 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280417
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  • 15
    Electronic Resource
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    Recent developments in hydrogen management during anaerobic biological wastewater treatment (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 585-602 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A comprehensive review of the microbial kinetics, energetics, and substrate specificities of anaerobic waste-water treatment systems is presented with descriptions of three different state-of-the-art reactor configurations. Each of these reactor systems is intended to enrich different populations of anaerobic acidogens and methan-ogens as a result of design and operational strategies for control of hydrogen and volatile acids. Imposition of these strategies results in different substrate utilization patterns, conversion kinetics, and operational stabilities as are currently being demonstrated in laboratory-scale investigations.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/bit.260280416
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  • 16
    Electronic Resource
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    The acetone butanol fermentation on glucose and xylose. II. Regulation and kinetics in fed-batch cultures (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 167-175 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetics in fed-batch cultures of acetone butanol fermentation by Clostridium acetobutylicum is compared on glucose, xylose, and mixtures of both sugars. The final conversion yield of sugars into solvents always increases with the sugar feeding rate. At low feeding rates, the sugar concentration in the medium becomes limiting, which results in a slower cellular growth, a slower metabolic transition from an acid to a solvent fermentation and, thus, a higher accumulation of acids. It is only at sufficiently high feeding rates that fed-batch fermentations yield kinetic results comparable to those of batch fermentations. With mixtures of glucose and xylose, because of a maintained low glucose level, both sugars are taken up at the same rate during a first fermentation period. An earlier accumulation of xylose when the fermentation becomes inhibited suggest that xylose utilization is inhibited when the catabolic flux of glucose alone can satisfy the metabolic activity of the cell. Kinetic results with batch and fed-batch fermentations indicate several important features of the regulation of C. acetobutylicum metabolism: an early inhibition by the produced acids; an initiation of solvent formation between 4 and 6 g/L acetic and butyric acid depending on the metabolic activity of the cell; a metabolic transition from acids to solvents production at a rate closely related to the rate of sugar uptake; during solvent production, a reassimilation of acids above a minimal rate of sugar consumption of 0.2 h-1; a final inhibition of the fermentation at a total butanol and acids concentration of ca. 20 g/L.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/bit.260280204
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  • 17
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    On-line adaptive control of a fed-batch fermentation of Saccharomyces cerevisiae (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 631-645 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The feasibility of applying an adaptive control technique to a fermentation process is investigated. The nonlinear, time-variant parameters of a fermentation process were estimated on-line as a series of linearized describing matrices. The matrices were used to update a suboptimal feedback law which controlled the process in real time over the linear region. Experiments were performed on a small-scale fully instrumented fermenter with the online, real-time adaptive control package. Results are presented for both single- and multivariable control, and indicate successful control of yeast cell growth.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/bit.260280502
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  • 18
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    Control of nitrate concentration in fermentations of Corynebacterium glutamicum (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 659-662 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A nitrate control system has been devised for the maintenance of stable nitrate concentrations throughout fed-batch fermentations of Corynebacterium glutamicum. The feedback control system was based on the use of a nitrate-ion-selective electrode to directly monitor the nitrate levels in the fermentor and an automatic controller to activate a nitrate feed pump. The electrode which was used for controlling the nitrate level was stable through-out the fermentation period. The apparent maximum specific growth rate, biomass production, protein production, biomass yields on glucose and nitrate, and amino acid production were all optimal at approximately 50mM nitrate.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/bit.260280504
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  • 19
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    Continuous hybridoma growth and monoclonal antibody production in hollow fiber reactors-separators (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 646-658 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Growth of a hybridoma culture, along with production of monoclonal antibody, was demonstrated over extended periods in polysulfone hollow fiber membrane modules. The molecular weight cutoffs of the membranes were 70,000, 50,000, and 100,000 daltons. The hybridoma cell line, designated 65/26, produced IgG (2b/κ) directed at mouse thymus cell surface antigen, TL.1. Cell growth occurred in the shell space of the reactor, using supplemented RPMI 1640 (20% fetal bovine serum) supplied from a separate reservoir vessel through the hollow fiber lumen. The reservoir contained 125 mL media, which was changed every 4 days. Concentrations of immunoglobulin were determined by an enzyme immunoassay (using protein A and alkaline phosphatase-labeled antibody conjugate). For the 10K, 50K, and 100K hollow fiber membrane modules, the maximum IgG concentrations detected in the 2.5-mL shell space were 47.5-80, 510, and 740 μg/mL, respectively. In the 125-mL reservoir for the 100K hollow fiber membrane module, the IgG concentration was measured at 260 μg/mL These values compare with an IgG concentration of 1 μg/mL when grown in a standard tissue culture flask and 3.2-7.6 μg/mL when grown in 100 ml media in a spinner flask. In addition, 10K and 50K hollow fiber membrane modules were run in a mode that decreased the fetal bovine serum supplement with time. Differences between these systems suggest that it is possible to obtain high IgG accumulation rates, both during and after the exponential growth phase of the hybridoma population.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/bit.260280503
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  • 20
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    Effects of mixing during acid addition on fractionally precipitated protein (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1056-1063 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Isoelectric fractionation of the two major proteins of soy is characterized. Fractions are acid precipitated and cen-trifugally collected at pH 6.0 (glycinin) and pH 4.8 (β-conglycinin). Two extremes in the speed of acid addition (rapid, with no mixing, and slow, via acid dialysis, with complete mixing) are compared to determine their effects on the properties of the precipitate. Total protein yield, fraction composition, and aggregate microstructure do not depend significantly on the method of acid addition. Particle size distribution and hindered settling behavior do differ and are explained using a model of aggregate strength. The rapid acid addition produces larger primary particles, because of higher supersaturation, and yields larger aggregates, because of higher interparticle potential and stronger aggregates. Further aggregation in low-shear hindered settling is faster for the slowly precipitated aggregate because few of these bonding sites could survive the high-shear precipitator, whereas more can contribute to aggregation during hindered settling.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/bit.260280716
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  • 21
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    INT-dehydrogenase test for activated sludge process control (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1080-1085 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dehydrogenase activity assay of activated sludge using the redox dye 2-(p-iodophenyl)-3-(p-nitrophenyl)-5-phenyltetrazolium chloride (INT) was investigated. INT-dehydrogenase activity (INT-DHA) was directly proportional to INT dosage and inversely proportional to bio-mass concentration over limited ranges. INT dosages exceeding 2.5m/M were toxic to dilute activated sludge suspensions. INT-DHA was greatest near pH 9, whereas the peak oxygen uptake rate (OUR) occurred at pH 8. Both INT-DHA and OUR varied inversely with sludge age, but INT-DHA was the more sensitive of the two parameters to this variable. Consistently good and highly significant correlations between INT-DHA and OUR of chlorine stressed activated sludge were found at sludge ages ranging 2.2-7.0 days.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/bit.260280719
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  • 22
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    Effect of pH oscillations on a competing mixed culture (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1127-1137 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two microorganisms, E. coli and S. cerevisiae, competing for glucose were maintained in a stable cycle of coexistence by alternating the growth advantage between the two organisms by oscillating the pH in a Chemostat. Pure culture experiments found S. cerevisiae to be insensitive to pH between 5 and 4.3 with a maximum specific growth rate (μmax) of 0.4/hr; while μmax of E. coli decreased from 0.6 h-1 at pH 5 to 0.1 h-1 at pH 4.3. Steady-state and cross-inoculation chemostat runs at a dilution rate of 0.17 h-1 confirmed the expectation that the mixed culture system is unstable at constant pH with E. coli dominating at pH 5 and S. cerevisiae dominating at pH 4.3. Three pH oscillation experiments were performed at D =0.17 h-1 with 1 g per liter glucose feed. The 16 h/16 h cycle was stable for six periods with a stable alternating cycle of E. coli and S. cerevisiae being quickly established. A 18 h pH 5/14 h pH 4.3 cycle was found to be stable with smaller yeast concentrations. A 6 h/6 h cycle was found unstable with yeast washout. Simulation results were compared with these runs and were used to predict the onset of instability. Oscillations of pH can force stable persistence of a competing mixed culture that is otherwise unstable. Thus, varying conditions are experimentally demonstrated to be one explanation for competitive coexistence.
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    URL: http://dx.doi.org/10.1002/bit.260280802
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  • 23
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    Effects of chemical modification on enzymatic activities and stabilities (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 256-268 
    Details
    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 chemical modification on the initial specific activity, residual activity, and deactivation kinetics of various enzymes is analyzed using a series mechanism. This straightforward multistate sequential model presented is consistent with the enzyme deactivation data obtained from different fields. The enzymes are placed in five different categories depending on the effect of chemical modification on initial specific activity and residual activity or stability. Wherever possible, structure-function relationships are described for the enzymes in the different categories. The categorization provides one avenue that leads to further physical insights into enzyme deactivation processes and into the enzyme structure itself.
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    Studies on the flocculation characteristics of Kluyveromyces marxianus (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 283-287 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 6 Ill.
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    Dilute acid hydrolysis of wheat straw hemicellulose at moderate temperature: A simplified kinetic model (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 288-293 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Wheat straw has been hydrolized with sulfuric acid at 34 and 90°C. The treatment at 90°C yields complete solubilization of hemicellulose to xylose and arabinose without significant amounts of furfural. The influence of acid concentration was studied and the kinetics of the acid-catalyzed hydrolysis has been modeled suggesting a two-consecutive reactions mechanism. This model is useful to explain the different behavior of the concentration of the two main sugars produced. The enhanced cellulose accessibility to enzymatic attack is also reported.
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    Extraction chemistry of fermentation product carboxylic acidsPresented in part before the 189th meeting of the American Chemical Society, Miami, Beach, FL, April 1985. (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 269-282 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Within the framework of a program aiming to improve the existing extractive recovery technology of fermentation products, the state of the art is critically reviewed. The acids under consideration are propionic, lactic, pyruvic, succinic, fumaric, maleic, malic, itaconic, tartaric, citric, and isocitric, all obtained by the aerobic fermentation of glucose via the glycolytic pathway and glyoxylate bypass. With no exception, it is the undissociated monomeric acid that is extracted into carbon-bonded and phosphorus-bonded oxygen donor extractants. In the organic phase, the acids are usually dimerized. The extractive transfer process obeys the Nernst law, and the measured partition coefficients range from about 0.003 for aliphatic hydrocarbons to about 2 to 3 for aliphatic alcohols and ketones to about 10 or more for organophosphates. Equally high distribution ratios are measured when long-chain tertiary amines are employed as extractants, forming bulky salts preferentially soluble in the organic phase.
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    Production of acetic acid by Clostridium thermoaceticum in batch and continuous fermentations (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 678-683 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Batch and continuous fermentations with Clostridium thermoaceticum (ATCC 39073) using automatic pH control were conducted. The value of μmax obtained from batch fermentation was about 0.14 h-1; acetate yield, which was both growth and non-growth associated, was about 2 mole of acetic acid/mole of glucose, compared with a theoretical maximum value of 3. This low yield, compared with literature data, may be explained by glucose loss through a combination of degradation routes. Continuous fermentation could be sustained for 1600 h or more without contamination problems. Continuous fermentation at high dilution rates indicates that μmax may be well above 0.17 h-1 when fresh feed medium is used. Acetate yields in continuous fermentation were about 77% of theoretical or 2.3 mole of acetic acid/mole of glucose.
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    Sugar cane bagasse as a possible source of fermentable carbohydrates. II. Optimization of the xylose isomerase reaction for isomerization of xylose as well as sugar cane bagasse hydrolyzate to xylulose in laboratory-scale units (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 684-699 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Both the forward and backward reactions of xylose isomerase (Sweetzyme Q) with xylose and glucose as substrates have been studied in terms of kinetics and thermodynamics. The relationship between the two reactions can thus be determined. Much attention has been given to the reaction with xylose as substrate. The optimal conditions of the xylose reaction in terms of pH, buffer, metal ions, substrate concentration, temperature, and ionic strength have been determined. These findings did not differ much from those reported for the glucose reaction. Equilibrium constants for the aldose to ketose conversion were more favorable in the case of glucose. The results obtained with continuous isomerization of xylose in columns packed with either Sweetzyme Q or Taka-Sweet were very similar to those obtained from batch isomerization processes. Particle size had a definite effect on reaction rate, which indicates that diffusion limitations do occur with the immobilized enzyme particles. Heat stability of Sweetzyme Q was good with t1/2 of 118, 248, and 1200 h at 70, 55, and 40°C, respectively. A novel method for the separation of xylose-xylulose mixtures with water as eluant on a specially prepared Dowex 1 × 8 column was developed. This technique has the capability of producing pure xylulose for industrial or research applications. A writ for a patent regarding this technique is at present prepared.
