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  • 2000-2004  (43)
  • 1985-1989  (1,725)
  • 1830-1839
  • 2000  (43)
  • 1988  (1,725)
  • Organic Chemistry  (765)
  • Engineering  (598)
  • Atomic, Molecular and Optical Physics  (222)
  • Life Sciences  (183)
Material
Years
  • 2000-2004  (43)
  • 1985-1989  (1,725)
  • 1830-1839
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  • 1
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The increasing requirements in wastewater treatment have led to the development of new wastewater treatment processes based on the know-how and experience in reaction and process engineering of the chemical industry. Due to their compactness, closed operation and high flexibility, these new processes show a large potential for process integration and significant cost reduction in particular for highly polluted industrial wastewaters.This paper discusses the HCR (high-performance compact reactor) - process, developed at the Mass Transfer Laboratory of the Technical University of Clausthal within the last decade. This process has been realized in more than 30 technical applications with a volume loading of up to 70 kg COD/m3 d and an energy consumption of about 0.4 kWh per kg CODelim.
    Additional Material: 10 Ill.
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  • 2
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 169-174 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nitrogen fixing Anabaena azollae strains isolated from four different Azolla cultures were characterized based on their total protein profile and RAPD profile to study the existing variation among them. As expected, the isolates showed almost similar protein banding patterns, but exhibited differences in 40-70 KDa protein subunits. Polymerase chain reaction of the DNA of the isolates, using four different primers, amplified specific sequences of DNA and showed clear polymorphism among the isolates. The RAPD profile generated the fingerprinting pattern characteristic of each strain based on the sequence of the primers used. Common band sharing observed between the strains A. azollae-RS-KK-SK-AM and A. azollae-RS-KK-SK-RP probably represents maternal inheritance of DNA to the progeny. The polymorphic bands were generated specifically for the isolates A. azollae-RS-KK-SK-RP and A. azollae-RS-KK-SK-AM with primers numbered 2 and 4, respectively, which could be developed as possible markers for these isolates.
    Additional Material: 1 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 175-183 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mature seed-derived callus from an elite Chinese japonica rice cv. Eyl 105 was transformed with a plasmid containing the selectable marker hygromycin phosphotransferase (hpt) and the reporter β-glucuronidase (gusA) genes via particle bombardment. After two rounds of selection on hygromycin (30 mg/l)-containing medium, resistant callus was transferred to hygromycin (30 mg/l)-containing regeneration medium for plant regeneration. Twenty-three independent transgenic rice plants were regenerated from 127 bombarded callus with a transformation frequency of 18.1%. All the transgenic plants contained both gusA and hpt genes, revealed by PCR/Southern blot analysis. GUS assay revealed 18 out of 23 plants (78.3%) proliferated on hygromycin-containing medium had GUS expression at various levels. Genetic analysis confirmed Mendelian segregation of transgenes in progeny. From R2 generations with their R1 parent plants showing 3:1 Mendelian segregation, we identified three independent homozygous transgenic rice lines. The homozygous lines were phenotypically normal and fertile compared to the control plants. We demonstrate that homozygous transgenic rice lines can be obtained via particle bombardment-mediated transformation and through genetic analysis-based selection.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 202-202 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 219-233 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The GRAM-positive bacterium Rhodococcus erythropolis K2-3 and the GRAM-negative Ochrobactrum anthropi K2-14 are capable of synergistically degrading 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB). The two strais execute this task in a symbiotic manner, but the nature of the interaction involved in the degradation is only partially understood as yet. An essential first step in elucidating the interaction is to be able to monitor the two strans separately, at the cellular level, within mixed populations. Therefore a method exploiting fluorescently labelled lectin probes was developed. Since Concanavalin A (Con A) binds specifically to R. erythropolis K2-3, it was selected and linked to the fluoresent dye Bodipy 630/650, which has an excitation maximum in the red part of the visible light spectrum. Forward light scatter (FSC) and DNA fluorescence from both strains were also measured to obtain simultaneous information about their physiological states. The three parameters were conveniently monitored by dual and triple excitation flow cytometry in conjunction with double fluorescent staining techniques. In addition, the strains were identified using an epifluorescence microscope. These techniques were found powerful tools for the population analysis of this mixed bacterial system.
    Additional Material: 7 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 235-274 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: A quite unconventional, innovative scientific methodology called “macroscopic pattern analysis” is presented in this paper. This approach is more adequate in the case of complex systems than the well-known microscopic, mechanistic approach. Complex systems are not only attracting more engineering interest, but their scientific treatment is increasingly wanted by society due to the manifold problems in Earth's ecosphere. The macroscopic pattern approach will be explained in depth and illustrated in some case studies from the ecosphere (sustainability, hurricanes and avalanches), where nature serves as a teacher for the solution of the sustainability problem. Then, a series of case studies on macropatterns are described showing the problem-solving capacity for anthropo- and technosphere: sustainability in society with an index of sustainability, the eco-social market economy with eco-tech as an instrument, biokinetics, bioreactor mixing and integrated bioprocessing with models, design of cars and houses and even quality of life as an attempt to quantify macropatterns.The innovations are briefly compared in their problem-solving capacity with known approaches such as the microscopic method in science, technology and society (free market economy), including the evaluation of other indices and cleaner production, industrial ecology and zero emission initiative. Finally, a deeper integration of sciences, ethics, arts and nature will be introduced based on the vision with macroscopic pattern analysis, where the different domains of human life are integratable to effect a reconciliation.
    Additional Material: 22 Ill.
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  • 9
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 17-29 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dynamic behaviour of biofilters intended to remove toluene and xylene from air was studied during transient states. Laboratory scale biofilters were filled with a mixture of peat, bark and wood and inoculated with a mixed microbial population. Toluene and xylene were applied both as single pollutants and as mixtures. Attention was focused on the evaluation of the following transients: the response of biofilters to step changes and peaks in pollutant concentrations, the effect of changes between single and multiple pollutant loadings and the response to shutdown periods.The biofilters demonstrated a good dynamic stability during transient states induced by change in inlet pollutant concentrations. Their time periods did not exceed three hours. No interaction between xylene and toluene degradation was observed during changes in loading with single pollutants or their mixture. The performance interruptions lasting less than 24 hours were found to have no significant influence on the removal efficiency of biofilters. When the biofilters were reacclimated after longer starvation periods, a short temporary decrease in efficiency whose minimum and duration were proportional to the length of a preceding shutdown period was observed. The longest starvation period (7 days) resulted in a reacclimation lasting 7 hours only. Adaptations of a microbial population to new operating conditions as well as sorption/desorption processes were suggested as the main factors influencing the dynamic reponse characteristics.
