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  • 1995-1999  (60)
  • 1990-1994  (356)
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  • 1
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 225-233 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The potential of using indigenous microorganisms in beach sediments to degrade petroleum hydrocarbons emanating from marine oil spillages in the Straits of Singapore was investigated. A field trial was conducted using oil contaminated beach sediments from Pulau Semakau - a small island 15 km south of Singapore. The results clearly show that the addition of inorganic nutrients to beach sediments significantly enhanced the activity of indigenous microorganisms (measured using the dehydrogenase enzyme assay and viable cell count techniques), as well as the removal of total recoverable petroleum hydrocarbons (TRPH) over a 50-day study period (with up to 44% in the case of nutrient addition). The potential of exploiting in-situ bioremediation techniques for oil spill clean-up operations in tropical marine environments is discussed.
    Additional Material: 3 Ill.
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  • 2
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The biosynthesis of bacterial cellulose by Acetobacter xylinum was optimized by numerically finding the maximum of an arbitrarily chosen second order polynomial model function of several variables (describing the dependence of the cellulose production on the concentrations of the medium components), using multivariable linear regression analysis. The chosen function appeared to describe the analyzed correlation sufficiently well. Consequently, three to six stages of optimization made the determination of the optimum medium compositions possible for 16 days of fermentation at 30°C in a medium based on fructose (wt%: fructose, 3.68; yeast extract, 5.02; (NH4)2NO3, 0.001; KH2PO4, 0.3; MgSO4 × 7 H2O, 0.05; resulting in a cellulose production equal to 0.505 wt.% - namely 5.6 times higher than before the optimization) and for 7 days fermentations at 30°C in a medium based on sucrose and ethanol (wt.%: sucrose, 5.0; ethanol, 1.36; yeast extract, 1.27; (NH4)2SO4, 0.5; KH2PO4, 0.3; MgSO4 × 7 H2O, 0.05; resulting in a cellulose production equal to 0.251 wt.% - namely 1.5 times higher than before the optimization).
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 91-100 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The stability of a polyphenol oxidase (PPO) preparation from the white-rot fungus Trametes versicolor during a process for the enzymatic decrease of the phenolic content of commercial canola meal (CM) was investigated. The effects of temperature, pH, protein origin and concentration, and meal particles were considered. The results showed that the thermal stability of the enzyme preparation was significantly increased in the presence of CM. The half-life times for the enzyme preparation, pre-incubated with CM at 50, 60, 70 and 75°C, were 45, 10.5, 3.5 and 1.5 hours, respectively; this represents an increase in the thermal stability of the enzyme preparation of up to four times in the presence of CM compared to the stability in the absence of CM. This effect was caused by the protective actions of both the CM particles and CM proteins, with the former responsible for 90% of the observed effect. The thermal stability of the enzyme in the presence of CM, from which 20% of the extractable proteins was extracted, was 5% lower compared to the stability in the presence of untreated CM. Changes in pH level from 5.0 to 3.2 resulted in a loss of stability comparable to that observed when the pre-incubation temperature was increased from 50 to 70°C.A semi-empirical model describing the changes in the concentration of the active enzyme pre-incubated in the presence and absence of CM at various incubation temperatures was proposed. A very good agreement between the model and experimental data was obtained. The proposed model, together with a general set of model parameters, can be used as a tool for the optimization of a process for the upgrade of CM by enzymatically decreasing the meal's phenolic content.
    Additional Material: 5 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 111-145 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: A non-comprehensive review of several technical developments in the field of aerobic biological waste-water treatment engineering is carried out, considering the active role the engineers have to play in this field. This paper brings together conventional and advanced problems in the field of aerobic biological waste-water treatment.Such an overview of biological waste-water treatment also precedes comments on some important aspects concerning the microorganisms responsible for waste-water treatment as well as considerations of the application of fundamentals and kinetics to the analysis of the biological processes used most commonly for aerobic biological waste-water treatment.A survey of the development of the biological activated-sludge process and some modifications are given. Some problems implied in the conventional activated-sludge waste-water treatment are analyzed, considering conventional processes and bioreactor models (the continuous stirred-tank reactor model and the plug-flow reactor models of the activated-sludge process) as well as aerated lagoons.Further, modifications of the activated-sludge process are presented. These include additional details on the bioreactor progress and applications, with emphasis on aspects concerning airlift bioreactors and their variants, deep-shaft bioreactors and reciprocating jet bioreactors which are considered as the third generation of bioreactors owing to their important advantages in design, operation and performance in waste-water treatment. Sequencing-batch reactors and aerobic digestion processes, including conventional aerobic digestion, high-purity oxygen digestion, thermophilic aerobic digestion and cryophylic aerobic digestion are also reviewed.Finally, some aspects regarding the operational factors that are involved in the selection of the reactor type are included.
    Additional Material: 11 Ill.
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  • 5
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the first part of the experiments, the mechanical properties of 1%, 2% and 3% carrageenan and 1%, 2% and 3% carrageenan/locust bean gum (LBG) gels stored in various concentrations of propionic and acetic acids and their mixtures were examined. The stability of these materials was measured by uniaxial compression between two parallel plates using the Instron Universal Testing Machine. A mathematical model explaining the dependence of the destroying force on the storage time was chosen for data analysis. Using this model, the average rate of gel deterioration was calculated. The structural properties of the examined gels were most influenced by the highest concentration of propionic and acetic acids and their mixtures (1% acetic acid and 2% propionic acid). The addition of LBG to carrageenan decreased the gel destroying force and increased its resistance to acids.In the second part of the experiments, the Propionibacterium freudenreichii subsp. shermanii NCFB 1081 and NCFB 566 were immobilized in a living state in 1%, 2% and 3% carrageenan and 1%, 2% and 3% carrageenan/LBG gels. The ammonia consumption, glucose utilization, production of propionic and acetic acids and the biosynthesis of vitamin B12 were examined. An increase in the productivity of propionic acid and a significant decrease in the vitamin B12 produced in the biosynthesis were observed when immobilized cells were used. The immobilization of cells enhanced the productivity of propionic acid by up to 40% compared to free cells. The best results were obtained for the second and third applications of immobilized cells in all concentrations of carrageenan gels and 2% and 3% carrageenan/LBG gels The results showed that carrageenan/LBG is a better support material for the immobilization of propionic acid bacteria than the pure carrageenan.
    Additional Material: 2 Ill.
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  • 6
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 171-177 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The bioaccumulation of cadmium by the white rot fungus Pleurotus sajor-caju onto dry biomass was investigated using aqueous media with concentrations in the range of 0.125 mM-1.0 mM The highest cadmium uptake (between 88.9 and 91.8%) was observed with aerobic fungal biomass from the exponential growth phase. Up to 1.0 mM cadmium gradually inhibited mycelium development, but never blocked it completely. Freeze-dried, oven-dried and non-metabolizing live Pleurotus sajor-caju biomass types were tested for their capacity to adsorb the test ion Cd2+ within the pH range of 4.5 to 6.0. Freeze-dried biomass proved to be the most efficient biomass type for Cd2+ metal adsorption. Therefore, Pleurotus sajor-caju may be used for heavy metal removal and bioremediation.
    Additional Material: 2 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 3-16 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetics of cellobiose hydrolysis was studied using β-glucosidase from Penicillium funiculosum, both free and immobilized on nylon powder, at different temperatures, pH values, enzymatic activities and initial cellobiose and glucose concentrations.The experimental results were fitted to a kinetic model by considering the substrate and product inhibitions as well as the thermal deactivation of β-glucosidase with a mean deviation of less than 10%. The immobilization of β-glucosidase led to an increase in the stability of the enzyme against changes in the pH value.
    Additional Material: 10 Ill.