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    Kinetic considerations about the study of alcoholic fermentations of starch hydrolysate (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 711-717 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Alcoholic fermentations of starch hydrolysate by two different yeast strains, Saccharomyces cerevisiae(var. Vinal) and Saccharomyces oviformis(IMAP 383), have been studied in batch runs. In order to evaluate the different inhibition phenomena due to both substrate and product, a new kinetic equation is suggested.
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    Induction and elimination of oscillations in continuous cultures of Saccharomyces cerevisiae (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 700-710 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Continuous cultures of Saccharomyces cerevisiae are known to exhibit oscillatory behavior in the oxidative region. Important findings of a series of experiments conducted to identify the causes for initiation of and the means for elimination of oscillations in these cultures are reported in this paper. These oscillations are seen to be connected to the growth kinetics of the microorganism and are induced at very low glucose concentrations and at dissolved oxygen (DO) levels that are neither high nor low (DO values between 20 and 78% air saturation at a dilution rate of 0.2 h-1 and pH of 5.5 at 30°C). The oscillatory behavior is encountered over a range of dilution rates (0.09-0.25 h-1 at 30°C for pH = 5.5 and DO = 50% air saturation). The oscillations can be eliminated by raising the DO level above a critical value or by lowering the DO level below a critical value.
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    Electroenzymatic reactors with coenzyme regeneration: A theoretical approach (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 728-735 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A comparison of the relative performance of production techniques using coenzyme or cofactor electrochemical regeneration demonstrates the superiority of those processes in which the enzymatic reaction and the regeneration are conducted in the same reactor as opposed to those in which the reaction and regeneration are separated. For the former type of reactor, a method of calculation is proposed. This method is based on the solution of equations which describe the phenomena in modules representing three areas: the surface of the electrode, a layer where occur simultaneously the transport of material and the enzymatic reaction, and the bulk of the solution. This method is suggested for three types of reactor: those in which an enzyme solution is held close to an electrode by a semipermeable membrane, those in which an enzyme-charged membrane is in contact with an electrode, and those in which the enzyme is in solution in the vessel into which the electrode is dipped.
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    Granulation of biomass in thermophilic upflow anaerobic sludge blanket reactors treating acidified wastewaters (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 718-727 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The development of granular sludge in thermophilic (55°C) upflow anaerobic sludge blanket reactors was investigated. Acetate and a mixture of acetate and butyrate were used as substrates, serving as models for acidified waste-waters. Granular sludge with either Methanothrix or Methanosarcina as the predominant acetate utilizing methanogen was cultivated by allowing the loading rate to increase whenever the acetate concentration in the effluent dropped below 200 and 700 mg COD/L, respectively. The highest methane generation rates, up to 162 kg CH4-COD/m3 day, or 2.53 mole CH4/L day, were achieved at hydraulic retention times down to 21 min, with granules consisting of Methanothrix. The formation of Methanothrix granules did not depend on the type of seed material, nor on the addition of inert support particles. The growth of granules proceeded rapidly with adapted seed material, even when the reactors were inoculated with low concentrations. With mesophilic seed materials growth of granules took much longer. Thermophilic Methanothrix granules strongly resemble mesophilic granules of the “filamentous” type. Some factors governing the thermophilic granulation process are discussed.
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    Theoretical growth yield estimates for recombinant cells (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 741-746 
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    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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    Effect of immobilization on the physical and kinetic properties of soluble and insoluble trypsin-albumin polymers (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 736-740 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Bovine trypsin was crosslinked to human serum albumin (HSA) with glutaraldehyde to form soluble and insoluble copolymers. The physical and kinetic properties of trypsin and trypsin-HSA polymers were compared. Trypsin was heat labile, retaining only 24% of its enzymic activity after heating for 5 min at 60°C. In contrast, under the same condition both the soluble and insoluble trypsin-HSA polymers showed enhanced resistance to heat in-activation, retaining 81 and 100% of their original activities, respectively. The trypsin-HSA polymers also showed shifts in pH optima, an increase in activation energy, and a broadening of their pH stability profiles.
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    Masthead (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986) 
    Details
    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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    URL: http://dx.doi.org/10.1002/bit.260280901
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    Deactivation theory (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1277-1285 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A general model of enzyme deactivations involving unimolecular processes is introduced. For most mechanisms of this type, the parameters of the general model can be expressed in terms of actual physical parameters. The number of physical parameters that can be determined from the deactivation data cannot exceed the number of independent constants in the general model. When there is an excess of physical parameters, then some parameters must be determined from independent methods of analysis. If this is not possible, then some parameters must be left as lumped parameters or global parameters. The general form of the model can be useful in determining the number of independent, potentially active forms of the enzyme present during deactivation. Some exceptions to the general model are due to higher-order processes such as dissociation, autolysis, and biological contamination.
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    Bubble entrainment aeration for high-foaming fermentation (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 756-760 
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    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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    Synergistic effects of ethanol, octanoic, and decanoic acids on the kinetics and the activation parameters of thermal death in Saccharomyces bayanus (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 761-763 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Masthead (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986) 
    Details
    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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    URL: http://dx.doi.org/10.1002/bit.260280601
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    Elimination of bicarbonate interference in the binding of U(VI) in mill-waters to freeze-dried chlorella vulgaris (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 764-767 
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    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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    Morphology of yeast cell wall as affected by genetic manipulation of β(1 → 6) glycosidic linkage (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 769-784 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The morphology of yeast cells as it is affected by the glycosidic linkages of constituent glucan was studied. Four different strains of Saccharomyces cerevisiae were studied. A cell wall matrix particle representing the intact original morphology and composed entirely of β-glucan was prepared. Using prepared cell wall glucan particles, the morphology and cell wall matrix structure were examined. Genetic modification of the cell wall structure during growth results in the alteration of the shape and hydrodnamic volume of the intact cell wall particles. The shape and hydrodynamic volume of the cell wall particles can also be modified by in vitro chemical and enzymatic treatment. The shape factor and hydrodynamic volume of the whole glucan cell wall matrix particles were evaluated quantitatively using a rheological analysis. An increased degree of β(1 → 6) cross-linking in the cell wall matrix induces a nearly 2-fold increase in the shape factor and a 10-fold increase in the compression modulus of the glucan particles. The disruption of β(1 → 6) glycosidic cross-linking causes the particles to swell by up to 18% of their original volume. This was used as a strategy to isolate a yeast mutant with a high β(1 → 6) glycosidic content in the cell wall glucan.
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    Mechanized systems for media dispensing, inoculation, and replication of microorganisms (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1310-1317 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two instruments were developed to mechanize the handling of anaerobic microorganisms for microbial mutant isolation. The instruments automatically dispense liquid or agar medium to large and small 96-well platesand petridishes. Protocols were developed for inoculating different microorganisms, and calibration curves of number of areas or wells inoculated versus cell concentration were prepared for bacteria, yeast and fungi (spores). Experiments with yeast auxotrophic mutants and fungal spores showed that microbe inoculation follows Poisson statistics in distributing a single microorganism per inoculation point. The isolation and identification of Yarrowia lipolytica auxotrophic, morphological, and temperature-sensitive or tolerant mutants demonstrated the use of the instruments for microbial screening.
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    Butanol fermentation liquor production and separation by reverse osmosisNames of manufacturers or trade names are provided for information only and do not constitute and endorsement by any agency or department of Texas A&M University or any agency or department of the government of the United States. (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 785-791 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The problem of dilute solvent concentration in butanol-acetone fermentations can be solved by using reverse osmosis to dewater the fermentation liquor. Polyamide membranes have a potential application in a butanol-acetone fermentation and exhibited rejection rates as high as 98%. Optimum rejection of butanol in the fermentation liquor occurred at recoveries of 20-45%. Flux ranged from 0.05 to 0.6 L m-2 min-1.
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    Steam-explosion pretreatment of wood: Effect of chip size, acid, moisture content and pressure drop (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 792-801 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Material balances for pentosan, lignin, and hexosan, during steam-explosion pretreatment of aspenwood, showed almost quantitative recovery of cellulose in the water-insoluble fraction. Dilute acid impregnation resulted in more selective hydrolysis of pentosan relative to undesirable pyrolysis, and gave a more accessible substrate for enzymatic hydrolysis. Thermocouple probes, located inside simulated aspenwood chips heated in 240°C-saturated steam, showed rapid heating of air-dry wood, whereas green or impregnated wood heated slowly. Small chips, 3.2 mm in the fiber direction, whether green or airdry gave approximately equal rates of pentosan destruction and solubilization, and similar yields of glucose and of total reducing sugars on enzymatic hydrolysis with Trichoderma harzianum. Partial pyrolysis, destroying one third of the pentosan of aspenwood at atmospheric pressure by dry steam at 276°C, gave little increase in yield of reducing sugars on enzymatic hydrolysis. Treatment with saturated steam at 240°C gave essentially the same yields of glucose and of total reducing sugars, and the same yields of butanediol and ethanol on fermentation with Klebsiella pneumoniae, whether or not 80% of the steam was bled off before explosion and even if the chips remained intact, showing that explosion was unnecessary.
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    Behaviors of southern red oak hemicelluloses and lignin in a mild sulfuric acid hydrolysis (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 811-817 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Removal and modification of southern red oak hemicelluloses and lignin in a 0.05%(w/v) sulfuric acid hydrolysis were investigated. The hydrolysis profile was to raise the reaction from room temperature to 150°C for in 38 min and to extend the hydrolysis at 150°C for 1 h. At the end of the hydrolysis, 25.5% of red oak components were dissolved, of which 58% was xylose and 17% lignin. As the hydrolysis proceeded from room temperature to 150°C, a part of red oak xylan was removed to yield an oligomer fraction having maximal yield and average molecular weight of 3460 at 150°C. This fraction and the bulk xylan extracted during the first 30 min at 150°C were further degraded to give a lower molecular weight oligomer fraction, of which the yield and average molecular weight (2610) were highest at the end of the bulk removal of xylan. Red oak lignin, syringyl and guaiacyl units in particular, was increasingly removed with the progress of the hydrolysis. Lignin derivatives and a part of red oak extractives soluble in the hydrolysate were identified.
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    Optimization of CSTRs in series by dynamic programming (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 818-823 
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    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 concerns the development of a simple yet effective procedure for optimizing the design of a reactor system employing CSTRs in series. The basic approach used in this work was to translate the problem of reactor design to a mathematical programming model. The resulting model was then solved by dynamic programming. The procedure was tested on an IBM 3033 computer and an IBM PC-compatible machine, the CORONA PC-II microcomputer. The results of this study indicate that the optimization procedure developed is very effective.
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    Coexistence of S. cerevisiae and E. coli in chemostat under substrate competition and product inhibition (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1742-1752 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mixed culture of Saccharomyces cerevisiae and Escherichia coli was established in a stable coexistence steady state in a chemostat under constant operating conditions. The species competed for glucose, the growth-limiting resource, and produced acetate and ethanol. The acetic acid was shown to be very inhibitory to E. coli in pure culture at pH 5 while ethanol inhibition was only marginal. No significant inhibition of S. cerevisiae growth was observed by either acetate or ethanol. Pure culture parameters were measured and used in the analysis. Linearized stability analysis for the case when both organisms produce the inhibitor showed that a transition through three stable outcomes was possible as the feed concentration is lowered. Experimental studies verified these predictions, and successive transitions from a yeast growth steady state, to a coexistence steady state, and to an E. coli growth steady state were obtained by lowering the glucose concentration in the feed from 10 to 5 to 2.5 g/L, respectively. This dynamic behavior is distinct from the outcomes of other competition-inhibition combinations and experimentally demonstrates for the first time that coexistence is possible due to substrate competition and product inhibition.