    Additional Material: 10 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 31-38 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: In this paper, the in vivo decolourization of the polymeric dye Poly R-478 by semi-solid-state cultures of Phanerochaete chrysosporium BKM-F-1767 (ATCC 24725) was investigated, employing corncob as a support. In order to stimulate the ligninolytic system of the fungus, the cultures were supplemented with veratryl alcohol (2 mM) or manganese (IV) oxide (1 g/l).Maximum manganese-dependent peroxidase (MnP) and lignin peroxidase (LiP) activities of around 2,000 U/l and 400 U/l were attained by the former, whereas the activities reached by the latter were of about 1,500 U/l and 200 U/l, respectively. Furthermore, laccase activity (around 150 U/l) was only detected in manganese (IV) oxide supplemented cultures.The polymeric dye Poly R-478 (0.02 w/v) was added to three-day-old cultures. A percentage of biological decolourization of about 85% was achieved using cultures supplemented with veratryl alcohol, whereas MnO2 cultures showed a rather lower percentage of around 58% after nine days of dye incubation. Moreover, a correlation between MnP activity and Poly R-478 decolourization could be observed, indicating that this enzyme is mainly responsible for dye degradation.In the present work, the in vivo decolourizing capability of the ligninolytic complex secreted by P. chrysosporium was investigated under the above-mentioned cultivation conditions, employing a model compound, such as the polymeric dye Poly R-478.
    Additional Material: 2 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 187-187 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 189-201 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Desulfovibrio vulgaris strain PY1 was isolated from a 3-chlorobenzoic acid (3CBA) degrading anaerobic enrichment culture, using anaerobic Percoll density centrifugation. When grown on pyruvate (20 mM), in the absence of sulphate and under strict anaerobic conditions, this organism converted not only the co-substrates benzoate (BA), 3-amino-BA and 3CBA to the corresponding alcohols but also ten other different halogenated benzoic acids, viz., 4-Cl-, 3-Br-, 4-Br-, 3-I-, 3-F-, 4-F-, 2,4-di-Cl-, 2,5-di-Cl-, 3,4-di-Cl- and 3,5-di-Cl-BA. This was verfied with HPLC and GC/MS spectrometric analyses. The yields of the co-substrate converted after 30 days of growth were between 20% and 88%, depending on the compounds which had been added at initial concentrations of 500 μM. Sulphate, sulphite, thiosulphate and disulphite inhibited the formation of 3-Cl-benzyl alcohol (3CBOH), i.e. a 97 to 99% inhibition, and nitrate and sulphur had no effect (a 7-10% inhibition). In cell-free extracts, the reduction of 3CBA to 3CBOH required strict anaerobic conditions, pyruvate or H2 as electron donors and the addition of methylviologen (MV), FAD, FMN or ferredoxin as electron carriers. The specific activity of the reduction of 3CBA to 3CBOH in crude extract was 5.3 nmol/(mg protein min). The reaction was not inhibited by additions of sulphate or sulphite (5 mM), but was completely inhibited at concentrations of 10 mM 3CBA or 50 mM BA. A carboxylic acid reductase (aldehyde dehydrogenase), which acted on non-activated 3CBA and was responsible for the reduction of 3CBA to 3-Cl-benzaldehyde, was found in the solube fraction (94% of the total activity). These results demonstrate that strain PY1 was able to effectively reduce a wide range of halogenated benzoic acids to the corresponding alcohols.
    Additional Material: 3 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 203-218 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The recent upsurge in information technology has provided the international community with an easy access to professional journals (e.g. Electronic Journal of Biotechnology at http://www.ejb.org; etc.), discussion groups (e.g. bioenergy@cret.org; digestion@crest.org; etc.) and recently to electronic international conferences (e.g. ICIBS; http://www.cid.harvard.edu/cidbiotech, etc.) as well as a series of biotechnological information material (e.g. http://www.psrast.org, etc.) to stay in contact and receive up-to-date information in biotechnology. There is no doubt that this new technology will be more cost effective in future and reach more people in communities around the globe.This review reports on one such an electronic conference aiming at bridging the communication gap between developed and developing countries. This conference dealt with integrated biosystems and has provided an excellent forum for more than 100 active participants from all regions of the world. As has been demonstrated in this review, the conference was able to show the very different approaches towards the use of biotechnology in developed and developing countries, cold and tropical climate regions owing to their different ecological, economical and societal problems. It also demonstrated very clearly that the field of molecular genetics and/or genetic engineering is not a priority issue in developing countries, but rather the need for clean technologies, multiproduct formation through socio-economic integrated biosystems, e.g. incorporating microbial waste management into agro-industries, in human activities and their roles in creating better health conditions, a better environment and sustain development.It is hoped that this review will lead to a greater use of the electronic facilities available to inform and educate both the northern and the southern communities more readily of their needs and requirements to improve understanding and efforts for a sustainable future.
    Additional Material: 4 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 275-288 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The purpose and scope of this article is to introduce capable zeolites into downstream processing of natural compounds, especially flavour compounds like 2,5-dimethyl-4-hydroxy-3(2H)-furan-3-one (Furaneol®Furaeol is a registered trademark of FIRMENICH, Ch). The synthesis and the recovery of Furaneol from L-rhamnose are presented. Therefore adsorption isotherms of the zeolites ZSM5 and DAY with varying modules have been determined and adsorption experiments using model and reaction mixtures of Furaneol synthesis were performed and will be discussed.
    Additional Material: 11 Ill.
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  • 16
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: A fermentation process for manufacturing 1,4-piperazinium-(L,L)-dilactate from renewable raw materials and a method for processing this product into L,L-dilactide are described. Lactic acid fermentation with Lactobacillus paracasei was modified in such a way that pH control occurred by using an aqueous solution of piperazine as a correcting agent instead of sodium hydroxide solution. The production of a stoichiometrically composed piperazinium lactate was possible when the pH was 5.0. From 5.0 kg of glucose and 2.15 kg of piperazine, 6.65 kg of 1,4-piperazinium-(L,L)-dilactate were formed in the fermentation process. Separation from fermentation broth, purification and concentration of the product in aqueous solutions were carried out by means of ultrafiltration, nanofiltration and electrodialysis. Total product retention by the membranes used was about 33%. The crystalline salt was obtained by vacuum evaporation. Processing of the 1,4-piperazinium-(L,L)-dilactate into L,L-dilactide was performed in a special glass reactor. A product yield of 70% was achieved. The purified product was characterized by elementary analysis, as well as solubility behaviour, polarity and spectroscopic data. An overall process consisting of the stages fermentation, purification and concentration of piperazinium dilactate as well as cyclization of the latter to dilactide is described.