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  • 10
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 27-36 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Ethanol has been reported to be a gaseous pollutant, originating from the agricultural industry. Interest in its biodegradation has increased over the last two decades. Most of the current studies have focused on its elimination by mixed cultures. This study is part of a broader project intended to utilize Candida utilis strains for gaseous ethanol elimination and to eventually bioconvert them into biomass and/or volatile metabolites. We present here the study of six strains (one from the ATCC and five from the ICIDCA collection) cultivated in a liquid medium, with initial ethanol concentrations of 16 g/l and 32 g/l. At 16 g/l, a maximum ethanol elimination rate of 0.13 g/l × h was obtained in four of the six strains (ATCC 9950, L/375-1, L/375-5 and L/375-10). This rate increased to 0.21 g/l × h with an initial ethanol concentration of 32 g/l. The L/375-5 strain was the best biomass producer (3.3 g/l) at 32 g/l, while the highest ethyl acetate production (0.80 g/l) was obtained with the L/375-1 strain. The L/375-25 and L/375-26 strains which showed very low ethyl acetate production were, by way of contrast, efficient acetaldehyde producers, with 0.54 g/l and 0.66 g/l measured in the broth. While biomass production reached its maximum after two days of culture, the production of acetic acid and ethyl acetate continued during the third day. The results for biomass and metabolite production obtained with the ICIDCA collection strains (L/375-1, L/375-5 and L/375-10) were better than those obtained with the ATCC 9950 strain, although the latter often has been reported to be particularly suitable for metabolite production.
    Additional Material: 5 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 77-78 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 59-68 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The ability of the Rhizobium sp., isolated from the root nodules of the leguminous pulse yielding shrub Cajanus cajan, to produce extracellular polysaccharides (EPS) was checked. A large amount of EPS (1, 128 μg/ml) was produced by the bacteria in yeast extract mannitol medium. Growth and EPS production started simultaneously, but the production reached its maximum level in the stationary phase of growth at 28 h. The EPS production by this Rhizobium sp. was much higher than by many other strains from nodules of Cajanus cajan which took a much longer time to reach maximum EPS production than this strain. The maximum EPS production (2,561 μg/ml) was obtained when the medium was supplemented with mannitol (1%), cetyl pyridinium chloride (2 μg/ml) and KNO3 (0.2%), in which the production was increased by 276% compared to the control. The EPS production rose in the period up to 65 h with increased mannitol concentration. The EPS contained arabinose, xylose and rhamnose monomers. The possible role of rhizobial EPS production in root nodule symbiosis is discussed.
    Additional Material: 3 Ill.
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  • 14
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 15
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 331-339 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Rhizobium sp., isolated from the root nodules of the leguminous fodder herb Melilotus alba, produced large amounts of extracellular polysaccharides (EPS) (963.5 μg/ml) in a yeast extract mannitol medium. Growth and EPS production started simultaneously, but EPS production reached its maximum during the stationary phase of growth of the bacteria, at 20 hours. EPS production was increased with all of the thirteen sugars tested. Different nitrogen sources, such as nitrates, glutamic acid, casamino acid and L-asparagine, increased the EPS production although it was inhibited by glycine, nitrite and ammonium salts. Among the vitamins and metal ions, only pyridoxal phosphate and ZnSO4 promoted EPS production. Attempts were made to optimize the cultural requirements for growth and maximum EPS production. Maximum EPS production (1457.0 μg/ml) was obtained when the medium was supplemented with glucose (1%), pyridoxal phosphate (2 μ g/ml), ZnSO4 × 7 H2O (10 μg/ml) and glutamic acid (0.1%). Under these conditions, the production was increased by 254.3% compared to the control. The EPS contained arabinose, xylose and rhamnose monomers. The presence of arabinose and xylose in the EPS produced by a Rhizobium sp. was uncommon.
    Additional Material: 2 Ill.
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  • 17
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the present work, the use of flame-burned WS as carriers of Z. mobilis and extracellular levansucrase and the effect of the cell fixation method by dehydration on system productivity were investigated. Lyophilization and convective drying of Z. mobilis biomass at 30°C to a moisture content of 10-14% gave the best results for the repeated batch fermentations of a sucrose medium to obtain levan and ethanol. Significant correlation between the product formation and the concentration of free cells in the fermentation medium was established. Clearly, the cells were weakly bound to the newly generated WS and were washed out into the medium during fermentation. Here the hypothesis is presented that components excreted from damaged cells during dehydration can intensify the reactivation of damaged living cells and influence the interactions between the cells and the wire surface.The passive immobilization of extracellular levansucrase in oxidized WS was also observed. The superiority of oxidized WS in comparison with non-treated WS is related to an increase in the number of OH groups. The potential regeneration of WS by burning after the termination of fermentation cycles was also considered.
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  • 18
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 146-146 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 19
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 157-161 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: A xylanase was removed from crude extract of the fungus Penicillium janthinellum under optimized conditions: 0.10M phosphate buffer, pH 7.0, 0.2 M BDBAC (N-benzyl-N-dodeceyl-N-bis (2-hydroxyethyl) ammonium chloride), 7.5% hexanole, 30°C and an agitation time of 1 minute. At 1.42 mg per ml protein concentration, 73% of the xylanase activity was recovered and a 7-fold enrichment factor was obtained. The enzyme had a molecular weight (MW) of 20.1 kDa and the isoelectric point (PI) revealed the presence of two protein bands with a PI of 6.0 and 6.5. The optimum pH and optimum temperature were 4.2 and 50°C, respectively. The low pH differential between the aqueous medium and the protein PI seemed to influence the xylanase transportation into the reversed micelles.
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  • 20
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 21
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 163-169 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The morphogenetic response of Hypericum perforatum seedlings to different auxin and cytokinin concentrations was studied. A stimulation of the concentration-dependent rooting ability was observed under the influence of indole-3-acetic acid and indole-3-butyric acid. Rooting was not enhanced by the effects of 2,4-dichlorophenoxyacetic acid and 1-naphtaleneacetic acid. Differentiated roots were isolated and cultured in liquid media with the same combination of growth-promoting auxins. Chromosome counts in root tip cells after long-term cultivation indicated a high degree of chromosomal instability. Multiple shoot formation occurred under the influence of 6-benzylaminopurine and kinetin. Adenine and 6-(γ,γ-dimethylallylamino)-purine did not stimulate shoot differentiation. No differences in the morphogenetic response to auxins and cytokinis were detected between diploid and tetrapoloid plants.
    Additional Material: 2 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 23
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 179-186 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Spores of Aspergillus niger were exposed to a pulsed electric field. After treatment by the electric field, the viability of the conidia of A. niger varied depending on the field strength, pulse width and frequency. In all cases, these parameters reduced the viability rate of the conidia from 2.0 × 107 to a range from 6.2 × 106 to 8.5 × 106 spores/ml (3.1 to 42.6%). After pulse treatment, the conidia were used as the inoculum for citric acid fermentation in shake flasks. The highest increase in citric acid yield (about 1.4-fold) was reached at a field strength of 2.85 kV/cm, a frequency of 1 Hz and a pulse width of 1 ms. When the parameters of the electric field increased there were important changes in the respiration rate of the Aspergillus niger mycelium (48-h-old) after electric shock treatment. The highest consumption of dissolved oxygen (22.9%) in the medium by Aspergillus niger mycelium was observed at an electric field strength of 2.85 kV/cm, a 1 Hz frequency, a pulse width of 1 ms and a 1-min exposure period. It seems that an electric-field stimulation of the conidia prior to inoculation may offer an important method of improving the efficiency of citric acid. The treatment of the conidia is both simple from the technical point of view and extremely rapid.
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  • 24
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 25
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effects of adding some inducers of lignolytic activity to semi-solid-state cultures of Phanerochaete chrysosporium BKM-F-1767 (ATCC 24725) were investigated. The inducers assayed were veratryl alcohol and solid manganese (IV) oxide. The microorganism was cultured on corncob, which functioned both as physical support and source of nutrients.Supplementing the cultures with veratryl alcohol created the situation where manganese-dependent peroxidase (MnP) and lignin peroxidase (LiP) activities of approximately 1,500 U/l and 200 U/l, respectively, could be attained. These activities were considerably higher than those obtained in the reference cultures (about 5 and 4-fold).In the same way, the addition of manganese (IV) oxide led to MnP and LiP activity levels of about 2,000 U/l and 300 U/l, respectively. These activities were also notably above (about 6 and 5-fold, respectively) those achieved in the reference cultures.Moreover, laccase activity (around 200 U/l) was only detected in veratryl alcohol or manganese (IV) oxide supplemented cultures.