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    Simultaneous utilization of methanol-glucose mixtures by Hansenula polymorpha in chemostat: Influence of dilution rate and mixture composition on utilization pattern (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1735-1741 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The utilization of mixtures of methanol (C1) and glucose (C6) of different composition by the methylotrophic yeast Hansenula polymorpha was studied in carbon-limited chemostat culture. For all mixtures tested a similar utilization pattern was observed: At low dilution rates both carbon sources were utilized simultaneously, but at high dilution rates the cells used glucose only and the unutilized methanol accumulated in the culture medium. When grown with C1 only, the cells exhibited a critical dilution rate Dc(C1) of 0.19 h-1, but when C1-C6 mixtures were used as the carbon and energy substrate, the yeast was able to completely utilize C1 at dilution rates considerably higher than Dc(C1). The dilution rate at which the transition from C1-C6 growth to C6 growth occurred (Dt) was strictly dependent on the composition of the C1-C6 mixture in the feed, and Dt increased with decreasing proportions of C1 in the mixture. During mixed substrate growth the formation of biomass from the two substrates was additive. The results reported indicate that the utilization of C1-C6 mixtures and hence Dt in H. polymorpha are subject to two different regulatory regimes. When the cells were growing with C1-C6 mixtures containing more than 60% C1, the transition form C1-C6 to C6 growth was most probably influenced by the maximum C1 oxidizing capacity of the cells, whereas for growth with mixtures containing less than 40% C1, a growth rate of 0.28-0.30 h-1 seemed to be the limiting barrier for the simultaneous utilization of the components of the binary carbon and energy substrate mixture.
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    Anaerobic calorimetry of Zymomonas mobilis using a heat-flux sensor (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1769-1773 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A relatively simple and inexpensive anaerobic calorimeter was designed and evaluated by using a Hy-Cal Engineering BI-7 bidirectional heat-flux sensor to measure heat output from magnetically stirred I-L flask fermentations. The production of ethanol and cumulative heat output by Zymomonas mobilis were both linearly proportional to glucose concentrations up to 160 g/L.
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    Regeneration of NAD+ cofactor by photosensitized electron transfer in an immobilized alcohol dehydrogenase system (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1774-1779 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The irradiation with visible light of a photosensitizer dye like methylene blue was used to regenerate by electron transfer the oxidized form of a pyridine nucleotide coenzyme (NAD+). The process has been studied on a common enzymatic reaction: ethanol oxidation by alcohol-NAD+ oxidoreductase immobilized on polyacrylamide gel or porous glass balls. In the experimental conditions used, the initial NAD+ recycling rates were 2.33 × 104 cycles/h (polyacrylamide) and 3 × 104 cycles/h (glass balls). A total number of 49.5 × 104 cycles was obtained for 13 runs of 2 h. The enzyme immobilization strongly increased its stability: after 28 days at 20°C, the residual activity was 25% of the initial value.
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    Ethanol production from starch by a coimmobilized mixed culture system of Aspergillus awamori and Zymomonas mobilis (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1761-1768 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The production of ethanol from starch by a coimmobilized mixed culture system of aerobic and anaerobic microorganisms in Ca-alginate gel beads was investigated. The mold Aspergillus awamori was used as an aerobic amylolytic microorganism and an anaerobic bacterium, Zymomonas mobilis, as an ethanol producer. By controlling the mixing ratio of the microorganisms in the inoculum size, a desirable coimmobilized mixed culture system, in which the aerobic mycelia grew on and near the oxygen-rich surface of the gel beads while the anaerobic bacterial cells mainly grew in the oxygen-deficient central part of the gel beads, was naturally established under the aerobic culture conditions, and ethanol could be directly produced from starch by the system. The ethanol productivity by the system in flask culture was particularly affected by the shear stress (dependent on the shaking speed) which controlled the mycelial growth on the surface of the gel beads. Under optimum culture conditions in the flask culture, the glucose produced was instantly consumed, and was not observed in the culture broth; the final concentration of ethanol produced from 100 g/L starch was 25 g/L and the yield coefficient for ethanol, Ypls, was 0.38. The ethanol productivity by the coimmobilized mixed culture system was compared with those by other various culture systems and the advantages of the system were clarified.
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    The application of a novel heat flux calorimeter for studying growth of Escherichia coli W in aerobic batch culture (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1780-1793 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The modification and principle of a novel heat flux calorimeter for the in situ, on-line measurement of the heat generated during microbial growth is described. Data concerning the physical characterization of the calorimeter as a fermentor, including stability and sensitivity of the heat signal, are presented. The calorimeter has been successfully applied to the study of the aerobic batch culture of Escherichia coli W on glucose under carbon and nitrogen limitation. A direct correlation between growth and heat evolution was obtained. Quantitative analysis of the data suggests that the new calorimetric technique could be used for monitoring growth and specific metabolic events, for convenient medium optimization, and as a basis for a novel fermentation process control system.
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    A model for the filterability of activated sludge supported by mixed-liquor biochemical data (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1801-1808 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A predictive model was developed to estimate the dewatering characteristics of waste-activated sludges. This model utilizes the COD-nitrogen ratio of the wastewater and the organic loading rate of the process to predict sludge filterability in terms of specific resistance. A completely mixed, continuous flow secondary treatment process with solids recycle was used for the cultivation of activated sludges. The sludge wasted from this process was used in Buchner funnel specific resistance determinations. The basic concepts involved in the development of the model were supported by sludge carbohydrate, protein, and surface charge data.
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    A method for estimating the rejection coefficient-molecular weight relationship of ultrafiltration membrane for a chain polymer by using gel permeation chromatography (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1809-1813 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An improved method is presented for estimating rejection coefficient-molecular weight relationship of an ultrafiltration membrane for a polydisperse chain polymer. It is based on the basic idea using gel permeation chromatography originally developed by Cooper and Van Derveer. The method, in which peak spreading of an elution curve of the polymer was taken into consideration, is available for evaluating the relationship over a wide range of the molecular weight through only one experiment in analyses of the retentate and filtrate.
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    Fabrication of reusable enzyme brushes for clinical analyses: Lactate dehydrogenase enzyme brush (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1611-1614 
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    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 procedure for the entrapment of enzymes in nylon-reinforced cellulose triacetate fibers and the fabrication of reusable enzyme brushes using such fiber bristles for the analytical determination of unknown samples have been described. As an example, enzyme brushes of lactate dehydrogenase were fabricated and were repeatedly employed for the determination of pyruvic acid in clinical samples in place of soluble enzymes. The above brush method compared well with that of wet enzymic analysis of pyruvate in clinical samples in accuracy, sensitivity, and reproducibility. The device also proved to be easy to handle, use, and reprocess for repeated analyses.
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    Photosynthesis in modulated light: Quantitative dependence of photosynthetic enhancement on flashing rate (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 988-995 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In order to predict the potential benefit associated with mixing devices designed to introduce periodic light modulations in dense cultures of microalgae, it is necessary to develop a quantitative understanding of the relationship between the frequency of the modulations and the resulting photosynthetic efficiency enhancement. To explore this relationship, the photosynthetic rate of cells of Phaeodactylum tricornutum from a dense steady state culture was determined as a function of modulation frequency, intensity of light received, and the proportion of the total cycle period during which the cells were illuminated. At high flash frequencies, the photosynthetic rate was determined by the average intensity received by the cells (full light intensity integration), while at low frequencies the cells responded to the instantaneous intensity (no light intensity integration). Full integration was approached asymptotically with increasing flash frequency. The frequency response could be described by a rectangular hyperbola, and the parameters of this hyperbola were nearly independent of the illumination intensity and the flash proportion. The saturation constant of the hyperbola, at which the response is one-half of the maximum, was 0.67 Hz.
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    Enzymatic formation of propylene bromohydrin from propylene by glucose oxidase and lactoperoxidase (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1007-1013 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The time course of the peroxidative bromination of propylene accompanied by in situ generation of hydrogen peroxide by glucose oxidase was examined to improve the productivity of propylene bromohydrin. To prevent the rapid inactivation of lactoperoxidase by excess hydrogen peroxide, it was effective to use lactoperoxidase in large excess as compared with glucose oxidase, and to raise the concentration of bromide ion. However, the rate of glucose consumption was lowered at high concentrations of bromide ion, and at higher mole fraction of oxygen as compared with propylene in the gas mixture. Therefore, it seemed that for the favorable production of bromohydrin there existed the optimal conditions for the concentration of bromide ion and for the composition of oxygen-propylene gas mixture. Such kinetic behaviors of the sequential enzymatic reactions were explained by a mechanism involving free hypobromous acid as a reactive intermediate. Furthermore, the stability of the coimmobilized enzymes with k-carrageenan gels was investigated in continuous operations. The half-life of the enzymes was ca. 60 h for the production of propylene bromohydrin.
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    Analysis of unstable recombinant Saccharomyces cerevisiae population growth in selective medium (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 996-1006 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Widely applied selection strategies for plasmid-containing cells in unstable recombinant populations are based upon synthesis in those cells of an essential, selection gene product. Regular partitioning of this gene product combined with asymmetric plasmid segregation produces plasmid-free cells which retain for some time the ability to grow in selective medium. This theory is elaborated here in terms of a segregated model for an unstable recombinant population which predicts population growth characteristics and composition based upon experimental data for stable strain growth kinetics, plasmid content, and selection gene product stability. Analytical solutions from this model are compared with an unsegregated phenomenological model to evaluate the effective specific growth rate of plasmid-free cells in selective medium. Model predictions have been validated using experimental growth kinetics and flow cytometry data for Saccharomyces cerevisiae D603 populations containing one of the plasmids YCpG1ARS1, YCpG1ΔR8, YCpG1ΔR88, YCpG1ΔH103, YCpG1ΔH200, pLGARS1, and pLGSD5. The recombinant strains investigated encompass a broad range of plasmid content (from one to 18 plasmids per cell) and probability α of plasmid loss at division (0.05 ≤ α ≤ 0.42). Experimental data for all strains considered is inconsistent with the hypothesis that plasmid-free cells are unable to grow in selective medium. For a given value of a, the fraction of plasmid-containing cells in the population decreases with increasing plasmid content and increases for less stable selection gene products. This conceptual framework and mathematical model will aid in strain development for greater effective stability.
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    Detailed study of anaerobic digestion of Spirulina maxima algal biomass (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1014-1023 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Biomass of the blue-green alga Spirulina maxima was converted to methane using continuous stirred tank digesters with an energy conversion efficiency of 59%. Digesters were operated using once-a-day feeding with a retention time (θ) between 5 and 40 days, volatile solid concentrations (Sto) between 20 and 100 kg VS/m3, and temperatures between 15 and 52°C. The results indicated a maximum methane yield of 0.35 m3 (STP)/kg VS added at θ 30 days and Sto 20 kg VS/m3. Under such conditions, the energy conversion of the algal biomass to methane was 59%. The maximum methane production rate of 0.80 m3 (STP)/m3 day was obtained with θ= 20 days and S = 100 kg VS/m3. The mesophilic condition at 35°C produced the maximum methane yield and production rate. The process was stable and characterized by a high production of volatile acids (up to 23, 200 mg/L), alkalinity (up to 20, 000 mg/L), and ammonia (up to 7000 mg/L), and the high protein content of the biomass produced a well buffered environment which reduced inhibitory effects. At higher loading rates, the inhibition of methanogenic bacteria was observed, but there was no clear-cut evidence that such a phenomenon was due to nonionized volatile acids or gaseous ammonia. The kinetic analysis using the model proposed by Chen and Hashimoto indicated that the minimum retention time was seven days. The optimum retention time increased gradually from 11 to 16 days with an increase in the initial volatile solid concentration. The kinetic constant K decreased with the improvement in the digester performance and increased in parallel with the ammonia concentration in the culture media.
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    Investigation of bacterial growth on mixed substrates: Experimental evaluation of cybernetic models (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1044-1055 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Cybernetic models, developed earlier by the authors, have been evaluated experimentally for the growth of Klebsiella oxytoca in batch cultures using mixed substrates from glucose, xylose, arabinose, lactose, and fructose. Based entirely on information procured from batch growth on single substrates, the models accurately predict without further parameter fitting, diauxic growth on mixed substrates, automatically predicting the order in which the substrates are consumed. Even triauxic growth on a mixture of glucose, xylose, and lactose is predicted by the model based on single substrate data. Growth on glucose-fructose mixtures appears to need a slightly modified strategy for cybernetic variables.