    Additional Material: 9 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 161-168 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Five different chemical reagents and γ-rays were tested for the sanitization of immobilized biocatalysts with high penicillin G acylase (PGA) activity. The most effective chemical reagents were N-cetyl-N,N,N-trimethylammonium bromide (CTAB) and 2-isopropyl-5-methylphenol (thymol). The optimum concentration of CTAB for the treatment of the immobilized enzyme was 0.25% [w/v] and 1 h, for immobilized cells 0. [w/v] and 3 h. The optimum concentration of thymol for the immobilized enzyme was found to be 0.1% [w/v] and 1 h, for immobilized cells 0.27% [w/v] and 2 h. The optimum dose of γ-rays for the sanitization of the immobilized enzyme was established as 3.2 kGy, for immobilized cells as 4.5 kGy.
    Additional Material: 5 Tab.
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  • 18
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 19
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 53-64 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: An advanced primary treatment process for a municipal waste water was systematically studied, using a bio-flocculation-adsorption, sedimentation and stabilzation process (BSS). It was shown that the organic removal efficiency was higher than that of the traditional primary treatment processes but lower than that of the traditional secondary treatment processes. Both adsorption and bio-flocculation played an important role in the removal of pollutants. The activated sludge within the bio-flocculation-adsorption tank could be considered a bio-flocculent which improved the quality of the effluent from the primary treatment process. As the effluent of the BSS process did not meet the requirements for a typical secondary effluent, the process may be regarded as an advanced (or enhanced) primary treatment process, suitable for waste water containing a high concentration of suspended solids and colloidal particles.
    Additional Material: 7 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 67-73 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The concentration of airborne fungal spores and bacteria as related to room temperature, humidity and occupancy levels within a library building in Singapore was determined. Measurement of indoor air quality with respect to microorganisms is of particular importance in tropical environments due to the extensive use of air-conditioning systems and the potential implications for human health. This study has revealed a number of interesting relationships between the concentrations of fungal spores and bacteria in relation to both environmental and human factors. The levels of fungal spores measured in the indoor environment were approximately fifty times lower than those measured outside, probably because of the lowered humidity caused by air-conditioning in the indoor environment. The variation in fungal spore concentration in the outdoor environment is likely to be due to the diurnal periodicity of spore release and the response to environmental factors such as light temperature and humidity. The indoor concentration of fungal spores in air was not clearly correlated to concentrations measured in air outside of the library building and remained relatively constant, unaffected by the difference in the numbers of occupants in the library. In contrast, the indoor concentrations of bacteria in air were approximately ten times higher than those measured outdoors, indicating a signficant internal source of bacteria. The elevated levels of indoor bacteria were primarily attributed to the number of library occupants. Increased human shedding of skin cells, ejection of microorganisms and particulates from the respiratory tract, and the transport of bacteria on suspended dust particles from floor surfaces probably accounts for the strong positive correlation between occupancy levels and the concentration of bacteria in internal air.
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  • 21
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 22
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 96-96 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 23
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 87-96 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Preliminary results on the novel use of the bacterium Thiobacillus ferrooxidans (ATCCJ 3598 and ATCC33020) for the micro-machining (or biomachinig) of metals are reported. Biomachning is a controlled microbiological process to selectively form microstrucutures on a metal work-piece by metal removal (or dissolution) using microorganisms. Applying copper and mild steel as work-pieces, it was shown that the mass removed increased proportionately with machining time. In another experiment, the work-pieces were coated with organic photo-resistive materials to mask (i.e. protect) certain regions of the metlas, thereby defining the microstructure to be formed. The unmasked regions were successfully biomachined; the final machined profile was shown to be similar to the coating image on the original metal. Although biomachining proceeded at a slower rate than chemical machining, the undesired leaching of the metal in the region under the masked area (termed undercutting) was not as severely encountered when compared with the latter. This work demonstrates the potential use of microorganisms for the biomachining of metals. As a “green process”, the innovative use of T. ferrooxidans for the micro-machining of metals opens up the possibility of biomachining as an alternative to conventional metal processing.
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  • 24
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: During the microbial treatment of a sandy model soil artificially contaminated with polycyclic aromatic hydrocarbons (PAHs), a large residual pollution was found. The remainig PAHs were sorbed into the micropores of the soil and were therefore not bioavailable. Using a lab-scale precolator, the microbially pretreated soil was subjected to aftertreatment with surfactants with the aim of further degradation of its pollution. Two commercial nonionic surfatants of the polyethoxylate type, Präwozell F1214/5 N and Sapogenat T-300, were used. The surfactants differ both in their physicochemical properties (CMC value, PAH solubilization capacity, adsorption onto soil) and in their microbial degradability. During aftertreatment under permanently aerobic conditions, only a weak PAH accumulation in the liquid phase was observed, which was due to a low solubilization rate as well as to simultaneous microbial degradation of the dissolved PAHs. Temporary anaerobiosis successfully suppressed the microbial degradation of both the surfactant and the solubilized PAHs, resulting in a more intensive PAH accumulation. But the PAH content of the soil - the essential criterion for evaluating the efficiency of surfactant application - was not decreased to a larger extent with surfactants than without them. To find out why the surfactants failed to act, the surfactant and hydrocarbon distribution among the liquid and solid phases was studied in mixtures of phenantherne-spiked solis and Präwozell-containig liquids; at heavy phenanthrene loading, the aqueous phase was saturated with PAH; at weak loading, it was unsaturated. Model-aided data analysis showed that the soil may contain PAH in two fractions: strongly sorbed into soil pores and, in the case of heavy loading, also weakly attached to the soil surface. The latter is easily extractable, resulting in a PAH-saturated liquid, while strongly adsorbed PAH is only partially dissolved due to competition between the micelles and the soil pores for the PAH. The microbially pretreated soil contains only strongly bound PAHs, which are as difficult to extract by surfactants as they are poorly accessible for microbes.
    Additional Material: 8 Ill.