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  • 26
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 27
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 45-56 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The culture behaviour of Thermus aquaticus was characterized. The response of the bacterium to various carbon (tryptone, glucose, glycerol) and nitrogen sources (yeast extract, NaNO3, (NH4)2SO4, leucine, thymine, thiamine, glutamic acid) was studied. Amino acids did not support growth, but CASTENHOLZ salt medium supplemented with yeast extract and glucose or tryptone resulted in good growth and production. A suitable medium composition giving the highest biomass concentration and enzyme yield was developed. The simple medium containing TYE-NaCl resulted in the highest biomass concentration, whereas CASTENHOLZ mineral medium supplemented with tryptone and yeast extract gave the highest specific activity and enzyme yield. The effect of inoculum age and size on growth was also investigated in order to improve the yield and process consistency. The use of shake flasks inoculated with precultures at their early or late stationary phase resulted in the same biomass concentration (0.56 ± 0.015 g/l) and similar maximum specific growth rates (0.258 ± 0.003 h-1). Inoculum sizes between 1 and 2.5 per cent were optimal for cell growth. As the other papers on thermophilic microorganisms, including the T. aquaticus YT-1 strain, gave qualitative information on growth, the results presented here cannot be compared with others on a quantitative basis. TaqI endonuclease was purified using a 5 step protocol including cell disruption, adsorption, precipitation, column chromatography and final dialysis. The enriched fraction had a specific activity of 33,600 U TaqI endonuclease per mg protein.
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  • 28
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 88-88 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 29
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 79-86 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Methylobacterium rhodesianum MB 126, a pink-pigmented facultatively methylotrophic bacterium that uses that serine pathway for the assimilation of reduced C1 compounds, is able to produce poly-3-hydroxybutyrate (PHB) under certain limitation conditions. Mutants of this bacterium, which were isolated after the treatment with sodium nitrite, are impaired in their ability to synthesize PHB, but produce another polymer in addition to PHB, namely an exopolysaccharide (EPS). This paper attempts to explain this surprising behaviour.
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  • 30
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 31
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 32
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 37-44 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Agar-agar, agarose, carrageenan and calcium alginate were used for the immobilization of Dunaliella salina cells. Out of the four, agar-agar was found to be the most effective and therefore the study was carried out on it using different pH values ranging from 6 to 10 and cell densities from 0.1 to 0.8 μg chlorophyll (chl, a) per bead to find which are is best suited for glycerol production. The maximum glycerol production of 9.2 μM/mg chl a was recorded in agar-agar immobilized algae and this was followed by 8.4 μM/mg chl a in calcium alginate. The maximum cell number 6.2 × 109/ml and the specific growth rate (μ) of 0.80 l/day were reached at pH 8 in agar-agar immobilized algae. It was shown that the maximum amount of glycerol was produced when the cell density was 0.8 μg chl a/ block. Changing the medium after 24 hours affected the rate of glycerol production at different pH values. Using a cell density of 0.8 μg chl a/block at 16 W/m2 light intensity increased the glycerol production in comparison with the use of free living cells.
    Additional Material: 4 Ill.
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  • 33
    Electronic Resource
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 235-250 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new low-cost β-galactosidase (lactase) preparation for whey permeate saccharification was developed and characterized. A biocatalyst with a lactase activity of 10 U/mg, a low transgalactosylase activity and a protein content of 0.22 mg protein/mg was obtained from a fermenter culture of the fungus Penicillium notatum. Factors influencing the enzymatic hydrolysis of lactose, such as reaction time, pH, temperature and enzyme and substrate concentration were standardized to maximize sugar yield from whey permeate. Thus, a 98.1% conversion of 5% lactose in whey permeate to sweet (glucose-galactose) syrup was reached in 48 h using 650 β-galactosidase units/g hydrolyzed substrate. After the immobilization of the acid β-galactosidase from Penicillium notatum on silanized porous glass modified by glutaraldehyde binding, more than 90% of the activity was retained. The marked shifts in the pH value (from 4.0 to 5.0) and optimum temperatures (from 50°C to 60°C) of the solid-phase enzyme were observed and discussed. The immobilized preparation showed high catalytic activity and stability at wider pH and temperature ranges than those of the free enzyme, and under the best operating conditions (lactose, 5%; β-galactosidase, 610-650 U/g lactose; pH 5.0; temperature 55°C), a high efficiency of lactose saccharification (84-88%) in whey permeate was achieved when lactolysis was performed both in a batch process and in a recycling packed-bed bioreactor. It seems that the promising results obtained during the assays performed on a laboratory scale make this immobilizate a new and very viable preparation of β-galactosidase for application in the processing of whey and whey permeates.
    Additional Material: 6 Ill.
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  • 34
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 35
    Electronic Resource
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 263-272 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: An acid α-amylase hyperproducing strain, designated as MIR-61, was isolated in a screening procedure from South American soil samples. MIR-61, a 60°C thermoresistant strain, was identified using 98 biochemical and morphological tests and characterized as Bacillus licheniformis by numerical taxonomy. Batch cultures of B. licheniformis MIR-61 showed extracellular α-amylase and α-glucosidase activities during the exponential growth phase.The production of α-amylase was studied at free and constant pH values at 37 and 45°C. Maximum α-amylase activity (4,767 kU/dm3 in a liquid medium) was detected at 45°C at a constant pH (7.0) in the late exponential phase. The α-amylase production by B. licheniformis MIR-61 is 10 to 300 times higher than the enzyme production reported in strains of the same species.Optimum α-amylase activity was found at 50 to 67°C in an acid pH range from 5.5 to 6.0. These properties would allow its use in starch industry processes.
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  • 36
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 37
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 38
    Electronic Resource
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 279-292 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The continuous aerobic degradation of phenoxyalkanoate herbicides by Sphingomonas herbicidovorans MH was investigated in a bubble reactor filled with modified polyurethane-foam (PU 90/51) as a carrier for the adsorptive immobilization of the bacterial cells. The PU-foam was applied in the form of plates (5 × 10 × 10 mm) and the amount added was equivalent to a PU-load of 1.25% [w/v]. Strain MH is capable of detoxifying the dichloro-substituted phenoxyalkanoates 2,4-DP, 2,4-D and 2,4-DB and the methylchloro-substituted phenoxyalkanoates MCPA, MCPP and MCPB. Degradation of the respective substrate was followed by HPLC analyses and by determination of the chloride release. No intermediates of the degradation pathways or “dead end” products were detected by HPLC analyses. The PU-bubble reactor with immobilized 2,4-DP-pre-grown cells was run continuously at 30°C at the high dilution rate of D = 0.5h-1 with 2,4-DP (0.2 g/l), and with subsequent changes to each of the other phenoxyalkanoates as a single substrate in the feed and with an intermittent return to 2,4-DP. Finally, after an intermediate substrate accumulation, 2,4-D, 2,4-DP, MCPA and MCPP could be degraded under the aforementioned conditions corresponding to a maximum degradation rate of Qphen = 100 mg/l × h. In the case of 2,4-DB, a slightly reduced conversion rate of about 94% could be calculated. In contrast to these results, 0.2 g/l of the more recalcitrant MCPB could not be metabolized at this high dilution rate of D = 0.5 h-1 by the biofilm of Sphingomonas herbicidovorans MH, but it was degradable at a reduced dilution rate of D = 0.25 h-1. Complete detoxification of a stoichiometric mixture of the dichloro- and the methylchloro-substituted phenoxyalkanoates including MCPB, respectively, at a total concentration of 0.2 g/l was achieved at D = 0.25 h-1, corresponding to a degradation rate of Qtot = 50 mg/l × h. Finally, the efficiency of the PU-immobilized cells of Sphingomonas herbicidovorans MH in detoxifying mixtures of all six herbicides could be increased to Qtot = 75 mg/l × h by the further addition of PU-foam particles corresponding to a final PU-load of 2.5% [w/v]. This PU-bubble reactor was successfully operated for more than 12 months to clean up synthetically concocted waste waters with fluctuations in phenoxyalkanoate concentration and composition.