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    Operation and pressure distribution of immobilized cell hollow fiber bioreactors (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1064-1071 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It has been cited in the literature on hollow fiber systems that pressure gradients persist, and the transmembrane flux of the hollow fiber system is dependent on the pattern of the pressure gradients. The pattern can be used to its advantage in immobilized enzyme systems. However, with immobilized living cell systems, the pressure gradients lead to a nonuniform environment within the hollow fiber cartridge and not necessarily favorable results. This article provides pertinent pressure-drop data on hollow fiber cartridges which are in flow configurations typical of immobilized cell culture work. The results illuminate operational problems that may arise in the culture of either anchorage dependent or independent cells. Possible solutions with crossflow systems are suggested.
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    Phosphorylation of yeast protein: Reduction of ribonucleic acid and isolation of yeast protein concentrate (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1690-1698 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Yeast nucleoproteins were chemically phosphorylated with phosphorus oxychloride (POCL3). Studies using 31P nuclear magnetic resonance (NMR) spectroscopy, stability to pH and lysine estimation all indicated that the ∊-amino group of lysine was the principal functional group phosphorylated. Phosphorylation of ca. 30% of the lysine residues resulted in removal of more than 85% of contaminant ribonucleic acid from protein precipitated at pH 4.2. Phosphorylation did not alter the amino acid composition of yeast proteins and was reversible under acidic conditions. Based on the data, a method for the preparation of phosphorylated yeast protein with low levels of nucleic acid is proposed.
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    Mechanistically detailed model of cellular metabolism for glucose-limited growth of Escherichia coli B/r-A (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1672-1689 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A structured mathematical model for cellular metabolism in Escherichia coli has been extended to encompass the mechanistic structure surrounding the kinetics and control of transcription and translation. The dependence of transcription on RNA polymerase and the mechanism of translation initiation have been explicitly included. This model correctly simulates cell growth, cell composition, and the timing of chromosome synthesis as a function of extracellular substrate concentration for glucose-limited balanced growth. Simulation results for the subpopulation of RNA polymerase engaged in transcription and for the distribution of this subpopulation among different promoter sites agree closely with experimental findings, as do calculated estimates of the active ribosomal fraction. In addition, the existence of an antitermination system for transcription of stable RNA operons is supported by model results. This model should provide a useful framework for investigating metabolic perturbations to E. coli, such as those resulting from insertion of extra-chromosomal vectors into the cells.
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    Immobilization of Acetobacter acoti on cellulose ion exchangers: Adsorption isotherms (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1166-1171 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The adsorptive behavior of cells of Acetobacter aceti, ATCC 23746, on DEAE-, ECTEOLA-, TEAE-, and DEHPAE-cellulose ion exchangers in a modified Hoyer's medium at 30°C was investigated. The maximum observed adsorption capacities varied from 46 to 64 mg dry wt/g resin. The Langmuir isotherm form was used to fit the data, since the cells formed a monolayer on the resin and exhibited saturation. The equilibrium constant in the Langmuir expression was qualitatively correlated with the surface charge density of the resin. The adsorption was also “normalized” by considering the ionic capacities of the resins. The exceptionally high normalized adsorption capacity of ECTEOLA-cellulose, 261 mg dry wt/meq, may be explained by an interaction between the cell wall and the polyglyceryl chains of the exchanging groups in addition to the electrostatic effects. The effect of pH on the bacterial adsorption capacity of ECTEOLA-, TEAE-, and phosphate-cellulose resins was studied and the pl of the bacteria was estimated to be 3.0.
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    Validity of quasi-steady-state and transfer-function representations for input-output relation in a Michaelis-Menten reaction (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1191-1199 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In relation to the input-output characteristics of enzymatic reactions in the cellular metabolism and biochemical reactors, the validity of the quasi-steady-state and transfer-function representations of reaction velocity has been examined for a basic Michaelis-Menten reaction employing computer simulation, that is, numerical integration of the rate equation. The well-known S-v relationship (relationship between substrate concentration and reaction velocity)derived on the quasi-steady-state assumption is found to be in general a good approximation to the actual velocity throughout the temporal progress of the reaction. The validity of the approximation depends on a ratio of the Michaelis constant to the total enzyme concentration in the reaction system rather than on the individual rate constants. A transfer-function representation is derived on assuming an exponential change in the reaction velocity for the indicial response to the substrate influx rate. The representation has a wider valid region with a decrease in influx rate than with an increase in the influx rate. The validity is most dependent on a ratio of total enzyme concentration to the steady-state concentration of the substrate. The analysis of the linear sensitivity of the reaction velocity to rate constants reveals that the characteristics of these valid representations in systems analysis change according to the phase of the reaction.
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    Mathematical model of extractive fermentation: Application to the production of ethanol (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1206-1212 
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    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 for the process of extractive fermentation. The model rigorously treats the material balance, reaction kinetics, and liquid-liquid equilibrium relationships. Convergence is promoted through use of the Quasi-Newton Method. Extractive fermentation is particularly attractive for those bioreactions where the cell growth and product formation is inhibited by the product or other secondary cellular products. The model is illustrated for the production of ethanol. The results show an increase in specific productivity and the ability to process a more concentrated feed. However, volumetric productivity is reduced in the presence of a low capacity solvent.
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    Optimal substrate feeding policy for a fed batch fermentation with substrate and product inhibition kinetics (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1421-1431 
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    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The optimal substrate feeding policy for the fed batch fermentation which is governed by product and substrate inhibited kinetics is presented. The conjunction point between nonsingular and singular arcs and the feeding policy along the singular arc are derived analytically in terms of the concentrations of substrate and product and the liquid volume. Thus, it is possible to determine the feeding rate by monitoring the state variables (i.e., closed loop control). As a specific example, an optimization study of the fed batch fermentation for ethanol production by Saccharomyces cerevisiae is presented. It is shown that the optimal feeding patterns are heavily dependent upon the initial conditions. The point selectivity provides the guideline for predicting the optimal feeding patterns and explaining the results of rigorous mathematical analysis.
    Additional Material: 15 Ill.
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    Growth kinetics of Dioscorea deltoidea and Catharanthus roseus in batch culture (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1555-1563 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Sugar-limited batch growth of Dioscorea deltoidea and Catharanthus roseus plant cell cultures was studied in a 14-L stirred tank fermentor. With dissolved oxygen concentration monitored and maintained at nonlimiting levels, growth rates and ratios of dry weight to fresh weight were found to be strongly influenced by sugar concentration. Linear relationships between respiration rate and growth rate were observed, and respiration rate was found to drop to a maintenance level after sugar had been fully depleted from the medium. Diosgenin biosynthesis by D. deltoidea was shown to be independent of growth rate. Ajmalicine biosynthesis in C. roseus was negligible during sugar-limited growth but was induced by inoculation into an 80-g/L glucose solution.
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    Saccharification of concentrated brewing bagasse slurries with dilute sulfuric acid for producing acetone-butanol by Clostridium acetobutylicum (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 1544-1554 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A comprehensive kinetic study of the acid hydrolysis of concentrated brewing bagasse slurries was performed. The use of the simple series reaction model was found to be suitable when a “heterogeneous correction” (pseudosubstrate-inhibition) is taken into account in slurries with low liquid-to-biomass ratios. Rate constants are shown to be dependent not only on temperature and acid concentration but essentially also on the initial biomass concentration. Actual rate constants, activation energies, and acid and substrate reaction orders are reported for xylan, arabinan, and α-glucan acid saccharification. There is a threshold acid loading necessary to overcome the 80% conversion, but no threshold has been found to overcome the “neutralizing” property of cellulosic materials. Reversible acid capture from brewing bagasse has been postulated. The highest monosccharide concentration into hydrolyzates has been found (65 g/L) after 10 h treatment, but economic considerations led us to treat a mean-concentrated slurry (156 g/L) with 0.3M H2SO4 at 96°C, thus obtaining 45.5 g/L monosaccharides in 5 h with 50% less furfural content. After pH regulation only, growth of Clostridium acetobutylicum has been obtained, although complete sugar comsumption has not been achieved. Experiments are now underway to reach complete digestion and to investigate the increase of enzymic accessibility into residual substrate rich in cellulose.
    Additional Material: 12 Ill.
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    Niederkoordinierte Phosphorverbindungen, 45. Gemischt substituierte Bismethylenphosphorane durch Einwirkung von Carbenoiden auf Phosphaalkene (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1977-1985 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Low Coordinated Phosphorus Compounds, 45. Mixed Substituted Bismethylenephosphoranes by the Reaction of Carbenoides with PhosphaalkenesThe known methylenephosphanes 1a-e react with lithio-α-chloroorganyls 2a, b to give the bismethylenephosphoranes 3a-f in high yields. The compounds 3c-f represent the first mixed substituted λ5σ3-bismethylenephosphoranes, that except 3e, f could be isolated. Products 3e, f rearrange to the new phosphiranes 6a, b. The reaction of the methylenephosphane 1b with diphenyldiazomethane (4) leads via spectroscopic conceivable dihydrodiazaphosphole 5 to compound 3e. The course of the reactions, the spectroscopic data as well as the X-ray structure analyses of 3d and 6a are discussed.
    Notes: Aus der Reaktion der bekannten Methylenphosphane 1a-e mit Lithio-α-chlororganylen 2a, b erhält man in sehr guten Ausbeuten die Bismethylenphosphorane 3a-f. Die Verbindungen 3c-f sind die ersten gemischt substituierten Vertreter der λ5σ3-Bismethylenphosphorane, die mit Ausnahme von 3e, f isoliert werden können. Die Verbindungen 3e, f lagern in die neuen Phosphirane 6a, b um. Die Reaktion des Methylenphosphans 1b mit Diphenyldiazomethan (4) verläuft über ein spektroskopisch erfaßbares Dihydrodiazaphosphol 5 zum Produkt 3e. Die Reaktionsverläufe, die spektroskopischen Daten sowie die Röntgenstrukturen von 3d und 6a werden diskutiert.
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    Gehinderte Ligandbewegungen in Übergangsmetallkomplexen, XXXIII. (η2- und η4-Dien)[2-(η5-cyclopentadienyl)ethyl]molybdän-Carbonyle (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1994-2005 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hindered Ligand Movements in Transition Metal Complexes, XXXIII. (η2- and η4-Diene)[2-(η5-cyclopentadienyl)ethyl]molybdenum CarbonylsTricarbonyl[2-(η5-cyclopentadienyl)ethyl]molybdenum (1) reacts photochemically with 1,3-butadiene (2), (E)-1,3-pentadiene (3) or 2-methyl-1,3-butadiene (4), respectively, to give the corresponding η2- and η4-diene complexes. Stepwise, dicarbonyl[2-(η5-cyclopentadienyl)ethyl](η2-diene)molybdenum (5, 8, 11) and carbonyl[2-(η5cyclopentadienyl)ethyl](η4-diene)-molybdenum (6, 9, 12) are formed. Insertion of 1,3-butadiene into the Mo—C-σ-bond of 5 yields dicarbonyl[6-(η5-cyclopentadienyl)-η3-(E)-2-hexenyl]molybdenum (7) as a by-product. Similarily, 8 reacts to the corresponding [6-(η5-cyclopentadienyl)-η3-(E,E)-1-methyl-2-hexenyl] chelate complex 10. The η2-diene ligands in 5, 8, 11 show hindered rotation around the axis through the center of the center of the coordinated CC-double bond and the central atom. Two different rotamers can be observed at low temperatures. The energy barriers were determined by band shape analyses to be ΔG300300≠ = 62.0 ± 0.2 kJ/mol for 5, ΔG280≠ = 66.2 ± 0.2 kJ/mol for 8, and ΔG298≠ = 61.0 ± 0.2 kJ/mol for 11. Complex 9 is obtained in one, 12 in both of the two possible diastereomeric forms.