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  • 25
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Autochthonous bacteriocenoses in semiarid soils in Patagonia were found to be capable of rapidly adapting to high contamination with crude oil. This adaptation at community level is due to the selective enrichment of hydrocarbon-utilizing bacteria always present in these soils. Immediately after a heavy contamination with crude oil, the authochthonous bacteriocenosis contained about 28% hydrocarbon-utilizing bacteria which could be classified into eight ecotypes with characteristic metabolic profiles. Mainly n-alkanes were used as growth substrates of representative strains. After seven months' exposure to crude oil, the bacteriocenosis consisted almost entirely of hydrocarbon-utilizing bacteria. At least fourteen ecotypes were distinguishable, and the majority of representative strains were able to metabolize a broad spectrum of aliphatic and aromatic hydrocarbons. Corresponding to the significant alteration of the physiological diversity, drastic changes to the taxonomic diversity were also found. Whereas at the beginning of the study the autochthonous bacteriocenoses were dominated by GRAM-positive genera of the Actinomycetales (Dietzia, Gordona, Nocardia, Rhodococcus, Streptomyces) with high ecological potency, after just two months' exposure to crude oil, GRAM- negative bacteria (especially Pseudomonas stutzeri) became predominant within the hydrocarbon-utilizing bacteriocenoses accompanied by some GRAM-positive genera of the Actinomycetales with a significantly lower abundance. These findings underline the importance of Pseudomonas and some genera of Actinomycetales for processes of natural attenuation and the technically supported in situ bioremediation of soil polluted by crude oil in Patagonia.
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  • 26
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 149-159 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Some parameters of the production of an alkaline protease by Rhizopus oryzae in the solid state fermentation of wheat bran were optimized. Using the optimum parameters of an inoculum age of 7 days, an incubation time of 9 days, an amount of CZAPEK-DOX (liquid medium) of 6 ml/g bran and an incubation temperature of 33°C, an activity of 50 U/g bran was achieved. The initial pH of the CZAPEK-DOX medium had little effect. Re-incubation of mouldy bran with only fresh CZAPEK-DOX yielded 3 times total activity compared to single-cycle fermentation. As for the effect of the amount CZAPEK-DOX medium, the water constituent contributed more to activity increase than did the salt component. The ARRHENIUS activation energies were 23 and 7.9 kcal/mole below and above the optimum of 33°C, respectively. In all the studies, along with protease production, variation of protein content and specific activity were also observed. Attempts were made to explain the effects and also gauge their implications for large-scale production.
    Additional Material: 4 Ill.
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  • 27
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 28
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 29
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Because of the growing utilization of renewable raw materials, the technical use of lignocellulosic fibres from wood and other annual plant materials is becoming increasingly important. The conventional production process of fibreboards is characterized by high-energy consumption and use of ecologically insecure synthetic lesins. Approximately 40 to 45% of the total energy expenditure are used for the thermo-mechanical pulping. Because of high plastication temperatures, an inactive lignin crust on the fibre surface is formed. For that reason, for glueing of the fibres, urea formaldehyde and melamin resins are usually used. The costs for the resin amount to approximately 50% of the entire material costs. In addition, environmental problems are caused. The aim of our investigation is the reduction of energy and resin consumption by enzymatic modification of wood chips and the enzymatic activation of the inherent bonding strength of the material. The first industrial use of fungi for the modification of wood was in the production of “Myco wood”. Pleurothus ostreatus and Trametes versicolor were applied for nonsterile delignification of beech wood. The present investigation of the authors deals with the mycological pre-treatment of wood chips in order to reduce the energy consumption during wood pulping. The screening results favour the brown rotter Gleophyllum trabeum for pinewood (Pinus silvestris) and the white rotter Trametes hirsuta for beech (Fagus silvatica). Both species show resistance against mould fungi. The use of submerged inoculum of these fungi has the advantage over wheat inoculum that the lag phase is less than 12 hours and that the addition of nutrients or fungicides is not necessary. Short-time wood chip incubation results in a 40% decrease of energy consumption during thermo-mechanical pulping and in improved fibreboard properties. Lignin reduction could not be determined by gravimetrical and x-ray microanalysis.Comparative investigations of fibre incubation using laccase, a submerged culture of Trametes versicolor and rape straw fibres show a high increase in bending and tensile strength and an improvement in the hygroscopic properties of glue-free fibre boards for the last two incubation kinds. Similar effects have been obtained incubating pine wood fibres for the production of fibre sheets with enzyme medium of Trichoderma reseei.
    Additional Material: 4 Ill.
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  • 30
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 335-350 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: During the 20th century, important relationships developed between the oil industry and both microbiological and biotechnological research. Basic microbiological research has played an important role in both the exploration and production sectors of the oil industry, but as the maturity of the industry has progressed, such contributions have been relegated with respect to their importance. With respect to refining and petrochemicals manufacture, process routes have been extensively researched, but only rarely have the biotechnological solutions developed satisfied the economic criteria that resulted in major investment. In fact, situations exist where investment has occurred, but project life was unrealistically short, suggesting a need for extreme caution when evaluating biotechnological processes for the oil industry. However, as far as engineered processes for both biotreatment and bioremediation are concerned, the fundamental research that has underpinned other areas of hydrocarbon microbiology will finally prove to be of both technical and economic value, in ensuring that the essential needs of treatment, rather than disposal, and restoration, rather than environmental destruction, can be satisfied by the oil and other industries involved in both geochemical manipulation and natural resource exploitation.
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  • 31
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The influence of different growth-limiting factors - namely the sources of carbon, nitrogen and phosphorus and the dilution (growth) rate - on the ice-nucleation activity of Pseudomonas syringe CCM 4073 was studied. A higher ice-nucleation activity was observed at a lower dilution (growth) rate (D = 0.1 h-1) than at a higher dilution (growth) rate (D = 0.3 h-1). Remarkable differences in ice-nucleation activity were found in its dependence on the growth-limiting factor. The highest ice-nucleation activity was observed under carbon limitation (T90 = -2.7°C), a medium activity under nitrogen limitation (T90 = -5°C) and lowest activity under phosphorus limitation (T90 = -12.3°C). After the addition of excess nitrogen or phosphorus to steady-state cultures, the ice-nucleation activity was restored.