    Additional Material: 5 Ill.
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  • 39
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 307-318 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The biodesulphurization of Mengen lignite by a mesophilic bacterium, Rhodococcus rhodochrus ATCC 53968, was investigated in a batch stirred and aerated reactor. The experiments were carried out at 28°C with an inoculum percentage, initial pH, initial sodium acetate and lignite concentration of the biodesulphurization medium of 8% [v/v], 6.5 mM, 20 mM and 20 g/l, respectively. Variations in the sulphur contents of the lignite relative to the biodesulphurization period were monitored. The effects of the stirring and aeration rates on the removal of different sulphur forms from coal were investigated in the ranges 450-1,200 rpm and 0.1-0.53 vvm and the optimum values were found to be 500 rpm and 0.18 vvm, respectively. An increase in the total sulphur reduction with increasing biodesulphurization time was observed. The maximum total sulphur removal percentage was found to be 15.2% at 1,200 rpm after four days of incubation. The highest total sulphur removal rate was calculated on the second day of microbial desulphurization for each run. The total and organic sulphur contents of the coal after biodesulphurization were correlated with the stirring and aeration rates by using the non-linear least squares regression method. In the experimental runs lasting 8 days, the highest organic sulphur reducing percentage of 10.1% was obtained at a stirring rate of 500 rpm and an aeration rate of 0.40 vvm.
    Additional Material: 6 Ill.
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  • 40
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Selected strains of basidiomycetes (Abortiporus biennis, Trametes versicolor and Cerrena unicolor) were shown to produce enhanced extracellular peroxidase (EP), superoxide dismutase (SOD) and laccase activities following the exposure of 10-day-old fungal cultures to separate high and low temperature stress. The stressful conditions also caused an increase in the concentrations of phenol compounds and superoxide anion radicals in these cultures. At first, peroxidase activity was observed at 12 hours from the moment of temperature stress application. Laccase activity appeared at 96 hours after the maximum levels of superoxide anion radicals (48 h) and SOD activity (36-72 h). The concentration of phenolic substances grew steadily during the period of cultivation. These relations between laccase, SOD and EP as well as superoxide radicals and phenol levels in the environment of ligninolytic fungi seems to be important in the course of the biosynthesis or biodegradation of lignin, as the consequence of adaptation of these basidiomycetes to environmental temperature conditions.
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  • 41
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 356-356 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 42
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 349-355 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Comamonas acidovorans MC1, which is capable of degrading the chiral phenoxypropionate herbicides 2-(2,4-dichlorophenoxy)propionate [dichlorprop, (RS)-2,4-DP] and 2-(4-chloro-2-methylphenoxy)propionate [mecoprop, (RS)-MCPP] and of degrading the phenoxyacetate herbicides 2,4-dichlorophenoxyacetate (2,4-D) and 4-chloro-2-methylphenoxyacetate (MCPA), was investigated with respect to the enzymatic basis of this broad substrate specificity. The initial steps of the degradation pathway of (RS)-2,4-DP and 2,4-D were studied. By applying either ion exchange chromatography or hydrophobic interaction chromatography it was possible to separate two enzyme fractions with etherolytic activity, which exhibited pronounced substrate specificity. One enzyme fraction was highly specific for the degradation of the R-enantiomer of 2,4-DP and did not essentially attack the S-configuration. The other enzyme fraction showed pronounced activity toward the cleavage of the S-enantiomer and additionally utilized 2,4-D with almost equal velocity; (R)-2,4-DP was even cleaved at a low rate by this enzyme. These results confirm the existence of phenoxyalkanoatedegrading enzymes with enantiospecific properties in strain MC1.
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  • 43
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 44
    Electronic Resource
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 191-203 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The population of poly-β-hydroxybutyrate-degrading microorganisms and the biodegradation of PHB in local landfill soils were examined in vitro and in vivo. Forty-two PHB-degraders consisting of 12 bacteria, 25 actinomycetes and 5 moulds were isolated. The total PHB-degraders averaged 4.7 × 107 and 20 × 104 colony forming units (cfu)/g for San Mateo wet and dry soils, respectively, and 2.3 × 107 and 8.5 × 104 cfu/g for Carmona wet and dry samples, respectively. The PHB-degraders formed 0-59% of the total microbial population in San Mateo and 8-42% in Carmona. Complete (100%) degradation of PHB powder was observed for Chryseomonas-27 and Aspergillus-39 on day 5 in shake flask culture and for Streptomyces-4 on day 7. Burial test in landfill soils showed a 90-91% weight loss of PHB film strips within four weeks; the weight loss of polypropylene film strips was up to 0.12% only. Scanning electron micrographs of degraded films revealed the attachment of microbial cells and fungal mycelium and spores on the surfaces. Holes and cavities were also noted due to the microbial degradation processes.
    Additional Material: 3 Ill.
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  • 45
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 205-210 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The application of biotechnology in environmental processes is an enormous subject that could remain the topic of a university lecture course for many years. For this reason I wish to limit my lecture to a few examples and to attempt to sketch out particularly promising opportunities for future development.
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  • 46
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 47
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 213-223 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Acinetobacter sp. E11, isolated from Port Dickson Beach, Malaysia, was able to grow in media containing crude oil as the sole carbon and energy source. Substrate specificity studies showed that the bacterium exhibited substrate preference as growth was observed only in media containing aliphatic hydrocarbons, while aromatic and cyclic hydrocarbons inhibited growth. With the aliphatic hydrocarbons, growth was seen only in the long-chain alkanes tested (pentadecane, dodecane and hexadecane). No growth was recorded in the short-chain alkanes (pentane, hexane and heptane) tested. With complex hydrocarbons, only crude oil and 4T SHELL engine oil supported growth. No growth was observed in kerosene and PETRONAS gasoline. The isolate could grow in up to 10% and 20% [v/v] of the crude oil and alkanes tested, respectively. Among the long-chain alkanes tested, hexadecane was the most preferred, followed by pentadecane and dodecane. Nitrogen and phosphorous supplements were essential for growth and the best growth was achieved with 3% nitrogen/phosphorous additions. Microscopic observation revealed that the bacterium adhered to the hexadecane and crude oil droplets. GC analysis showed that the bacterium was able to degrade more than 60% of the hydrocarbons in the crude oil in 15 days at 37°C compared to the uninoculated media.
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  • 48
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 49
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 50
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 293-304 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The mineralization of a non-ionic alcohol ethoxylate (AEO) surfactant was investigated over the concentration range occurring in rinsing water from surfactant production processes. For this, an experimental set-up for respirometric batch experiments was developed. The set-up and the method were validated by experiments with glucose as the single carbon source. It was possible to calculate substrate decay from the time course of exogenously consumed oxygen during respirometric batch experiments. The kinetic coefficients calculated by respirometry showed a lower standard deviation than those calculated from emasured glucose concentrations.The degradation mechanism of AEO was investigated by identification of metabolities, occurring during the mineralization process of AEO, using Flow Injection Mass spectrometry (FI-MS). It was concluded that the degradation of AEO occurs in two main steps. First, the enzymatic hydrolysis of AEO into alcohol and polythylene glycol (PEG) is performed. Second, the mineralization of both substances takes place, while the mineralization of the alcohol is faster than that of the PEG. The mineralization kinetics were investigated in respirometric batch experiments. The model used is based on double MONOD kinetics for the substrates being produced by hydrolysis (μmax1 = 0.047 h-1, Ks1 = 15 mg/l DOC for alcohol; μmax2 = 0.027 h-1, KS2 = 4 mg/l DOC for PEG). The validation of the model by calculating the results obtained from measurements in a continuously operated lab scale CSTR with bacteria recycle was successful.
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  • 51
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 69-75 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: An increase in the molar growth yield (YX/S = 14.3-20.3 g/mol) on glucose (25 mM) was achieved after the transition of Zymomonas mobilis ATCC 29191 from anaerobic to aerobic steady state growth at dilution rates of D = 0.31-0.40 1/h and under oxygen-unlimited conditions. The transfer of anaerobically or aerobically grown steady state cells into a fresh medium resulted in the higher values of YX/S. A positive correlation was established between biomass and acetaldehyde yield within the range of 5-9 mM acetaldehyde in the medium. An inhibitory effect of the exogenously added acetaldehyde (Ki = 16.7 ± 2.8 mM) on the ATPase activity was observed in vitro, using cell-free extracts of anaerobically grown Z. mobilis. The results obtained provide evidence that the increased values of biomass yield could be explained by the redirection of ATP usage during aerobic growth of Z. mobilis.