    Notes: Tricarbonyl[2-(η5-cyclopentadienyl)ethyl]molybdän (1) reagiert photochemisch mit 1,3-Butadien (2), (E)-1,3-Pentadien (3) bzw. 2-Methyl-1,3-butadien (4) zu den korrespondierenden η2- und η4-Dien-Komplexen. Stufenweise werden Dicarbonyl[2-(η5-cyclopentadienyl)ethyl](η2-dien)molybdän (5, 8, 11) und Carbonyl[2-(η5-cyclopentadienyl)ethyl](η4-dien)molybdän (6, 9, 12) gebildet. Insertion des 1,3-Butadiens in die Mo—C-σ-Bindung von 5 ergibt Dicarbonyl[6-(η5-cyclopentadienyl)-η3-(E)-2-hexenyl]molybdän (7) als Nebenprodukt. Gleichermaßen reagiert 8 zu dem entsprechenden [6-(η5-Cyclopentadienyl)-η3-(E,E)-1-methyl-2-hexenyl]-Chelatkomplex 10. Die η2-Dien-Liganden in 5, 8, 11 zeigen gehinderte Rotation um die Achse durch die Mitte der CC-Doppelbindung und das Zentralatom. Zwei unterschiedliche Rotamere können bei tiefen Temperaturen beobachtet werden. Die Energiebarrieren wurden durch Linienform-Analyse zu ΔG300≠ = 62.0 ± 0.2 kJ/mol für 5, ΔG280≠ = 66.2 ± 0.2 kJ/mol für 8 und ΔG298≠ = 61.0 ± 0.2 kJ/mol für 11 ermittelt. Komplex 9 ist in einer, 12 in beiden der zwei möglichen diastereomeren Formen erhältlich.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19861190620
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    Über sterisch gehinderte freie Radikale, XV. Das erste unsymmetrische Dimere aus zwei stabilen Radikalen: 3-(tert-Butylphenylmethylen)-6-(triphenylmethyl)-1,4-cyclohexadien aus tert-Butyldiphenylmethyl und Triphenylmethyl (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2006-2012 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sterically Hindered Free Radicals, XV. The First Unsymmetrical Dimer from Two Different Stable Radicals: 3-(tert-Butylphenylmethylene)-6-(triphenylmethyl)-1,4-cyclohexadiene from tert-Butyldiphenylmethyl and TriphenylmethylThe quinonoid title compound 6 is formed in an equilibrium to 95% and can be isolated, when the two title radicals 1 and 3 are generated in solution. The reason for this is the sterically less strained position of the bulky tBu group at the sp2-C atom of the methylene group. The structure of 6 is proved by 1,5-H migration giving 8 and autoxidation of the latter at -10°C giving tBuOH and 4-tritylbenzophenone (12). The synthesis of several analogous compounds are described.
    Notes: Die chinoide Titelverbindung 6 entsteht im Gleichgewicht zu 〉95% und kann isoliert werden, wenn die beiden Titelradikale 1 und 3 in Lösung erzeugt werden. Ursache hierfür ist die räumlich günstigere Unterbringung der sperrigen tBu-Gruppe am sp2-C-Atom der Methylengruppe. Die Struktur von 6 wird durch 1,5-H-Verschiebung zu 8 sowie dessen Autoxidation bei -10°C zu tBuOH und 4-Tritylbenzophenon (12) bewiesen. Synthesen analoger Verbindungen werden beschrieben.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190621
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    Stereoselective synthesis of alcohols, XXIII. Transfer of chirality on addition of (α-chloroallyl)boronates to aldehydes (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2013-2024 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereoselektive Synthese von Alkoholen, XXIII. Chiralitätsübertragung bei der Addition von (α-Chlorallyl)boronsäureestern an AldehydeDie Darstellung des (α-Chlorallyl)boronsäureesters 4 mit 92% e.e. wird beschrieben. Seine Addition an achirale Aldehyde ergab die Homoallylkohole 6 mit 82-92% e.e. Bei der Addition von ent-4 an Isopropylidenglycerinaldehyd (22) führte die kooperative Diastereoseitendifferenzierung zum Produkt 23 hoher Diastereomerenreinheit. In der Reaktion von 4 mit 22 ergab die Stereokontrolle durch das Reagenz den Alkohol 25 mit einer Diastereomerenreinheit von 77%.
    Notes: The preparation of the (α-chloroallyl)boronate 4 of 92% e.e. is described. Its addition to achiral aldehydes resulted in the homoallyl alcohols 6 of 82-92% e.e. Cooperative diastereoface selectivity on addition of ent-4 to isopropylideneglyceraldehyde (22) gave the product 23 of high diastereomeric purity. Reagent control of stereoselectivity on addition of 4 to 22 resulted in 25 of 77% diastereomeric purity.
    Additional Material: 1 Tab.
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    Reaktionen mit Aziridinen, 36. Arenhydride, 2. SN2- und SET-Reaktionen von N-Acylaziridinen mit Diphenylmethanid und „Naphthalinhydrid“ (Anion von Dihydronaphthalin) (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2050-2054 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions with Aziridines, 36 Arene Hydrides 2. SN2 and SET Reactions of N-Acylaziridines with Diphenylmethanide and „Naphthalene Hydride“ (Anion of Dihydronaphthalene)Diphenylmethane is incompletely deprotonated by sodium naphthalenide in THF so that some „naphthalene hydride“ 4 (anion of 1,4-dihydronaphthalene) remains present in the deprotonation equilibrium. The generated diphenylmethanide anion 3a reacts with the N-acylaziridines 6a-c to form the expected amidoethyl derivatives 7a-c in yields of less than 50%. The formation of by-products from 6b and 6c can be rationlized on the basis of classic ionic mechanisms. However, for 6a the by-product N-ethylbenzamide clearly points to a SET mechanism with „naphthalene hydride“ 4 as the electron source and with the radical 8 as a hydrogen source.
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    URL: http://dx.doi.org/10.1002/cber.19861190624
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    Der Einfluß von Phenylgruppen auf die Homokonjugation im Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anion. Eine 13C-NMR-Studie (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2025-2049 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Effect of Phenyl Groups on the Homoconjugation in the Bicyclo[3.2.1]octa-3,6-dien-2-yl Anion. A 13C NMR StudyThe effects of deuterium atoms in the positions 2 and 4 of exo-6-bromo- (11) and endo-6-methoxytricyclo[3.2.1.02,7]oct-3-ene (12) as well as exo-4-methoxybicyclo[3.2.1]octa-2,6-diene (13) on their 13C chemical shifts are in line with the previous interpretation of the effects in correspondingly deuterated bicyclo[3.2.1]octa-3,6-dien-2-yl anions 1, and thus provide evidence for the homoconjugative interaction in 1. 3-Phenylbicyclo[3.2.1]octa-2,6-diene (16) and endo- (19a) as well as exo-4-phenylbicyclo[3.2.1]octa-2,6-diene (19b) have been prepared from bicyclo[3.2.1]oct-6-en-3-one (14) and bicyclo[3.1.0]hex-2-ene-endo-6-carbaldehyde (17), respectively. 2,4-Diphenylbicyclo[3.2.1]octa-2,6-diene (6) and 19a, b were deprotonated by methyllithium and n-butyllithium, respectively, whereas the proton abstraction from tricyclo[6.3.1.02,7]dodeca-2,4,6,9-triene (4) and from 16 required potassium tert-butoxide/n-butyllithium. As products the corresponding bicyclo[3.2.1]octa-3,6-dien-2-yl anion derivatives have been identified. By means of potassium tert-butoxide/n-butyllithium 19a, b were converted into 21K, i.e. the anion with K+ as counterion. The NMR spectra of 21Li turned out to depend upon the temperature in the range between +45 and -30°C in contrast to those of 21K. The 13C NMR spectra of the anions and of the corresponding hydrocarbons are discussed in detail in relation to the spectra of the unsubstituted species 1 and 2. In particular, the wide variations of the chemical shifts of C-6,7 depending upon the substituents of the allylic moiety of the bicyclo[3.2.1]octa-3,6-dien-2-yl anion system give strong support for the bishomoaromatic nature of these anions.
    Notes: Die Effekte von Deuteriumatomen in den Positionen 1 und 4 von exo-6-Brom- (11) und endo-6-Methoxytricyclo[3.2.1.02,7]oct-3-en (12) sowie exo-4-Methoxybicyclo[3.2.1]octa-2,6-dien (13) auf deren 13C-chemische Verschiebungen stützen die frühere Interpretation der Effekte bei entsprechend deuterierten Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anionen 1 und belegen so die homokonjugative Wechselwirkung in 1.  -  Ausgehend von Bicyclo[3.2.1]oct-6-en-3-on (14) und Bicyclo[3.1.0]hex-2-en-endo-6-carbaldehyd (17) stellte man 3-Phenyl- (16) bzw. endo-4-Phenyl-(19a) und exo-4-Phenylbicyclo[3.2.1]octa-2,6-dien (19b) dar. 2,4-Diphenylbicyclo[3.2.1]octa-2,6-dien (6) und 19a, b wurden mit Methyllithium bzw. n-Butyllithium, Tricyclo[6.3.1.02,7]dodeca-2,4,6,9-tetraen (4) sowie 16 mit Kalium-tert-butoxid/n-Butyllithium deprotoniert, wobei die entsprechenden Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anionderivate 7, 21Li, 5 und 22 entstanden. Aus 19a, b wurde mit Kalium-tert-butoxid/n-Butyllithium auch 21K, d. h. das zugehörige Anion mit K+ als Gegenion erhalten. Die NMR-Spektren von 21Li erwiesen sich im Gegensatz zu jenen von 21K im Bereich von +45 bis -30°C als temperaturabhängig. Die 13C-NMR-Spektren der Anionen und der zugehörigen Kohlenwasserstoffe werden im Vergleich mit den Spektren der unsubstituierten Verbindungen 1 und 2 ausführlich diskutiert. Insbesondere die starken Variationen der chemischen Verschiebungen von C-6,7 in Abhängigkeit von den Substitutenten am Allylteil des Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anionsystems bieten ein starkes Argument für die bishomoaromatische Natur dieser Anionen.
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    URL: http://dx.doi.org/10.1002/cber.19861190623
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    Masthead (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986) 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190701
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    3-Alkylchinolizinium-iodide aus metalliertem α-Picolin und 3-Ethoxyacroleinen (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2062-2065 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3-Alkylquinolizinium Iodides from Metalated α-Picoline and 3-Ethoxyacroleins2-Alkylquinolizinium iodides 4 are obtained in good overall yields by treating lithiated 2-methylpyridine 1 with 2-alkyl-3-ethoxyacroleins 2. 3-Alkyl-4-ethoxy-1-(2-pyridyl)-3-buten-2-ols 3 are isolated as primary products which readily cyclize to give the title compounds 4 upon heating in aqueous hydrogen iodide.
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    URL: http://dx.doi.org/10.1002/cber.19861190627
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    Functionally substituted vinyl carbanions, 29. Reaction of a β-lithiated acrylate with oxetanes as electrophiles (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2066-2068 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Funktionell substituierte Vinylcarbanionen, 29. Reaktion einer β-lithiierten Acrylsäure mit Oxetanen als Electrophilβ-Lithiiertes β-(Ethylthio)acrylat 1A reagiert mit den Oxetanen 2 bzw. (±)-5 in Anwesenheit von Bortrifluorid-Ether zu den entsprechenden γ-hydroxypropyl-substituierten Derivaten 3 bzw. 6. Von den 2-Alkyl/phenyl-3-ethoxy-oxetanen (±)-5 reagieren die erythro-Derivate deutlich rascher als die threo-Derivate.
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    1,3-Dioxetanylium-Ionen als Zwischenstufe bei der anodischen Oxidation O-benzoylierter α-Hydroxyessigsäuren? (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2173-2177 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Anodic Oxidation of O-Benzoylated α-Hydroxyacetic Acids Concerning the Structure of the Cationic IntermediateAnodic oxidation of ([carbonyl-18O]benzoyloxy)acetic acid (1b) at graphite electrodes in methanol leads to the substitution product methoxymethyl benzoate (3) as well as the fragmentation product methyl benzoate (4) recovering all labeled oxygen in the carbonyl groups. This result proves that the 1,3-dioxetanylium ion 2′ is not involved in the non-Kolbe electrolysis of O-benzoylated α-hydroxyacetic acids. The cationic intermediate 2 is of open-chain structure.
    Notes: Die anodische Oxidation von ([Carbonyl-18O]Benzoyloxy)essigsäure (1b) an Graphitelektroden in Methanol liefert unter Erhaltung des markierten Sauerstoffs in der Carbonylposition das Substitutionsprodukt Benzoesäure-methoxymethylester (3) und das Fragmentierungsprodukt Benzoesäure-methylester (4). Damit wird die Beteiligung eines 1,3-Dioxetanylium-Ions 2′ an der Elektrolyse von O-benzoylierten α-Hydroxyessigsäuren ausgeschlossen. Die kationische Zwischenstufe 2 ist offenkettig.