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  • 32
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 33
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 65-65 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 34
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 35
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 41-52 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Studies were carried out to evaluate the feasibility of using coffee industry residues, viz. coffee husk, coffee leaves and spent coffee ground as substrates in solid state fermentation (SSF) to cultivate edible mushrooms Pleurotus. Eight strains of Pleurotus ostreatus and two strains of Pleurotus sajor-caju were screened on a medium prepared from aqueous extract of coffee husk and agar. Based on best mycelial growth (9.68 mm/day) and biomass production (43.4 mg/plate in 9 days at 24°C), the strain P. ostreatus LPB 09 was selected for detailed studies. SSF was carried out using these substrates under different moisture conditions (45-75%) and spawn rates (2.5-25%). In general, although a 25% spawn rate appeared superior, the 10% spawn rate was recommended for all the three substrates in view of the process economics, as there was not any significant difference in the increase with 10 to 15%. The ideal moisture content for mycelial growth was 60-65% for coffee husk and spent coffee ground, and 60-70% for coffee leaves. The biological efficiency (BE), which is defined as the ratio of the weight of fresh fruiting bodies to the weight of dry substrate, multiplied by 100, and which indicates the fructification ability of the fungus for utilizing the substrate, was best with coffee husk. With coffee husk as the substrate, the first fructification occurred after 20 days of inoculation, and the biological efficiency reached about 97% after 60 days. When coffee leaves were used as the substrate, no fructification was observed even upon prolonged cultivation. With spent ground as the substrate, the first fructification occurred 23 days after inoculation and the biological efficiency reached about 90% in 50 days. There was a significant decrease in the caffeine and tannin contents (61 and 79%, respectively) of coffee husk after 60 days. It was remarkable to observe that caffeine was adsorbed onto the fruiting body (0.157%), indicating that it was not completely degraded by the fungal culture. However, no tannins were found in the fruiting body, indicating that the fungal strain was capable of degrading them. The results showed the feasibility of using coffee husk and spent coffee ground as substrates without any pre-treatment for the cultivation of edible fungi in SSF, and provided one of the first steps towards an economical utilization of these otherwise unutilized or poorly utilized residues.
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  • 36
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 75-81 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Serratia marcescens biovar A2/A6 is able to produce a red pigment as a secondary metabolite which has antimicrobial activity. This paper describes its growth and biopigment formation in batch cultures, in media containing different concentrations of lactic acid and beef extract as carbon and nitrogen sources, respectively. An unstructured model has also been developed to describe its growth, lactic acid uptake and biopigment formation. The comparison of simulated and experimental data shows that the proposed model predicts reasonably well the system behaviour over a range of conditions.
    Additional Material: 2 Ill.
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  • 37
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 97-98 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 38
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    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 39
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 334-334 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 40
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The impact of hydrocarbon remediation on several enzyme activities (catalase, dehydrogenase, lipase, protease, urease, alkaline phosphomonoesterase, fluorescein diacetate hydrolysis) and microbial properties (biomass-C, respiration, N-mineralization, qCO2, microbial counts) was evaluated in a laboratory study over a period of 10 weeks. A pristine soil was contaminated with diesel oil (10 mg/g soil) or with a mixture of phenanthrene and naphthalene (total amount 1 mg/g soil) and supplemented with inorganic nutrients to give a C:N ratio of 20:1. The corresponding controls consisted of uncontaminated nutrient-supplemented soil. Oil contamination caused a significant initial increase of all biological parameters measured. In the presence of PAHs, biomass-C, respiration, protease activity and heterotrophic counts were significantly enhanced, while urease activity was depressed. N-mineralization was initially, however, reversibly inhibited in the presence of oil and PAHs.The measured parameters behaved differently over time: Biomass-C, respiration and alkaline phosphomonoesterase activity reached a maximum activity after about 2-5 weeks, corresponding to the period during which the majority of hydrocarbons disappeared, and declined thereafter to the background level. Activities of catalase and dehydrogenase also followed this pattern, however, were characterized by fluctuations. Activities of lipase, protease, urease and fluorescein diacetate hydrolysis increased and remained almost constant throughout the incubation period.
    Additional Material: 10 Ill.
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  • 41
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 351-368 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The action resonance theory (ART), a hypothesis based on a logical extension of EINSTEIN's theory of Brownian movement, suggests that the genotype × environment interaction can be modelled as forceful encounters of the gene-products of an organism with its environment. This model has implications for molecular and cell biology, morphogenesis, evolutionary development via mutation, the mechanism of natural selection and overall function of ecosystems, extending SCHRÖDINGER's programme for molecular biology. Action, a thermodynamic property with the same physical dimensions as angular momentum and PLANCK's quantum of action, is proposed to be reversibly generated as a result of the molecular exchange of quanta, which become resonant at equilibrium, corresponding to an optimum degree of entropy and action for living systems. Because the theory can potentially predict solutions to unsolved problems such as the folding of proteins it has strong implications for successful genetic modification of organisms and for biotechnology in general; the design of a programme of research to test this theory is proposed. A key element in this research programme, improving productivity and sustainability, would be the need to select genetically modified strains in the ecological environment or niche in which they are required to function.
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  • 42
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 43
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Continuous counter-current chromatographic processes have been successfully used in the petrochemical and sugar industry over the last 30 years. Only recently has simulated moving bed (SMB)-technology attracted widespread interest in the pharmaceutical industry, mainly as a very efficient system for chromatographic enantioseparation. The application of this technique to the downstream processing of biotechnological products requires some specific changes to meet the special demands of bioproduct isolation. Production processes are set up on an multi-ton scale, for example, for the purification of fructose with both yield and purity higher than 90%. Examples for other mono- and oligosaccharides are reported. In the purification of fatty acids or fat soluble vitamins, SMB technology under supercritical fluid conditions gives additional benefits and increases the productivity by a factor of four when a pressure gradient is applied. Another field of operation is the isolation of drug compounds from natural sources where different batch- and SMB-chromatographic steps could be successfully combined. First examples are reported for cyclosporine A and paclitaxel isolation. Finally, step-gradient elution modes can be used continuously, as demonstrated for the isolation of monoclonal antibodies.
    Additional Material: 6 Ill.