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  • 52
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 53
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 86-87 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 54
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 55
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 101-109 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pleurotus sajor-caju (FR.) SINGER was cultivated on different organic wastes, namely sericulture waste, Populus deltoides MARSH, and Eupatorium adenophorum SPRENG. Paddy straw was taken as the control and all the data were compared with it. The mineral contents of the fruiting bodies of Pleurotus sajor-caju and the substrates on which the mushroom was grown were analyzed. Among the eight minerals determined (calcium, phosphorus, potassium, magnesium, sodium, iron, manganese and zinc), the potassium content was highest followed by phosphorus, magnesium and sodium. Analysis of the mineral contents of the substrates before cultivation had also been carried out. The mineral contents of the fruiting bodies of Pleurotus sajor-caju were found to be different on different substrates. It was also observed that the mineral contents of the fruiting bodies of Pleurotus sajor-caju increase when cultivated on substrates with higher mineral contents. The maximum mineral contents per 100 g of the substrates before cultivation were Ca - 347 mg; P - 151 mg; K - 1,805 mg; Na - 127 mg; Mg - 227 mg; Fe - 53 mg; Mn - 10 mg and zn - 3.1 mg. The mineral contents of the fruiting bodies of Pleurotus sajor-caju per 100 g ranged as follows: Ca - 25.1 mg to 35.3 mg; P - 448 mg to 602 mg; K - 2,146 mg to 2350 mg; Na - 139 mg to 229 mg; Mg - 153 mg to 224 mg; Fe - 9.74 mg to 20.75 mg; Mn - 2.5 mg to 4.0 mg and Zn - 2.2 mg to 3.1 mg.
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  • 56
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 19 (1999), S. 357-363 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: An alternative microbiological method for the production of malate from fumarate is presented. The yeast Dipodascus magnusii was used for this bioconversion.The optimum cell growth temperature was 28°C and the working volume 120 ml. The highest level of fumarase activity during bioconversion was achieved at a pH of 7.5 and a temperature of 37°C. These conditions were determined as optimal. Using sodium fumarate (1M), the maximum specific productivity of malic acid obtained was 1.72 g/(gDCW × h) for intact cells. In the case of ammonium fumarate, it was 2.25 g/(gDCW × h).
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  • 57
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 58
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 59
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 60
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 61
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 17-22 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A large number of 1,n-bis(alkylthio)alkanes, R′S(CH2)nSR″, was investigated by pulse radiolysis in aqueous solutions. The sulphur-centred radical cations, which were obtained on oxidation of the dithia compounds by ·OH radicals, are stabilized via 2σ/1σ* three-electron interaction between two sulphur atoms. Intramolecular stabilization is the only process observed for n = 2-4, whereas for longer chain compounds with n 〉 4 some intermolecular sulphur-sulphur interaction is also indicated. The stability and yields of the three-electron-bonded species also depend on the nature of the substituents R′ and R″, and for the intermolecular systems are a function of solute concentration. The results corroborate earlier investigations and demonstrate, in particular, that the optical parameters are a very sensitive measure of changes in electron density and structure of the three-electron-bonded systems.
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  • 62
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 23-34 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stereochemistry and mechanism of solvolysis of optically active tert-butylphenylphosphinothioic-O-trifluoromethanesulphonate (1) in solvents of different ionizing power were studied. It was found that in solvents of high ionizing power and low nucleophilicity 1 ionizes with the formation of a phosphathiacylium cation (2) as the reaction intermediate. Product resulting from the reaction of 2 with anisole was isolated and characterized.
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  • 63
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    Journal of Physical Organic Chemistry 3 (1990), S. 35-37 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Studies on the stereochemistry of silver-ion-assisted solvolysis of a new optically active tert-butylphenylphosphinothioic iodidate demonstrated that the reaction proceeds with inversion of configuration at the phosphorus atom. Evidence for phosphathiacylium cation formation as a reactive intermediate is presented.
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  • 64
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    Journal of Physical Organic Chemistry 3 (1990), S. 38-40 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Studies on the photochemically induced hydrogen-tritium exchange in o-methyl-substituted phenyl ketones are reported. It is shown that the tritium exchange can be beneficial for probing transient photoenol formation, particularly when photochemical side-reactions are occurring.
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  • 65
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Alkaline hydrolysis of diethyl alkylphosphonates and alkyl diethylphosphinates was studied in aqueous dimethyl sulphoxide. The behaviour of these acyclic phosphorus esters is very similar to that of some cyclic phosphorus esters. Rate constants were measured at three temperatures over a 30°C range, and the activation functions of the reaction were estimated. The basic hydrolytic process was proved to be a bimolecular AE reaction. Multiple regression analyses involving rate constants and substituent parameters gave, as a rule, poor results using steric constants derived from carbon compounds. However, the substituent steric effect on the rate of hydrolysis of phosphonates and phosphinates studied correlated very well with ΔΔE, representing the difference in steric energy calculated by molecular mechanics. It is attributed to the various degrees of susceptibility of carbon and phosphorus atoms to the steric hindrance of the substituents. Moreover, Newman's rule of six for the hydrolytic reaction of carboxylates was completely eliminated in phosphorus ester hydrolysis.
    Additional Material: 2 Ill.
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  • 66
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    Journal of Physical Organic Chemistry 3 (1990), S. 62-68 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The free energy dependence of the kinetic deuterium isotope effect of proton-transfer reactions in solution is usually analysed in terms of the Marcus model. By means of modern computer techniques, the more general quantumstatistical mechanical model is also amenable to routine application. The differnces in the basic assumptions of the two approaches concerning the kinetic isotope effect are discussed. Reaction series for which both the Brønsted relation and the free-energy dependence of the kinetic isotope effect are available are analysed by means of the two models using one set of parameters for both free-energy relations.
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  • 67
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    Journal of Physical Organic Chemistry 3 (1990), S. 69-76 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Strong 1H and 13C nuclear polarizations are observed when aqueous solutions of synthetic water-soluble porphyrins are irradiated in the presence of tyrosine and some of its derivatives. These polarizations are strongly pH dependent. Evidence is also shown for the formation, in the dark, of a complex between the reactants. The association constants are evaluated from the NMR chemical shifts on the aromatic tyrosine protons induced by the presence of the porphyrins. The nature of the intermediate radical pair generating the CIDNP effects is discussed. An electron-transfer reaction from tyrosine to the excited triplet state of the porphyrin, or within the porphyrin-tyrosine excited complex, is expected to be the primary step in the reaction. It is followed by subsequent proton transfer within the initial ion radical pair. The spin polarizations arise principally from the back-transfer step, as the reactants are the only products which are polarized.
    Additional Material: 4 Ill.
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  • 68
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    Journal of Physical Organic Chemistry 3 (1990), S. 95-109 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intersecting-state model previously used to interpret proton transfers in ground and excited states and enzyme catalysis was applied to the general acid-base catalysis of carbon acids. The results are consistent with the predictions published for these systems and provide a new physical meaning for the Brønsted coefficients. It is shown that in addition to the linear free energy effect, the Brønsted coefficients are also influenced by the tightness of the transition states and by electronic effects. The model suggests that the increased reactivity of carbon acids towards proton transfer in non-hydrogen-bonding solvents is caused by an added electronic effect on the thermodynamics of the reactions. The curvatures of the Brønsted plots are interpreted in terms of an entropic contribution to the position of the transition state.