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    Neue Synthesen von 2-Acylbenzofuranen, 2-Acylindolen, 2-Indolycarbonsäureestern und 2-Chinolonen durch intramolekulare Wittig-Reaktion (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2069-2074 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New Syntheses of 2-Acylbenzofurans, 2-Acylindoles, 2-Indolylcarboxylates, and 2-Quinolones by Intramolecular Wittig ReactionThe title compounds are obtained by intramolecular Wittig reaction of 2-(α-ketoacyloxy)-, 2-(α-ketoacylamino)-, or 2-[(ω-alkoxycarbonylacyl)amino]benzyltriphenylphosphonium salts, respectively.
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    URL: http://dx.doi.org/10.1002/cber.19861190629
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    Beiträge zur Chemie des Bors, 173. Über Salze des Bis(diisopropylamino)bor(1+)-Kations (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2075-2079 
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    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, 173. Salts of the Bis(diisopropylamino)boron(1+) CationBromobis(diisopropylamino)borane (1) reacts with aluminium and gallium tribromide to produce stable salts of type [(iPr2N)2B]EBr4 (2, 3). Silver triflate converts 1 into bis(diisopropylamino)[(trifluoromethyl)sulfonyloxy]borane (4), while silver tetratriflatoborate produces a mixture of 4 with the salt [(iPr2N)2B]B(OSO2CF3)4 (6). Furthermore (diisopropylamino)bis[(trifluoromethyl)sulfonyloxy]borane (7) is formed.
    Notes: Bis(diisopropylamino)borbromid (1) reagiert mit Aluminium-oder Galliumtribromid zu den stabilen Salzen [(iPr2N)2B]EBr4 (2, 3), während 1 mit Silber-triflat Bis(diisopropylamino)-[(trifluormethyl)sulfonyloxy]boran (4) liefert. Silber-tetratriflatoborat setzt sich mit 1 zu einem Gemisch von 4 mit dem Salz [(iPr2N)2B]B(OSO2CF3)4 (6) um. Ferner entsteht (Diisopropylamino)bis[(trifluormethyl)sulfonyloxy]boran (7).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190702
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    Synthese und physikalische Eigenschaften neuer 1,3-Dithiolylium-4-methanide und 1,3-Thiazolium-5-methanide (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2094-2103 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Physical Properties of Novel 1,3-Dithiolylium-4-methanides and 1,3-Thiazolium-5-methanidesThe synthesis and physical properties of the novel title compounds of type 9 from carboxylic acid derivatives 3 and CH acidic compounds 4 are described.
    Notes: Die Synthese und physikalischen Eigenschaften der neuen Titelverbindungen vom Typ 9 aus Carbonsäure-Derivaten 3 und CH-aciden Verbindungen 4 werden beschrieben.
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    URL: http://dx.doi.org/10.1002/cber.19861190704
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  • 83
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    Neue schwefelverbrückte Dreiringverbindungen vom Typ der Dianion-sulfide und der Thiocarbonyl-ylide (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2104-2113 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Novel Sulfur-bridged Three-membered Ring Compounds of the Type of the Dianion Sulfides and of the Thiocarbonyl YlidesReaction of the potassium salts of the thiodeltates 4a,b with the deltaines 5a,b results in the formation of novel dianion sulfide salts 1a-c. Thiocarbonyl ylide 7a-d and 8a-d, respectively, with cyclopropenium and deltate functions are prepared by the reaction of the thiones 6a-d with the deltaines 5a,b or of the cyclopropenium salt 9 with the potassium thiodeltate 4a. Interestingly, treatment of the sulfur-bridged dianion 1d with the dication 10 also yields the thiocarbonyl ylide 7d. The spectroscopic data of the new compounds 1, 7, and 8 are discussed, the 13C NMR data of the thiocarbonyl ylides are compared with those of the dianion and dikation sulfides.
    Notes: Neue Dianion-sulfide 1a-c entstehen bei der Reaktion der Kaliumsalze von Thiodeltaten 4a,b mit den Deltainen 5a,b. Die Darstellung neuer Thiocarbonyl-ylide 7a-d bzw. 8a-d mit Cyclopropenium- und Deltatfunktionen gelingt durch Umsetzung der Thione 6a-d mit den Deltainen 5a,b oder aus dem Cyclopropenium-Salz 9 mit dem Kalium-thiodeltat 4a. Interessanterweise entsteht das Thiocarbonyl-ylid 7d auch durch Umsetzung des schwefelverbrückten Dianions 1d mit dem Dikation 10. Die spektrometrischen Daten der neuen Verbindungen 1,7 und 8 werden diskutiert und die 13C-NMR-Daten der Thiocarbonyl-ylide mit denen der Dianion- und Dikation-sulfide verglichen.
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  • 84
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    Metallaheterocumulene, IV. 2-Azaallyliden-Komplexe  -  neuartige Verbindungen mit einem gewinkelten CNCR2-Fragment als Komplexligand (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2080-2093 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metallaheterocumulenes, IV. 2-Azaallylidene Complexes  -  Novel Compounds with a Bent CNCR2 Fragment as Complex Ligand(2-Azoniaallenylidene)pentacarbonyltungsten tetrabromoaluminate complexes [(CO)5W(CNCR2)]+AlBr4- (2-AlBr4) (CR2=C(C6H4Br-4)2 (a), CPh2 (b), C(C6H4OMe-4)2 (c), C(C6H4)2O (d), C(2,4,6-C6H2Me3)2 (e)) Which are synthesized by the reaction of (CO)5W[C(OEt)N=CR2] (1) with AlBr3, react with freshly distilled tetrahydrofuran to give neural trans-bromo(2-azaallylidene) complexes trans-Br(CO)4W(CNCR2) (3) and small amounts of (CO)5W—C≡N—[CR2]2—N≡C—W(CO)5 (4). The compounds 4 correspond to the product of a reductive dimerization of two cations 2. If 1b (or the corresponding methoxy compound 5) reacts with BBr3 instead of AlBr3/THF 4b is the main product. The spectroscopic data of 3 and the results of an X-ray analysis of 3b show that the replacement of a CO ligand in the cations 2 by Br- with formation of 3 results in a drastic change of the bonding situation within the CNCR2 ligand. 3a-e are the first compounds in which a strongly bent CNCR2 fragment functions as a complex ligand. The aminocarbyne complex trans-Br(CO)4W≡CNPh2 (7) was synthesized by BBr3-induced fragmentation of (CO)5W[C(NPh2)N=C(Ph)OMe] (6).
    Notes: (2-Azoniaallenyliden)pentacarbonylwolfram-tetrabromoaluminat-Komplexe [(CO)5W(CNCR2)]+AlBr4- (2-AlBr4) (CR2=C(C6H4Br-4)2 (a), CPh2 (b), C(C6H4OMe-4)2 (c), C(C6H4)2O (d), C(2,4,6-C6H2Me3)2 (e))  -  darstellbar durch Umsetzung von (CO)5W[C(OEt)N=CR2] (1) mit Albr3  -  reagieren mit frisch destillierten Tetrahydrofuran zu neutralen trans-Bromo(2-azaallyliden)-Komplexen trans-Br(CO)4W(CNCR2) (3) und wenig (CO)5W—C≡N—[CR2]2—N≡C—W(CO)5 (4). Die Verbindungen 4. entsprechen dem Produkt einer reduktiven Dimerisierung zweier Kationen 2. 4b wird zum Hauptprodukt der Umsetzung, wenn 1b (oder der entsprechende Methoxy-Komplex 5) mit BBr3 anstatt AlBr3/THF umgesetzt wird. Wie die spektroskopischen Daten von 3 sowie die Ergebnisse der an 3b durchgeführten Röntgenstrukturanalyse zeigen, führt der Austausch eines CO-Liganden in den Kationen 2 gegen Br- unter Bildung von 3 zu einer drastischen Veränderung der Bindungsverhältnisse im CNCR2-Liganden. 3a-e sind die ersten Verbindungen, in denen ein stark gewinkeltes CNCR2-Fragment als Komplexligand fungiert. Durch BBr3-induzierte Fragmentierung von (CO)5W[C(NPh2)N=C(Ph)OMe] (6) wurde der Aminocarbin-Komplex trans-Br(CO)4W≡CNPh2 (7) dargestellt.
    Additional Material: 1 Ill.
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    Reaktionen von Cyanformamidinen mit Hexafluoraceton (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2127-2134 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Cyanoformamidines with HexafluroacetoneHexafluoroacetone(HFA) reacts with N,N-dialkylcyanoformamidines in one step under mild conditions to form 4-(dialkylamino)-2,5-dihydro-5-imino-2,2-bis(trifluoromethyl)oxazoles 1a-d. 1a,b react further with HFA to yield the N′-(hydroxyhexafluoroisopropyl)-substituted derivatives 2a,b. Under the catalytic influence of copper powder in DMF 1a,b, rearrange to give 1,2-dihydro-2,2-bis(trifluromethyl)-5H-imidazol-5-ones 3a,b in good yields. The activation parameters of the hindered rotation of the C-4—N bond of 1a,c and 3a are reported.
    Notes: Hexafluoraceton (HFA) reagiert mit N,N-Dialkylcyanformamidinen in einem Reaktionsschritt unter milden Bedingungen zu 4-(Dialkylamino)-2,5-dihydro-5-imino-2,2-bis(trifluormethyl)oxazolen 1a-d. 1a,b könne mit weiterem HFA zu den N′-(hydroxyhexafluorisopropyl)substituierten Derivaten 2a,b umgesetzt werden. Unter der katalytischen Wirkung von Kupferpulver in DMF gelingt die Umlagerung von 1a,b in 1,2-Dihydro-2,2-bis(trifluormethyl)-5H-imidazol-5-one 3a,b in guten Ausbeuten. Von 1a,c und 3a wurden durch 1H-DNMR-Untersuchungen die Aktivierungsparameter der gehinderten Rotation um die C-4—N-Bindung bestimmt.
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    URL: http://dx.doi.org/10.1002/cber.19861190707
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    Heterocyclische β-Enaminoester, 41. Vinylogieprinzip bei 6,7-Dihydro-1H-azepinen; Cycloaddition und neuartige Umlagerung zu 2,3,3a,7a-Tetrahydroindolen.  -  Thermische [2 + 2]-Cycloadditionen mit 4-R-TAD (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2114-2126 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclic β-Enamino Esters, 41. Vinylogeous Principle on 6,7-Dihydro-1H-azepines; Cycloaddition and Novel Rearrangement to 2,3,3a,7a-Tetrahydroindoles.  -  Thermal [2 + 2]-Cycloadditions with 4-R-TADThe conjugated π-Systems of 6,7-dihydrooxepines, -thiepines, and -azepines (1-5) show a remarkable alternance of their 13C NMR shifts. In a cycloaddition-ring enlargement sequence the 6,7-dihydroazepine 3 reacts with acetylenedicarboxylates at the 4,5-double bond to afford first the intermediary 8,9-dihydro-1H-azonines 6B. These give in turn the indoles 7a,b via thermal 6π-electron cyclization. Under subsequent rearrangement 2,3,3a,7a-tetrahydroindoles 8a,b are formed. The structure of 8a is established by X-ray diffraction. In a polar [2 + 2]-cycloaddition 4-R-1,2,4-triazoline-3,5-dione (4-R-TAD) gives with 3 and 5 the [1,2,4]triazolo[1′,2′:1,2]diazet-[3,4-d]azepines 10a-d and 11a,b resp., and with the bis-TAD 12 the 2:1-adduct 13. Treatment of 10a with phenyl isocyanate originates the carbodiimide 14 which is converted with basic ring closure into the pyrimido[4,5-b]azepine 15.