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  • 44
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stereoisomeric Sinensiaxanthins and Sinensiachromes: Separation and Absolute ConfigurationThe so-called sinensiaxanthins and sinensiachromes, important apocarotenols from various fruits, have been separated into 2 and 4 stereoisomers, respectively, and their absolute configurations have been determined: (3S,5R,6S)-5,6-epoxy-5,6-dihydro-10′-apo-β-carotene-3,10′-diol (2), its (9Z)-stereoisomer 7, the (8R)- and (8S)-epimers of (3S, 5R)-5,8-epoxy-5,8-dihydro- 10′ -apo-β-carotene-3, 10′-diol (4 and 5), and their (9Z)-stereoisomers 3 and probably 6. Thus, sinensiaxanthins are cleavage products from (Z/E)-isomeric antheraxanthins or violaxanthins (scission at C(9′)-C(10′)) and sinensiachromes analogously from mutatoxanthins or auroxanthins.
    Additional Material: 4 Ill.
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  • 45
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantioselective Saponification of Diacetates of 2-Nitro-1,3-propanediols by Pig-Liver Esterase and Preparation of Enantiomerically Pure Derivatives of 2-Nitro-allylic Alcohols (Chiral Multiple-Coupling Reagents)The reproducible enantioselective saponification of open-chain and cyclic diacetates of meso-2-nitro-1,3-propanediols (see 4b-13b) with pig-liver esterase (PLE) gives monoacetates (see 4c-l3c) of 〉 95% enantiomeric excess. The Re enantiotopic acetate group appears to be saponified preferentially, as proved by the X-ray crystal structure analysis of three camphanoates 4d, 6d, and 7d. Elimination of H2O or AcOH from the hydroxy acetates thus available gives derivatives of nitro-allylic alcohols (see 20-24, 27, and 29) which are subjected to diastereoselective Michael additions or SN2′ substitutions.
    Additional Material: 4 Ill.
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  • 46
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 72-76 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four new pterocarpinoids, sphenostylin A, B, C, and D (1-4), have been isolated from the CHCl3 extract of the root bark of Dolichos marginata ssp. erecta (Leguminosae) by preparative liquid chromatography. The structures have been established by spectroscopic methods (UV, 1H-NMR, 13C-NMR, EI-MS, DCI-MS, CD) and chemical transformations. The isolated compounds showed weak antifungal activity against Cladosporium cucumerinum.
    Additional Material: 1 Tab.
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  • 47
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Homophthalic acid (1) undergoes reaction with 1,2-, 1,3-, and 1,4-diamines to give condensed 1(2H)-isoquinolinones like 2, 4, 13, and 25, which exhibit marked enamine character. These are attacked by electrophiles at the N or C terminus. Some notable reactions of imidazoisoquinolone 2 are those with maleic and acrylic acids to form the tetracycles 48 and 51, respectively. With propiolic acid, 5 underwent an interesting reaction to form the benzimidazonaphthyridine 53. An equally interesting behaviour was elicited from 2 in its reaction with formaldehyde, when in addition to the expected methylene-bridged molecule 59, the novel spiro derivative 60 was formed by the dimerisation of a presumed azadiene intermediate 63.
    Additional Material: 2 Ill.
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  • 48
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 120-123 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 1H- and 13C-NMR data of the dimeric anhydride 1 of 2,3-O-isopropylidene-β-D-ribofuranose are reported together with the 1H-NOE values. The data show that the products of the polymerization of 1,5-anhydro-2,3-O-isopropylidene-β-D-ribofuranose are α- and β-D-ribofuranans and not an α-D-ribofuranan and a β-D-ribofuranan and a β D ribo-pyranan as claimed before [2] [3].
    Additional Material: 3 Tab.
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  • 49
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,6-Diphenylpyridine forms, as twofold-deprotonated, terdentate ligand, complexes with Pt(II) and Pd(II), having two adjacent five-membered metallocycles. As mono-deprotonated, bidentate ligand, it forms cis-bis-complexes having a chirality axis. Pt(II) complexes undergo thermal and photochemical oxidative addition reactions, yielding stable Pt(IV) compounds. Pd(II) complexes yield substitued 2,6-diphenylpyridine in photochemical reactions.
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  • 50
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 168-194 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ability to incorporate alkyl, alkenyl, aryl, and heteroatomic groups into substrates for the silicon-directed Nazarov cyclization and their subsequent reactions has been investigated. In general, most of the groups are compatible with the conditions for the cyclization and do not interfere even when directly attached to the divinyl ketone. The influence of substituents on the rate of the cyclization has been addressed and is consistent with a simple mechanistic picture. O- and N-Containing functions are tolerated except when attached to the α-vinyl C-atom of the divinyl ketone. The diastereoface-directing effect of a fused cyclobutane is discussed.
    Additional Material: 7 Tab.
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  • 51
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A 1:1 mixture of the racemic trans- and cis-1-p-menthene-3,8-diols ((±)-3 and (±)-4, resp.) was readily prepared in 3 steps starting from 3-methyl-2-cyclohexen-1-one. The relative configuration of the diols, purified via the corresponding cyclocarbonates, was assigned by 1H-NMR spectroscopy and found to be at variance with tentative claims in the literature. Optically active samples of 3 and 4 were prepared by resolution of the racemates with (R)-1-phenylethylamine. The absolute configuration of the resulting diols was determined by chemical correlation with standards of known absolute configuration.
    Additional Material: 4 Tab.
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  • 52
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 224-236 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of Enantiomerically Pure, α-Alkylated Lysine, Ornithine, and Tryptophan DerivativesThe imidazolidinones 9 and 10 as well as the oxazolidinone 18a were prepared in several steps by known methods from lysine and ornithine with an overall yield of ca. 20%. After double deprotonation with LDA, the corresponding dianionic derivatives could be diastereoselectively alkylated with electrophiles (MeI, C6H5CH2Br, C6H5CHO, CH3CHO). Acid hydrolysis led to the two enantiomeric 2-methyl- and 2-benzyllysines and to the enzyme inhibitor (S)-2-methylornithine. Several α-alkylated tryptophan derivatives were obtained through alkylation of the heterocycles derived from various amino acids with 1-(tert-butyloxycarbonyl)-3-(bromomethyl)indole (26). Alkaline hydrolysis of the five-membered auxiliary ring of 30b followed by treatment with HCl afforded (S)-2-methyltryptophan (31).
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  • 53
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrogenation of Flavylium Salts: Formation of Heptacyclic compounds; X-Ray Crystal Structure of 2-[10b,10c,16,16a-Tetrahydro-16,16a-dimethyl-10b,16-methylene-5aH-di[1]benzopyrano[4,3-b:3′,4′ -c; 2,3:2′,3′][1]benzoxepin-5a-yl]phenolThe hydrogenation of flavylium salts 1 either by catalytic reduction or by chemical reduction afforded the unexpected heptacyclic compound 2, the structure of which was determined by X-ray analysis. The latter was confirmed by 1H-NMR and mass spectra.