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  • 69
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    Journal of Physical Organic Chemistry 3 (1990), S. 110-118 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas-phase nitration of thiophene (1) and N-Methylpyrrole (2) was studied by radiolytic tecniques, supported by chemical ionization mass spectrometry. The substrate and positional selectvities of protonated alkyl nitrtes (CH3NO3H+, CF3CH2NO3H+) were deduced from competitive reactions with bezene performed under different conditions. The apparent kS/kB ratios, which are independent of the pressure and unaffected by the presence of a strong base (NEt3), depend on the nature of the electrophile, passing for 1 and 2 from 7·2 and 6·4, respectively, with CH3NO3H+ to 1·1 and 1·0, respectively, with the more reactive fluorinated caution. Predominant (88%) α-substitution takes place in 1, whereas no appreciable positional discrimination is displaced by 2. The results suggest that the electrophilic attack can also occur a the heteroatom, and point to the same mechanism postulated for gasphase nitration of aromatic substrates, the reactivity being essentially governed by electrostatic interactions within the ‘encounter pair’.
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  • 70
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    Journal of Physical Organic Chemistry 3 (1990), S. 485-488 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The interconversion between two equivalent enol forms of 3-hydroxyphenalenone took place predominantly through a diketo form with a free energy of activation of ca 14 kcal mol-1 in DMSO solution determined by 125·8 MHz13C NMR measurement. On the other hand, the corresponding interconversion in 2-carboxy-3-hydroxyphenalenone was not frozen on the time scale of 13C NMR spectroscopy down to -60°C. This acceleration in the interconversion rate of the latter may be interpreted by a double proton switching between the hydrogen-bonded 2-carboxyl and 3-hydroxyenone moieties.
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  • 71
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Literature data on the change in the selectivity values, kE/kw, for several solvolysing systems in ethanol (E)-water (W) on addition of acetone were analysed. It is suggested that acetone acts as a basic cosolvent for both ethanol and water and that the change in the activity coefficients on changing the solvent composition is mainly responsible for the observed effect.
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  • 72
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of reactions between 2-phenylethyl benzenesulphonates (2-PEB) and benzylamines in acetonitrile at 65·0°C have been studied; the mechanism was examined on the basis of the sign and magnitude of cross-interaction constants ρij and βij. In contrast to the reactions of 2-PEB with anilines in methanol, participation of the aryl-assisted pathway was negligible, with a strong indication that the reaction proceeds largely by an intermolecular SNi mechanism with a four-centre transition state (TS). The effect of substituents on the TS variation was in accord with the predictions of the quantum mechanical model.
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  • 73
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    Journal of Physical Organic Chemistry 3 (1990), S. 534-544 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solvent polarity of a series of organic salts in their molten state has been determined using the solvatochromic dyes: pyridinium N-phenolate betaine, the basis of the ET scale, and N,N-diethyl-4-nitroniline, one of the primary standards for the π* scale. Each of these dyes was dissolved in the following liquids: lithium acetate-sodium acetate-potassium acetate eutectic; ethylammonium chloride; dimethylammonium cloride; diethylammonium nitrate; ammonium trifluoracetate; tetraethylammonium acetate; tetrabutylphosphonium chloride; octyltributylphosphonium chloride; dodecyltributylphosphonium chloride; tetrabutylammonium bromide; tetrabutylphosphonium bromide; octyltributylphosphonium bromide; dodecyltributylphosphonium bromide; octyltributylphosphonium iodide; dodecyltributylphosphonium iodide; tetrahexylammonium benzoate; methyltrioctylphosphonium dimethylphosphate; and methyltrioctylammonium chloride. The ultraviolet and visible spectra were measured for each of these. In addition, data were collected as a function of temperature and in the presence of neutral and ionic additives. In general, these molten salts represent solvent polarities equivalent to moderately polar aprotic solvents such as acetone and acetonitrile. The salts with cations capable of being hydrogen bond donors gave considerably higher values, equivalent to or higher than water, the solvent with the highest value on the ET scale. These and the eutectic mixture are thought to involve specific dye-solvent interactions which cause these anomalously high values.
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  • 74
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    Journal of Physical Organic Chemistry 3 (1990), S. 581-586 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Pyrimidine dimers, which form by a symmetry allowed (πs2 + πs2) photocycloaddition reaction, are subject to photosensitized cycloreversion by electron donors, such as indoles. In a linked dimer-indole system, photoinitiated electron transfer occurs intramolecularly from indole to dimer to produce a charge-separated species (dimer-.-indole+.). This species undergoes cycloreversion in competition with back electron transfer. Studies of the temperature dependence and solvent dependence of this competition have allowed the relative values of the activation parameters for the competing processes to be determined. In water (5-65°C) the free energy of activation of splitting minus that of back electron transfer (ΔΔG≠ = ΔGspl≠ - ΔGbet≠) was found to be 1·3 kcal mol-1. The enthalpy of activation difference (ΔΔH≠) was found to be 1·1 kcal mol-1 and the entropy of activation difference (ΔΔS≠) was found to be -0·51 cal mol-1 K-1. In EPA (diethyl ether-isopentane-ethanol, 5:5:2; -85 to 25°C) the value of ΔΔG≠ remained the same, but the entropy and enthalpy contributions were different (ΔΔH≠ = 0·72 kcal mol-1; ΔΔS≠ = -1·8 cal mol-1 K-1). The results have been interpreted in terms of the effect of the polarity of the solvent on the transition states for the two competing processes. Enthalpy effects retard splitting more in water than in EPA, whereas entropy effects favor back electron transfer more in EPA than in water. Potential implications of these results for the mechanism of enzymatic photocycloreversion of pyrimidine dimers in DNA are considered.
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  • 75
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    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 76
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    Journal of Physical Organic Chemistry 3 (1990), S. 627-634 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reactions of a series of 3-(p-substituted phenyl)-1-phenylprop-2-yn-1-ones with piperidine and morpholine in methanol were studied and their rates measured. The products were 3-piperidino- and 3-morpholino-3-(p-substituted phenyl)-1-phenylprop-2-en-1-ones. 1H NMR spectra were used to determine the configurations of the obtained products. A good Hammett correlation was obtained with ρ values of 1·15-1·10 and 1·15-0·53 for piperidine and morpholine, respectively, which suggest a carbanionic character of the transition state. A two-step mechanism is postulated for these nucleophilic additions.
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  • 77
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The 19F NMR spectra of 30 substituted α,β,β-trifluorostyrenes (Y-TFSs, 1) covering a diverse range of substituents are reported and discussed. Values (δF1, δF2, Δδ3 - 1 and Δδ3 - 2) derived from the 19F NMR chemical shifts of the fluorine atoms of 1 are found to correlate very well with σI and σR0. The results of the correlations of the 19F chemical shifts with dual (σF and σR) and triple parameter (σF, σR and σα) treatments are compared. An unresolved substituent parameter σmb, is proposed for applications to systems in which the substitutent Y interacts with a multiple bond and is compared with σ+.
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  • 78
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Direct kinetic measurements of the C-protonation rates of 1,2,5-trimethyl- and 3,4-dimethyl-pyrroles allow the first comparison of the relative kinetic proton affinities of unsubstituted and substituted positions of the pyrrole ring.
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  • 79
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    Journal of Physical Organic Chemistry 3 (1990), S. 697-702 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The potential energy surface for the addition of the hydride ion to hydrogen isocynide reported previously was re-examined. An improved energy surface was explored at the MP2/6-31 + + G** level while relative energies were estimated at the MP4SDTQ/6-311 + + G** level and corrected for zero-point vibrational contributions. The calculated results show the existence of transition structures for both cis and trans-additions of H- to the carbon end of HN≡C even though the corresponding barrier heights are small. These transition structures did not exist at a lower level of theory (HF/4-31G) employed previously.The cis addition is calculated to be favoured over the trans addition by 10 kcal mol-1. The overall addition is thus strongly stereoselective, if not purely stereospecific. This result confirms our previous analysis of the stereoelectronic effect in the addition-elimination process involving imidoyl anions as intermediates. Recent experimental work on the addition of OH- to ArN≡C is discussed.