    Notes: 6,7-Dihydrooxepine, -thiepine und -azepine (1-5) zeigen eine ausgeprägte Alternanz ihrer 13C-NMR-Verschiebungen im konjugierten π-System. Das 6,7-Dihydroazepin 3 reagiert mit Acetylendicarbonsäureestern zunächst unter Cycloaddition-Ringerweiterung an der 4,5-Doppelbindung zu den intermediären 8,9-Dihydro-1H-azoninen 6b. Diese ergeben sogleich unter thermischem 6π-Elektronenringschluß die Indole 7a,b. Nach erneuter Umlagerung entstehen 2,3,3a,7a-Tetrahydroindole 8a,b; die Konstitution von 8a wird durch Röntgenstrukturanalyse ermittelt. Mit 4-R-1,2,4-Triazolin-3,5-dionen (4-R-TAD) entstehen aus 3 und 5 in polarer [2 + 2]-Cycloaddition die [1,2,4]Triazolo[1′,2′:1,2]diazet[3,4-d]azepine 10a-d und 11a,b mit dem Bis-TAD 12 das 2:1-Addukt 13. 10a ergibt mit Phenylisocyanat das Carbodiimid 14 und beim basischen Ringschluß das Pyrimido[4,5-b]azepin 15.
    Additional Material: 5 Tab.
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    Neue Reagenzien, XXXVII. (α-Lithioalkyl)diphenylarsanoxide: Synthese und Anwendung zur indirekten nucleophilen Haloalkylierung (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2135-2142 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Reagents, XXXVII. (α-Lithioalkyl)diphenylarsane Oxides: Synthesis and Application for the Indirect Nucleophilic HaloalkylationDue to ready accessibility and high nucleophilicity (α-lithioalkyl)diphenylarsane oxides (2) are favorable reagents for the synthesis of many organoarsenic compounds. In organic synthesis they are recommendable as reagents for indirect nucleophilic haloalkylation reactions (Hal=Cl, Br, I).
    Notes: (α-Lithioalkyl)diphenylarsanoxide (2) sind wegen ihrer bequemen Zugänglichkeit und hohen Nucleophilie günstige Reagenzien zur Darstellung zahlreicher Organoarsenverbindungen. In der organischen Synthese sind sie als Reagenzien für indirekte nucleophile Haloalkylierungen (Hal=Cl, Br, I) empfehlenswert.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19861190708
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    Neue Reagenzien, XXXVIII. Über die extreme Diastereoselektivität bei der Addition von (α-Lithioalkyl)diphenylarsanoxiden an Benzaldehyd und Acetophenon (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2143-2149 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Reagents, XXXVIII. Addition of (α-Lithioalkyl)diphenylarsane Oxides to Benzaldehyde and Acetophenone with Extreme DiastereoselectivityIn contrast to α-lithiated alkyldiphenylphosphane oxides, the α-lithiated alkyldiphenylarsane oxides 3a and b react extremely diastereoselectively with benzaldehyde to give the alcohols erythro-4a and erythro-4b, respectively. Analogously, 3b reacts extremely diastereoselectively with acetophenone, whereas by reaction with aliphatic aldehydes a mixture of two diastereomeric alcohols (erythro:threo = 1.5-1.7:1) is formed.
    Notes: Im Gegensatz zu α-lithiierten Alkyldiphenylphosphanoxiden reagieren die α-lithiierten Alkyldiphenylarsanoxide 3a und b hoch diastereoselektiv mit Benzaldehyd zu den Alkoholen erythro 4a bzw. erythro-4b. Auch mit Acetophenon reagiert 3b extrem diastereoselektiv, während bei der Umsetzung mit aliphatischen Aldehyden ein Diastereomeren-Gemisch anfällt (erythro:threo = 1.5-1.7:1).
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19861190709
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    Neue Reagenzien, XXXIX. Optimierung der Diastereo- und Aldehydselektivität von Horner-Reagenzien durch Modifizierung der Struktur (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2150-2158 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Reagents, XXXIX. Optimization of the Diastereo- and Aldehyde Selectivity of Horner-Type Reagents by Modification of the StructureIntroduction of an ortho-substituent in the phenyl residues of (α-lithiobutyl)diphenylphosphane oxide (7) increases the diastereoselectivity in the reaction with benzaldehyde. (α-Lithiobutyl)bis(2-methoxyphenyl)phosphane oxide (9) gave the erythro-product 12 even exclusively by reacting with benzaldehyde.  -  Exchange of the lithium atom of (lithiomethyl)-diphenylphosphane oxide (17) for chromium or titanium brought about much better aldehyde selectivity in competition experiments with benzaldehyde and acetophenone.
    Notes: Durch Einführung eines ortho-Substituenten in die Phenylreste von (α-Lithiobutyl)diphenylphosphanoxid (7) wird die Diastereoselektivität bei der Umsetzung mit Benzaldehyd gesteigert. (α-Lithiobutyl)bis(2-methoxyphenyl)phosphanoxid (9) reagierte mit Benzaldehyd sogar ausschließlich zum erythro-Produkt 12.  -  Der Austausch des Lithiumatoms von (Lithiomethyl)diphenylphosphanoxid (17) gegen Chrom oder Titan führte zu stark erhöhter Aldehydselektivität bei Konkurrenzversuchen mit dem Substratpaar Benzaldehyd/Acetophenon.
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    Enantioselective diastereospecific synthesis of anti-α-alkyl-β-hydroxy esters through cuprate opening of glycidic esters (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2178-2190 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Enantioselektive diastereospezifische Synthese von anti-α-Alkyl-β-hydroxycarbonsäureestern durch Cuprat-Ringöffnung von GlycidesternEine über die Zwischenglieder 4-7 ablaufende diastereospezifische Kettenverlängerung von Aldehyden 1 zu anti-α-Alkyl-β-hydroxyestern 2 wird beschrieben. Durch Verwendung der Sharpless-Epoxidierung kann 2 mit Enantiomerenüberschüssen von 〉90% in Form beider Antipoden erhalten werden.
    Notes: A diastereospecific chain elongation of the aldehydes 1 of anti-α-alkyl-β-hydroxy esters 2 via the intermediates 4-7 is described. By means of the Sharpless epoxidation, 2 may be obtained with 〉90% ee in either enantiomer.
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    URL: http://dx.doi.org/10.1002/cber.19861190713
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    Synthesen mit Cyclobutadienen, 13. Azapentafulvene aus 2,3,4-Tri-tert-butylcyclobutadien-1-carbonsäureestern und Isonitrilen (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2159-2172 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese with Cyclobutadienes, 13. Azapentafulvenes from 2,3,4-Tri-tert-butylcyclobutadiene-1-carboxylic Esters and IsonitrilesFrom kinetically stabilized cyclobutadienes 6a and b and isonitriles 7a-c the azapentafulvenes 9a-d are obtained. In contrast, 6a reacts with 7d exclusively to form the constitution isomeric azapentafulvene 11e. Both isomers (9f and 11f) are realized in the reaction of 6a with 7e. The structural assignment of the isomers 9 and 11 is based on 13C NMR investigations as well as on an X-ray analysis performed for 9a. Hydrolysis of 9 and 11 yields the tri-tert-butyl substituted cyclopentadienones 20a,b and 21. By photochemical means 21 is transformed into the isomer 20a, which can also be obtained directly from the cyclobutadiene 6a and carbon monoxide.
    Notes: Aus den kinetisch stabilisierten Cyclobutadienen 6a bzw. b und den Isonitrilen 7a-c erhält man die Azapentafulvene 9a-d. Im Gegensatz dazu reagiert 6a mit 7d ausschließlich unter Bildung des konstitutionsisomeren Azapentafulvens 11e. Beide Möglichkeiten (9f und 11f) werden bei der Umsetzung von 6a mit 7e wahrgenommen. Die Strukturzuordnung der Isomeren 9 und 11 beruht auf 13C-NMR-Untersuchungen sowie auf der Röntgenstrukturanalyse für 9a. Hydrolyse von 9 und 11 macht die tri-tert-butylsubstituierten Cyclopentadienone 20a,b und 21 zugänglich. Photochemisch läßt sich 21 in das Isomere 20a umwandeln, das auch unmittelbar aus dem Cyclobutadien 6a und Kohlenmonoxid erhalten werden kann.
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    Stereoselektive Aldolreaktion mit chiralen sekundären Acetamiden (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2191-2207 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereoselective Aldol Reaction with Chiral Secondary AcetamidesThe deprotonated acetamides 4a-c und 5a-c are added to prochiral carbonyl compounds. The influence of the solvent, of the reaction temperature, and of the enolate gegenion on the ratio of the isomeric products 8/9, 18/19, and 26/27, respectively, are studied. The highest degrees of diastereoselectivity are observed, when the titanium enolate of the acetamide 4a or the threefold deprotonated N-acetyl-α-phenylglycinol (5a) is used. The diastereomers 18a-d, formed in excess in the addition of 5a to aldehydes, are isolated in a pure form by a single recrystallization, and afford the enantiomerically pure β-hydroxy carboxylic acids 3a-d. Thereby, the chiral auxiliary, α-phenylglycinol (14), is recovered.
    Notes: Die deprotonierten Acetamide 4a-c und 5a-c werden an prochirale Carbonylverbindungen addiert. Dabei wird der Einfluß von Lösungsmittel, Temperatur und Enolat-Gegenion auf das jeweilige Verhältnis der isomeren Produkte 8/9, 18/19 und 26/27 untersucht. Die höchsten Diastereoselektivitäten lassen sich mit dem Titan-enolat des Amids 4a und dem dreifach deprotonierten N-Acetyl-α-phenylglycinol (5a) erzielen. Die bei der Addition von 5a an Aldehyde im Überschuß gebildeten Diastereomeren 18a-d können durch einmaliges Umkristallisieren rein erhalten werden und liefern nach alkalischer Hydrolyse die enantiomerenreinen β-Hydroxycarbonsäuren 3a-d. Dabei wird der chirale Hilfsstoff, α-Phenylglycinol (14), zurückgewonnen.
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    URL: http://dx.doi.org/10.1002/cber.19861190714
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    Reaktion von Azibenzilen mit Nonafluorbutansulfonsäureanhydrid (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2220-2232 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Azibenzils with Nonafluorobutanesulfonic AnhydrideReaction of azibenzils 1a-e with nonafluorobutanesulfonic anhydride (Nf2O) yields mainly vinylene bis(nonafluorobutanesulfonates) E,Z-2a-e and benzils 3a-e. The presence of a non-nucleophilic amine prevents decomposition of the azibenzils by traces of acid in the anhydride. Compounds 2 stem from an inital O-sulfonylation of the azibenzils, whereas C-sulfonylation perhaps leads to the benzils. Diazodiphenylmethane is decomposed by Nf2O to give tetraphenylethylene, benzophenone, and benzophenone azine.
    Notes: Die Azibenzile 1a-e reagieren mit Nonafluorbutansulfonsäureanhydrid (Nf2O) hauptsächlich zu den Vinylen-bis(nonafluorbutansulfonaten) E,Z-2a-e und den Benzilen 3a-e. Um die Zersetzung der Azibenzile durch Säurespuren im Anhydrid zu vermeiden, ist der Zusatz eines nicht nucleophilen Amins erforderlich. Die Produkte 2 gehen aus einer einleitenden O-Sulfonylierung der Azibenzile hervor, für die Bildung der Benzile könnte eine C-Sulfonylierung verantwortlich sein. Diazodiphenylmethan wird durch Nf2O zu Tetraphenylethylen, Benzophenon und Benzophenon-azin zersetzt.
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    URL: http://dx.doi.org/10.1002/cber.19861190716
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    Zur Frage der Stellungsisomerie bei disubstituierten Bullvalenen (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2339-2349 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Concerning the Question of Positional Isomerism in Disubstituted BullvalenesWe report about 15 new disubstituted bullvalenes (2, 4, 5, 11, 12, 14-20, 22-24) and discuss their substitution pattern together with 9 known species (1, 3, 6-10, 13, 21). The results which are partly unexpected are put together phenomenologically. We have no reasonable explanation for some results, i.e. only a few substituents with „complementary“ properties like the pair CH2OH/Br or CH3/CN in compounds 16 and 18, respectively, prefer a vicinal arrangement at a double bond.
    Notes: Wir berichten über 15 neue disubstituierte Bullvalene (2, 4, 5, 11, 12, 14-20, 22-24) und diskutieren ihr Substitutionsmuster gemeinsam mit dem von 9 bekannten Vertretern (1, 3, 6-10, 13, 21). Die teilweise unerwarteten Ergebnisse werden phänomenologisch geordnet. Für einige Befunde fehlen befriedigende Erklärungen. So bevorzugen z. B. nur manche Substituenten mit „komplementären“ Eigenschaften wie das Paar CH2OH/Br oder CH3/CN in den Verbindungen 16 bzw. 18 eine vicinale Anordnung an der Doppelbindung.