    Additional Material: 2 Ill.
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  • 54
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational Analysis of Tripeptide Models: The Influence of α,α-disubstituted α-Amino Acids on the Secondary Structure. X-Ray Analysis and Conformational Energy CalculationsThe X-ray analysis of tripeptide Z-Ile-Val(2-Me)-benzocaine (1f) reveals the presence of a type-III β-turn. Moreover, MMP2 calculations on tripeptides, e.g. Z-Ile-Aib-benzocaine (1c), Z-Ile-D-Val(2-Me)-benzocaine (1g), Z-Ile-Gly(2,2-Pr2)-benzocaine (1h), Z-Ile-Gly-benzocaine (1a), and 1f, fit well into the frame of NMR and CD investigations. They allow considerations on the relative stability of different types of β-turns depending on the peptide sequence, e.g. the kind of α,α-disubstituted amino-acid moieties.
    Additional Material: 4 Ill.
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  • 55
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 292-297 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of (-)-(R)-Nephthenol and (-)-(R)-Cembren AStarting for L-serine,(-)-(R)-nephthenol((-)-2) and (-)-(R)-cembren A((-)-3) were synthesized.
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  • 56
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Single crystals of the N,N,N′,N′-tetramethylethylenediamine (TMEDA) complex 6 of the title compound have been isolated. Compound 6 decomposes in the crystalline state above -20°. From the bond lengths and angles obtained by X-ray crystal-structure analysis (data collected at -70°), compound 6 is best described as a (E)-1-(tert-butylthio)-1-lithio-2-butene with the double bond acting as an additional ligand on lithium (unsymmetrical allylic group). The S-atom is in a cisoid arrangement in a common plane with the four C-atoms of the butenyl system. The t-Bu group and the Li-atom are located above and below this plane. The structure is discussed with respect to the reactivity of 6 (α/γ reactivity). The gross structure is reproduced surprisingly well by an ab initio SCF MO calculation of the model lithiopropene-1-thiol 7(HS instead of t-BuS, CH2 instead of CHCH3, no solvation of Li). The prominent difference is the symmetry of the allyllic moiety in the calculated structure.
    Additional Material: 6 Ill.
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  • 57
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Note on the Synthesis of an Optically Active ACE Inhibitor with Amino-oxo-benzazepine-1-alkanoic-Acid Structure by Means of an Enantioconvergent Crystallization-Based ResolutionAn enantioselective synthesis of the potent angiotensin-converting enzyme inhibitor (1′S,3S)-3-[(1′-(ethoxy-carbonyl)-3′-phenylpropyl)amino]-2,3,4,5-tetrahydro-2-oxo-1H-1-benzazepine-1-acetic acid hydrochloride (3) is described which user a crystallization-based resolution of a racemic amino intermediate with concomitant racemization of the unwanted enantiomer.
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  • 58
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    Helvetica Chimica Acta 71 (1988), S. 363-368 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polycyclopentanes as Steroid AnalogaThe synthesis of linearly annellated pentaquinanes from a readily available triquinane is reported.
    Additional Material: 1 Tab.
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  • 59
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    Helvetica Chimica Acta 71 (1988), S. 395-403 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of an Optically Active Penem Intermediate by Asymmetric AmidoalkylationThe amidoalkylation of an optically active, cationic glycine derivative with methyl acetoacetate furnishes an intermediate 10a (Scheme 2) that is transformed in six steps to the optically active, silyl-protected 4-acetoxy-3-(1-hydroxyenthyl)-2-azetidinon 18a, a well known intermediate in penem synthesis.
    Additional Material: 3 Tab.
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  • 60
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optically pure 5,6-dimethylidenebicyclo[2.2.1]hept-2-yl derivatives have been prepared. The sign of the Cotton effects associated with lowest-energy transition of 2-(dicyanomethylidene)-((-)-(1S,4S)-15), (E)-2-(methoxyimino)-((+)-(1S,4S)-16), (Z)-2-(methoxyimino)-5,6-dimethylidenebicyclo[2.2.1]heptane ((-)(1S,4S)-17), and 2,3,5-trimethylidenebicyclo[2.2.1]heptane ((-)-(1R,4S)-18) is opposite to the chirality constituted by the coupling of the electric transition moments of the two homoconjugated π-chromophores (Kuhn-Kirkwood dipole-coupling mechanism). When the substituents at C(2) are not π-functions, no general rule can be retained for the chiroptical properties of the 5,6-dimethylidenebicyclo[2.2.1]hept-2-yl systems as shown for dimethyl acetal (-)-(1S,4S)-19, ethylene acetal (+)-(1R,4R)-20, exo and endo methyl ethers (+)-(1R,2S,4R)-21 and (+)-(1R,2R,4R)-22, and for spirol[5,6-dimethylidenebicyclo[2.2.1]heptane-2.2'-oxiranes](-)-(1S,2S,4S)-23 and (-)-(1S,2S,4S)-24.
    Additional Material: 2 Ill.
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  • 61
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: About forty novel phenyl benzoates also incorporating a trans-1,4-disubstituted cyclohexane ring and a chiral centre have been prepared. The dependence of the liquid-crystal transition temperatures of this new class of compounds on lateral substituents, diverse central linkages, chain lengths, and position of the chiral centre has been studied systematically. The synthesis and liquid-crystal transition temperatures of these new compounds are described in detail.
    Additional Material: 7 Tab.
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  • 62
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    Helvetica Chimica Acta 71 (1988), S. 486-492 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [4 + 2] Cycloadditions of α,β-Unsaturated Hydrazones to Pyridine-2,3-dicarboximides via 1-(Dimethylamino)-1,4-dihydropyridine DerivativesThe [4 + 2] Cycloaddition of α,β-unsaturated hydrazones of type 1 (1-aza-1,3-butadienes) with 2-halogenomaleimides 4 affords 1,4-dihydropyridines 6 which, after treatment with an acid, yield highly substituted pyridine-2,3-dicarboximide derivatives 7 (Scheme 1).
    Additional Material: 3 Tab.