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  • 80
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The peak potentials of substituted α,α,α-trifluoroacetophenones were measured in acetonitrile with 0·1 M tetrabutylammonium perchlorate. The cyclic voltammograms indicated an irreversible electrochemical process for the first wave (Epc1) and a partially reversible one for the second wave (Epc2) when the scan rate was slower than 100 mV s- 1. Excellent linear correlations were observed for Epc1 with σ constants (ρ = 0·526, r = 0·999) and for Epc2 with σ- constants (ρ = 0·605, r = 0·998), respectively. Therefore, unknown σ values such as -0·36 for 3, 4-ethyleneoxy can be estimated from these correlations. The mechanism of the electrode process probably involves a single electron transfer and the formation of a pinacol.
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  • 81
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    Journal of Physical Organic Chemistry 3 (1990), S. 746-750 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The deprotonation reaction mechanism of methyl diethylphosphonoacetate in the presence of lithium salts and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was examined by infrared spectroscopy. It was found that the intermediate species formed by chelation of the bidentate phosphonate with a lithium cation or an ion pair of the salt deaggregated by DBU takes part in the reaction path. The role of the anion X- is to induce the elimination of a protonated DBUH+X- ion pair and that of the solvent is to compete with the bidentate phosphonate in cation solvation. A similar mechanism via a related intermediate is proposed to interpret the results obtained by other workers on the catalysis by Ba(OH)2 of the Wittig-Horner reaction.
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  • 82
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    Journal of Physical Organic Chemistry 3 (1990), S. 765-783 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enumeration and development of conceptual tools for understanding the chemical properties of practical benzenoid hydrocarbons is stressed. Currently known isomer numbers for benzenoids having up to 60 carbons are summarized. Although there are well over 2 million isomers in this range, only approximately 500 benzenoid hydrocarbons have been characterized.
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  • 83
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    Journal of Physical Organic Chemistry 3 (1990), S. 789-798 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The acetylation (with acetic anhydride-pyridine in tetrahydrofuran) of the ortho, meta and para isomers of bis(hydroxymethyl)benzene (1) was studied. Third-order rate constants k1 (formation of monoacetate 2 from 1) and k2 (formation of diacetate 3 from 2) for all three isomers were determined, as were the rate constants for acetylation of benzyl alcohol and its ortho- and para-ethyl derivatives under the same conditions. The compositions of the final product mixtures (comprising 1, 2 and 3) were ascertained as a function of the initial ratio of acetic anhydride to 1. Comparisons were made with predictions based on a previously published independent functional groups model, which assumes that k2/k1 = 0·50. All three isomers gave product mixtures whose compositions were in generally good agreement with predictions based on the model. For the para and meta isomers the ratios k2/k1 were determined experimentally to be 0·548 and 0·521, respectively. The k2/k1 ratio for the ortho isomer was found to be 0·605, and its k1 and k2 values were lower than those for the para and meta isomers. Possible explanations for the anomalous behavior of the ortho isomer are discussed.
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  • 84
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    Journal of Physical Organic Chemistry 3 (1990), S. 812-816 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chlorocyclohexane does not react in the dark with diphenylphosphide ions in liquid ammonia, but it reacts under irradiation to give the substitution product. Bromocyclohexane reacts slowly in the dark, but this reaction is strongly accelerated by light, and inhibited by p-dinitrobenzene. 3-Bromo-2-tetrahydropyranyl allyl ether (used as a radical probe) reacts with diphenylphosphide ions under irradiation to give both the straightforward and the cyclized substitution products. This photostimulated reaction is also inhibited by p-dinitrobenzene. It is suggested that the chlro-bromocyclohexanes and related compounds react under irradiation by the SRN1 mechanism of nucleophilic substitution.
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  • 85
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    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 86
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    Journal of Physical Organic Chemistry 3 (1990), S. 260-265 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Subtilisin BPN′ catalyzes the hydrolysis in protium and deuterium oxides of p-NO2C6H4OCOCL2NHCO2CH2C6H5(L = H, D) in the pH(D) range 5·0-8·5 (H2O) and 5·4-9·0 (D2O), according to simple Michaelis-Menten kinetics. The parameter kcat/Km exhibits pH(D) inflection points of 7·17 ± 0·05 (H2O) and 7·69 ± 0·08 (D2O), and kcat shows 6·88 ± 0·05 (H2O) and 7·50 ± 0·07 (D2O). The ‘normal’ ΔpK values of 0·5-0·6 indicate no unusual effects of D2O on enzyme properties. The solvent isotope effects (H2O/D2O) on the limiting values of the rate constants at high pH(D) are 1·13 ± 0·07 for kcat/Km and 1·29 ± 0·05 for Kcat. These small effects indicate no more than minor contributions of general acid-base catalysis for rate-limiting events for either kcat/Km or kcat. The β-deuterium secondary isotope effects (2H/2D) are roughly estimated by extrapolation as 0·95 ± 0·01 for kcat/Km, corresponding to substantial tetrahedral character in the transition state, and 1·03 ± 0·03 for kcat, consistent with no tetrahedral character. Models consistent with these results have as rate-limiting events for kcat/Km nucleophilic attack by active-site imidazole and for kcat, among other possibilities, the release of carboxylate product from the imidazolium form of the enzyme.
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  • 87
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    Journal of Physical Organic Chemistry 3 (1990), S. 279-284 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The gas-phase thermal decomposition of diacetyl compounds, (CH3CO)2X with X = O and S, was investigated theoretically using the semiempirical MO methods MNDO and AM1. The initial decomposition of the diacetyl compounds proceeded through a six-membered ring transition state involving the keto form with a slightly lower activation enthalpy for diacetyl sulphide (X = S); the process via an enolic form of the transition state was kinetically unfavourable. In the initial decomposition of the diacetyl compounds and in the subsequent pyrolysis of acetic and thioacetic acid, ketene formation was found to be the most preferred path, where the ease of Cα—X bond cleavage is relatively more important than nucleophilic attack on the β-hydrogen in determining the overall reactivity. In the methane formation process, the reactivity was entirely dependent on the X—H bond strength in CH3COXH where X = S, NH and O.
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  • 88
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The antioxidant activity of 2-hydroxyestradiol was measured quantitatively and compared with those of other estrogens in oxidations of methyl linoleate in homogeneous solution and in aqueous dispersions, oxidations of soybean phosphatidylcholine liposomal membranes and oxidative haemolysis of rabbit erythrocytes, all induced by free radicals generated from a radical initiator. Similar antioxidant activities of estrogens were observed, irrespective of the oxidation system. 2-Hydroxyestradiol was found to be a potent radical scavenger and its antioxidant activity was close to that of α-tocopherol, the strongest natural antioxidant. Other phenolic estrogens such as estrone, estriol and β-estradiol showed a modest antioxidant activity and testosterone did not act as an antioxidant.
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  • 89
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    Journal of Physical Organic Chemistry 3 (1990), S. 339-345 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2-Diazopropane, generated by photolysis of 2-methoxy-2,5,5-trimethyl-Δ3-1,3,4-oxadiazoline, was trapped in situ by cycloaddition to norbornene, endo- and exo-5-methylnorbornene, endo- and exo-5-phenylnorbornene, endo- and exo-5-methoxycarbonyl norbornene and endo- and exo-dicyclopentadiene. In all cases, only exo addition was observed. In spite of the exo approach of diazopropane to the norbornene double bond, endo substituents at C-5 and/or C-6 influenced the regiochemistry of addition whereas exo substituents did not. The results are interpreted in terms of a concerted, asynchronous mechanism in which C—C bond formation runs well ahead of N—C bond formation, as predicted from theory. The regiochemical control exercised by apparently remote endo substituents provides a new experimental criterion for asynchrony or synchrony of cycloadditions that are known to be concerted.
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  • 90
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    Journal of Physical Organic Chemistry 3 (1990), S. 346-348 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas-phase acidities of acrolein and methyl acrylate were measured by bracketing in a flowing afterglow/SIFT apparatus. For acrolein ΔG°acid = 369 ± 4 kcal mol-1 and for methyl acrylate ΔG°acid = 373 ± 4 kcal mol-1. These acidities are substantially lower than those of the saturated analogs propionaldehyde and methyl acetate, respectively, even though hydrogens attached to sp2-hybridized carbon are intrinsically more acidic than those attached to sp3-hybridized carbon. Resonance stabilization of the neutral form by conjugation of the C=C double bond with the carbonyl group and allenic destabilization of the anionic form of the two acids can account for the relatively low acidities.