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    URL: http://dx.doi.org/10.1002/cber.19861190724
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  • 95
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    Zur Regio- und Stereoselektivität neuer thermischer [3 + 2]-Cycloadditionen mesoionischer 1,3-Oxathiol-4-one an Alkine und Alkene (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2317-2338 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Regio- and Stereoselectivity of Novel Thermal [3 + 2] Cycloaddition Reactions of Mesonionic 1,3-Oxathiol-4-ones to Alkynes and AlkenesAs potential carbonyl ylides, the 1,3-oxathiolyium-4-olates 1c or 1d combine with dibenzoylacetylene or 1-(diethylamino)-1-propyne via nonisolable [3 + 2] primary adducts of type 2, which release COS to give the furan derivatives 3a or b, respectively. On the other hand, some representative of 1 reacts with symmetrically and unsymmetrically substituted olefinic substrates with regio- and/or stereoselective formation of the isolable [3 + 2] primary adducts 4-16. In the example of the reactions of 1c with trans- and cis-cyclooctene, the stereospecificities and the competition constant are determined. Furthermore, the thermolyses of the cycloadducts 4b,5,6, and 7a,b are investigated. The addition directions, derived from the FMO and PMO theory, are compared with the experimentally realized regiochemistry.
    Notes: Als potentielle Carbonyl-ylide vereinigen sich die 1,3-Oxathiolylium-4-olate 1c oder 1d mit Dibenzoylacetylen oder 1-(Diethylamino)-1-propin über nicht isolierbare [3 + 2]-Primäraddukte vom Typ 2 unter COS-Abspaltung zu Furan-Derivaten 3a bzw. b. Demgegenüber reagieren einige Vertreter von 1 mit symmetrisch und unsymmetrisch substituierten olefinischen Substraten regio- und/oder stereoselektiv zu isolierbaren [3 + 2]-Primäraddukten 4-16. Am Beispiel der Umsetzung von 1c mit trans- und cis-Cycloocten werden die Stereospezifitäten und die Konkurrenzkonstante ermittelt. Weiterhin werden die Thermolysen der Cycloaddukte 4b, 5, 6 und 7a,b untersucht. Die aus der FMO- und PMO-Theorie abgeleiteten Additionsrichtungen werden mit der experimentell realisierten Regiochemie verglichen.
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    Hydrogenolyse kleiner Kohlenstoffringe, XIII. Über die Hydrierung von Homocubanderivaten (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2350-2361 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hydrogenolysis of Small Cycloalkanes, XIII. Hydrogenation of Homocubane DerivativesTwo dihydro products 5a and 7a are formed by hydrogenation of homocubane (6a) with Pd-, Pt-, and Rh-catalysts. Only the unsymmetric 7a reacts further to give twistbrendane (8a). In addition, ca. 20% brendane (11a) is obtained by hydrogenation of homocuneane (9a), which is formed from 6a by rearrangement on the catalyst. The yield of the symmetric dihydro product 5b is raised up to 40% in the case of hydrogenation of the ethylene acetal 6b of the 9-ketone on Rh/Al2O3. With the ester 6d no 5d is obtained but 7d and 8d only.
    Notes: Die Hydrierung von Homocuban (6a) mit Pd-, Pt- und Rh-Katalysatoren führt zu zwei Dihydroverbindungen 5a und 7a, von denen nur das unsymmetrische Hauptprodukt rasch zu Twistbrendan (8a) weiterreagiert. Durch Umlagerung von Homocuban zu Homocunean (9a) und dessen Hydrierung entstehen daneben auch bis zu 20% Brendan (11a). Im Falle des 9-Keton-Ethylenacetals 6b kann über Rh/Al2O3 der Anteil am symmetrischen Dihydroprodukt 5b bis 40% betragen, im Falle des Carbonsäureesters 6d erhält man dagegen nur 7d und 8d, aber kein 5d.
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    URL: http://dx.doi.org/10.1002/cber.19861190725
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    Aliphatic azo compounds, XV. cis- and trans-tetracyclopropyl- and tetra-tert-butylazomethanes (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1911-1918 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aliphatische Azoverbindungen, XV. cis- und trans-Tetracyclopropyl- und Tetra-tert-butylazomethanDie Produkte und die Kinetik der Thermolysen der Titelverbindungen 3 und 5 wurden untersucht. Wie die trans-Isomeren, so zerfallen auch die cis-Azoverbindungen in Radikale ohne begleitende cis-trans-Isomerisierung. Der Einfluß der Strukturvariation auf die Reaktivität wird diskutiert. Durch Bestrahlen von trans-Tetra-tert-butylazomethan (trans-5) bei 60-120°C in Benzol oder Chlorbenzol läßt sich fast quantitativ 1,1,2,2-Tetra-tert-butylethan darstellen.
    Notes: The products and the kinetics of the thermolysis of the title compounds 3 and 5 were investigated. Like the trans-isomers, the cis-azo compounds also undergo homolytic decomposition without accompanying cis-trans-isomerization. The observed structure-reactivity relationships are discussed. On irradiation of trans-tetra-tetr-butylazomethane (trans-5) at 60-120°C in benzene or chlorobenzene an almost quantitative yield of 1,1,2,2-tetra-tert-butylethane is obtained.
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    URL: http://dx.doi.org/10.1002/cber.19861190613
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    Pentacarbonylchrom-Komplexe von 1H-Isoindolen (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1919-1930 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pentacarbonylchromium Complexes of 1H-IsoindolesThe 1H-isoindoles 1e-k are converted into the pentacarbonylchromium complexes 4e-k by means of ligand exchange reactions with pentacarbonyl(η2-cis-cyclooctene)chromium (3). Likewise, the 2H-isoindoles (2a-d) which are able to undergo tautomerism are complexed in the 1H-form 4a-d. This reaction allows, for the first time, to isolate even unsubstituted 1H-isoindole (1a) from the equilibrium with 2H-isoindole (2a) as a stable derivative 4a. The structure 4 of the pentacarbonyl(η1-1H-isoindole)chromium complexes is elucidated from the analytical and spectroscopic data (IR, 1H and 13C NMR, MS) as confirmed by means of an X-ray structure analysis of the 3-ethoxy-1H-isoindole complex 4e.
    Notes: Die 1H-Isoindole 1e-k werden durch Ligandenaustausch mit Pentacarbonyl(η2-cis-cycloocten)chrom (3) in die Pentacarbonylchrom-Komplexe 4e-k übergeführt; tautomeriefähige 2H-Isoindol (2a-d) werden ebenfalls in der 1H-Form komplexiert (4a-d). Diese Reaktion erlaubt erstmals, auch das unsubstituierte 1H-Isoindol (1a) aus dem Gleichgewicht mit 2H-Isoindol (2a) in Form eines stabilen Derivats 4a zu isolieren. Die Struktur 4 der Pentacarbonyl(η1-1H-isoindol)chrom-Komplexe ergibt sich aus den analytischen und spektroskopischen Daten (IR, 1H- und 13C-NMR, MS) und wird durch eine Röntgenstrukturanalyse des 3-Ethoxy-1H-isoindol-Komplexes 4e bestätigt.
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    URL: http://dx.doi.org/10.1002/cber.19861190614
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    Cycloadditionen, 6. Intramolekulare Diels-Alder-Reaktion bei Allencarboxaniliden; Variation des zur Carboxamidgruppe geminal stehenden Restes (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1953-1963 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cycloadditions, 6. Intramolecular Diels-Alder Reaction of Allenecarboxanilides; Variation of the Residue Geminal to the Carboxamide GroupThe 2,3-butadienanilides 6a-h, unsubstituted in the ω-position, are synthesized by the ynamine way and submitted to thermolysis. They isomerize without exception by intramolecular Diels-Alder reaction more or less quickly, irreversibly, and quantitatively to give the tricyclic lactams 8a-h, the aniline nucleus functioning as diene in all cases. The structures of 8 are confirmed by spectroscopic data and by an X-ray analysis (8b).
    Notes: Die in ω-Position unsubstituierten 2,3-Butadienanilide 6a-h werden auf dem Inaminweg synthetisiert und der Thermolyse unterworfen. Sie isomerisieren ohne Ausnahme in einer intramolekularen Diels-Alder-Reaktion mehr oder weniger rasch, irreversibel und quantitativ zu den tricyclischen Lactamen 8a-h, wobei der Anilinkern jeweils als „Dien“ fungiert. Die Strukturen 8 werden spektroskopisch und durch eine Röntgenstrukturanalyse (8b) bestätigt.
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    URL: http://dx.doi.org/10.1002/cber.19861190616
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    Neuartig chelatisierte Organodiboroxane und Organoboroxine aus Triorganoboroxinen und enolisierbaren 1,3-Diketonen (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1931-1952 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Novel Chelated Organodiboroxanes and Organoboroxins from Triorganoboroxins and Enolizable 1,3-DiketonesTrialkylboroxins (RBO)3 (1) [1a: R=CH3; 1b: R=C2H5] react with enolizable 1,3-diketones (R′CO)2CH2 [2a: R′=CH3; 2b: R′=C6H5] at ≈ 20°C with fast degradation of the boroxin rings to give the monochelated diboroxanes 3 of the composition HOB(R)OB(R)OC(R′)CHC(R′)O [3aa: R=R′=CH3; 3ba: R=C2H5, R′=CH3; 3bb: R=C2H5, R′=C6H5] in yields up to 85%. The solid 3 with H-bridged bicyclic structures are in equilibrium with partially ring opened compounds in solution (1H, 11B, 13C, and 17O NMR data). From 1b with 2a or from triphenylboroxin (1c) with 2b the double chelated diboroxanes [RB(R′CO)2CH]2O [4ba: R=C2H5, R′=CH3; 4cb: R=R′=C6H5] are obtained. 1c reacts with 2a or 2b at 〉 140°C under slow protolysis of the B-phenyl residues to form the single and double chelated boroxins 5 and 6 having the compositions R2B3O3(R′CO)2CH [5ca: R=C6H5, R′=CH3; 5cb: R=R′=C6H5] and RB3O3[(R′CO)2CH]2 [6cb. R=R′=C6H5].  -  4, 5, and 6 with fully or partially chelated boron atoms are stable up to 〉 200°C.  -  The molecular structures of 4cb and 5ca were determined by X-ray analyses.
    Notes: Aus Trialkylboroxinen (RBO)3 (1) [1a: R=CH3; 1b: R=C2H5] bilden sich bei ≈ 20°C mit enolisierbaren 1,3-Diketonen (R′CO)2CH2 [2a: R′=CH3; 2b: R′=C6H5] unter raschem Abbau der Boroxin-Ringe in bis zu 85proz. Ausbeute die monochelatisierten Diboroxane 3 der Zusammensetzung HOB(R)OB(R)OC(R′)CHC(R′)O [3aa: R=R′=CH3; 3ba: R=C2H5, R′=CH3; 3bb: R=C2H5, R′=C6H5]. Die festen 3 mit H-verbrückter bicyclischer Struktur stehen in Lösung im Gleichgewicht mit partiell ringgeöffneten Verbindungen (1H-, 11B-, 13C- und 17O-NMR-Daten). Aus 1b erhält man mit 2a und aus Triphenylboroxin (1c) mit 2b die zweifach chelatisierten Diboroxane [RB(R′CO)2CH]2O [4ba: R=C2H5, R′=CH3; 4cb: R=R′=C6H5]. 1c reagiert mit 2a oder 2b bei 〉 140°C unter langsamer Protolyse der B-Phenylreste zu den einfach und zweifach chelatisierten Boroxinen 5 und 6 mit den Zusammensetzungen R2B3O3(R′CO)2CH [5ca: R=C6H5, R′=CH3; 5cb: R=R′=C6H5] und RB3O3[(R′CO)2CH]2 [6cb: R=R′=C6H5]. 4, 5 und 6 mit vollständig bzw. partiell chelatisierten Bor-Atomen sind bis 〉 200°C stabil.  -  Die Molekülstrukturen von 4cb und 5ca wurden durch Röntgenstrahlbeugungsanalysen bestimmt.
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    URL: http://dx.doi.org/10.1002/cber.19861190615
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