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  • 91
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 349-357 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The 4,9-dimethyltricyclo [3.3.1.02,8]nona-3,6-dien-9-yl (4,9-dimethyl-9-barbaralyl) cation (3) was generated from 4,9-dimethyl-9-barbaralol (5) at -135°C in two different superacid mixtures [FSO3H—SO2CIF—SO2F2(1:6:1) and FSO3H—SO2CIF—SO2F2—CHCl2 (2:10:10:1 by volume)]. Its 1H and 13CNMR spectra show a strong temperature dependence in the range -150 to -125°C. The changes in band shapes with temperature show that the following exchanges take place: 4-methyl with 9-methyl, C-4 with C-9, C-1 with C-3 and C-2 with C-8. C-5, C-6 and C-7 are found not to exchange rapidly either with each other or with the other carbons in 3. The mechanism of this novel rearrangement is suggested to involve the bicyclic 2,7-dimethylbicyclo [3.2.2] nona-3,6,8-trienyl cation and the secondary barbaralyl cation 4,6-dimethyltricyclo [3.3.1.02,8] nona-3,6-dien-9-yl as intermediates rather than 7,8-dimethyl bicyclo [3.2.2] nona-3,6,8-trienyl cation, which does not have a methyl group on the allyl cation moiety. Comparisons with rearrangement mechanisms for other barbaralyl cations were also made. The rate constant for the degenerate rearrangement of 3 is 160 s-1 at -140°C, which corresponds to ΔG≠s = 26 kJ mol-1 (6·3 kcal mol-1). At -125°C ion 3 rearranges non-degenerately to the 1,4-bishomotropylium cation 1,8-dimethylbicyclo [4·3·0] nona, 2,4,7-trienyl (4) with k = 3 × 10-4 s-1. A mechanism for this rearrangement and the synthesis and purification of the ion precursor 4 are also reported.
    Additional Material: 1 Ill.
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  • 92
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 390-396 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dephosphorylation of p-nitrophenyl diphenylphosphate (pNPDPP) by OH- in aqueous cationic micelles of cetyltrimethylammonium hydroxide (CTAOH) is inhibited by tert-butyl hydroperoxide (t-BuO2H), which reduces the binding of OH-, and whose anion is a relatively ineffective nucleophile. Reaction is faster in microemulsions of CTACl, n-octane and OH-, with t-BuO2H as cosurfactant, than in otherwise similar microemulsions with t-butyl alcohol as cosurfactant. Dephosphorylation by m-chloroperoxybenzoate ion is slower in microemulsions of cetyltrimethylammonium mesylate or benzenesulfonate, with n-octane and tert-butyl alcohol, than in cationic micelles, but a wide range of concentrations can be examined. The reaction rates qualitatively follow the concentration of peroxy acid relative to surfactant, and inert anions slow the reaction. Dephosphorylation by peroxyphthalate dianion in micelles of CTACl fits a pseudophase kinetic model, except in very dilute surfactant where reaction is faster than predicted.
    Additional Material: 3 Ill.
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  • 93
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The four possible diastereomeric 5,7-oxido-6-hydroxyiminocholestanes and their O-acetates have been synthesized. The stereochemistry of one of the latter has been proved unequivocally by x-ray diffraction. Their 1H and 13C NMR and also their circular dichroism spectra are discussed. It is now also possible to determine unequivocally the stereochemistry of the ring-junction geometry and the oxime E or Z stereochemistry.
    Additional Material: 4 Ill.
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  • 94
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 509-518 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 9,10-Dicyanoanthracene (DCA) sensitized the photooxygenation of 1,4-diphenyl-1,3-butadiene(1a) and its 4,4′-dimethoxy derivative (1b) to afford the corresponding endoperoxides 2 and the other oxidized products such as aldehydes and epoxides. The mechanism of the DCA-sensitized photooxygenation of 1 was diversified by solvent polarity. In non-polar solvents the reaction involves an exciplex intermediate, which leads to formation of triplet DCA (3DCA*) with an efficiency of 0·64 in the case of 1a. The resulting 3DCA* acts as a sensitizer for the generation of singlet oxygen (1O2) and thus 1O2 reaction occurs exclusively to give 2. On the other hand, single electron-transfer quenching of 1DCA* by 1 is feasible in polar acetonitrile and a primary ion pair can be formed. Competing with fast back electron-transfer deactivation, the primary ion pair produces free ions in limited yield to furnish electron transfer oxygenation. In the case of the DCA-1a system, free ions were produced with an efficiency of ca 4%. Thus, in acetonitrile, electron-transfer oxygenation partly took place to give the other oxidized products, whereas the 1O2 pathway was still valid and responsible for the formation of 2. The effect of solvent polarity was apparently less pronounced in the case of 1b because the reactivity of 1b toward 1O2 is about five times higher than tht of 1a. For such 1O2-reactive substrates, the electron-transfer pathway would become dominant only when the substrate concentration is impractically high.
    Additional Material: 7 Ill.
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  • 95
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The second-order rate constants of the reactions between benzenesulphonyl chlorides and anionic nucleophiles, benzoates and cinnamates, in methanol at 30·0°C are reported. A marked increase in rate found with a p-nitro substituent in the substrate indicated the development of an electron-rich centre on the S atom in the transition state. The two types of cross-interaction constants, ρxy and λxy, suggested that bond formation in the SN2 transition state with anionic nucleophiles is greater than that for the corresponding reaction with aniline nucleophiles.
    Additional Material: 5 Tab.
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  • 96
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: pKa′ Values are reported for two 2H-pyrroles and their 3H-pyrrole isomers. The latter have basicities of the same order as similarly substituted pyridines, whereas the former are 2-2·5 pK units more basic, 2,2,3,5-tetramethyl-2H-pyrrole having a pKa′ of 8·40, close to that for 2-aminoimidazole. Possible reasons are given.
    Additional Material: 1 Tab.
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  • 97
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 599-605 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new criterion for the reactivity of π electron systems is proposed. The method incorporates and modifies ideas of Coulson and Fukui et al. about free valence. The proposed reactivity index includes covalent and lonic components and is suitable for elctrophilic, radical and nucleophillic attack. The method is tested for a few simple π systems and differences from Coulson and Fukui et al. are discussed. Finally, it is applied to the electrophilic attack of a series of substituted benzenes and to nucleophilic attack of a series of subsituted benzoic acid esters.
    Additional Material: 3 Ill.
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  • 98
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 703-710 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ionization constants of nine amphoteric 5-pyridylmethylenehydantoins were measured in 80% (w/w) dimethyl sulphoxide-water at 25 °C. The effects of structure and Z/E configuration on both pKaI and pKaII values are discussed. The especially low basicity and acidity of the Z-isomers of the N-unsubstituted and 3-methyl-substituted 5-(2-pyridylmethylene)hydantoin are attributed to the formation of intramolecular N(1)—H…N hydrogen bond in the s-cis conformation of these compounds. The existence of N(1)—CH3…N attraction is also postulated for the Z-isomer of 1-methyl-5-(2-pyridylmethylene)hydantoin.
    Additional Material: 4 Ill.
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  • 99
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 732-736 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A bond energy scheme has been developed and two previously existing schemes have been extended for the calculation of heats of formation of aliphatic amines using ab initio 6-31G* energies in place of experimental data. The results are in good agreement with those obtained experimentally and suggest that this method can be used to predict heats of formation of molecules of this class with an accuracy competitive with good quality experiments, and with probable errors of less than 1 kcal mol-1.
    Additional Material: 7 Tab.
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  • 100
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 737-745 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ab initio SCF-MO method was employed to examine the possibility of a reaction pathway without a carbocation intermediate in the pinacol rearrangement. The molecular geometries of the transition states were obtained for the 1,2-hydride shift together with H2O elimination, starting from the various methyl-substituted protonated 1,2-diols. It was found that the activation energies depend strongly on the substitutents. A comparison of the relative energies between β-hydroxycarbonium ions and the transition states of the concerted mechanism suggests that the stepwise mechanism is less favourable than the concerted path in each case.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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