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  • 63
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    Helvetica Chimica Acta 71 (1988), S. 498-501 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Irradiation (λ 〉 340 nm) of the title compound 2a in t-BuOH affords 3,3,10,10-tetramethyl-2,8-dioxatricyclo-[4.3.2.01,6]undecane-5,9-dione (3) via photoextrusion of 2-methylpropene and subsequent photocycloaddition of 2a to the alkene. The same regioisomer 3 is formed selectively and in much higher yields on irradiating 2a in the presence of excess 2-methylpropene. Irradiation of 3 (λ = 300 nm) in t-BuOH in the presence of the same alkene gives a 6:1 mixture of spirooxetanes 7a and 7b but not α-cleavage products. In 2-propanol, 2a is photoreduced to a 2:1 mixture of diastereoisomeric hydrodimers 9.
    Additional Material: 1 Tab.
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  • 64
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    Helvetica Chimica Acta 71 (1988) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 65
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    Helvetica Chimica Acta 71 (1988), S. 602-608 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A General Synthesis for Mono-C-Functionalized TetrazamacrocyclesA new synthesis, under usual conditions of concentration, medium, and temperature, of a series of mono-C-functionalized tetraazamacrocycles is given. The method may easily be generalized. The new procedure allows the modification of the length of the side-chain or the size of the cavity by choosing fitted staring materials. The key intermediate has a tosylated linear side-chain susceptible to be transformed into a large variety of functional groups.
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  • 66
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantiomerically pure methyl 5-bromo-5-deoxy-2,3-O- isopropylidene-β-D- (D-5b) and -β-l-ribofuranoside (l-5b) have been derived from (-)-(1R,2S,4R)-2-exo-cyano-7-oxabicylo[2.2.1]hept-5-en-endo,-yl (1′S)-camphanate (1) and (+)-(1S,2R,4S)-2-exo-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-endo-yl(1′R)-camphanate (2), respectively, in 5 synthetic steps and 28% overall yield. Hydrolysis of D-5b and L-5b afforded methyl 2,3-O isopropylidene-β-D-ribofuranoside (D-5a) and methyl 2,3-O-isopropylidene β-L-ribofuranoside (L-5a), respectively. The intermediate (+)-(1R,4R,5R,6R) 5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((+)-7) and its enantiomer(-)-7 were also obtained enantiomerically pure by resolution of (=)-7 by the Johnson-Zeller method. In bothe approaches, the chiral auxiliaries ((-)- and (+)-camphanic acids, or (+)-(S)-N,S-dimethyl-S-phenylsulfoximide) were recovered at an early stage of the synthesis.
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  • 67
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Solvolysis Mechanism of cis - and trans-2-Arylcylopentyl p-Toluenesulfonates. The Step: 1-Deuterium Isotope Effects, Basic Salt Effects, and Special Salt EffectWe have studied the first step of the solvolysis of cis and trans-2-arylcyclopentyl p-toluenesulfonates in HCOOH, AcOH, and EtOh. All substrates show a high kinetic 1-deuterium isotope effect (kH/kD(1) 〉1.15). This fact indicates that first step leads to classical intimate ion-pair Which dissociates to a solvet-separated ion-pair, without participation either of solvent, the 2-aryl group, or a H-atom at C(2). The slight influence of added basic ions on reaction rate allows us to exclude any direct solvent attack on the covalent substrate even in the most favorable case, i.e. ethanolysis of 2-(p-nitrophenyl)cylopentyl-p-toluenesulfonates. Furthermore, solvent-separated ion pair formation is indicated by the special salt effect induced by LiClO4.
    Notes: No abstract.
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  • 68
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    Helvetica Chimica Acta 71 (1988) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 69
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optically active (4S,8S)-4, 8-bis(hydroxymethyl)-1,5,7-triazabicyclo[4.4.0]dec-5-ene ((S,S)-1) has been synthesized in nine steps from L-asparagine with a total yield of 5.1%. Similarly, the enantiomer (R,R)-1 has been prepared from D-asparagine. (S,S)- and (S,S)-1 are representative examples of rigid and functionalized bicyclic guanidine systems and constitute useful intermediates in the construction of chiral selective anion-receptor molecules.
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  • 70
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and antifungal activity of a novel series of 3-aryl-5-[(aryloxy)alkyl]-3-[(1H-imidazol-1-yl)-methyl]-2-methylisoxazolidines and related compounds, are discussed. The synthesis of the title compounds was accomplished via a 1,3-dipolar cycloaddition of α-substituted ketonitrones with l-alkenyl phenyl ethers (Scheme 2 and 3). The compounds were evaluated for in vitro antifungal activity in solid agar cultures against a broad variety of yeast and systemic mycoses and dermatophytes. While antifungal activity was evident throughout the series, in general, derivatives having halogen atom(s) in either or both aryl rings demonstrated the highest potency, especially against Trichophyton rubrum and Candida albicans. The dichloro analog 20 (PR 967-248) was found to possess the most useful activity. Its minimum inhibitory concentration (MIC) values ranged between 0.2 and 2.0 μg/ml, as compared to 0.2-20.0 μg/ml for the standard drug ketoconazole (4).
    Additional Material: 1 Ill.
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  • 71
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    Helvetica Chimica Acta 71 (1988), S. 742-748 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Olefins with captodative substitution are reactive dienophiles in Diels-Alder reactions with normal and inverse electron demand. This is shown for reactions of 2-(tert-butylthio)acrylonitrile (1) with various dienes and heterodienes, e.g. 1,3-cyclohexadiene, hexachloro-1, 3-cyclopentadiene, acrolein, methacrolein, and methyl vinyl ketone (Schemes 2 and 3). In case of the hetrodienes, 3,4-dihydro-2H-pyrans are formed beside small amounts of tetrahydrothiophenes; however, with methyl vinyl ketone, both reaction pathways are equally followed. The high reactivity of captodative olefins in Diels-Alder reactions are rationalized on the basis of Sustmann's FMO model under consideration of Viehe's concept of captodative substitution of alkenes.
    Additional Material: 1 Tab.
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  • 72
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    Helvetica Chimica Acta 71 (1988), S. 783-787 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel rearrangement of 2(5H)-furanones is described. When refluxed in aq. Ethanolic solution in the presence of excess KOH, the 2,5-dihydro-2-oxofuran-3-carboxamides 6 underwent a novel rearrangement to the corresponding 4,5-dihydro-4-oxo-2-(phenylamino)-3-furancarboxylic acids 1 in moderate-to-excellent yields.
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  • 73
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    Helvetica Chimica Acta 71 (1988), S. 788-807 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Short Total Syntheses of (±)-Sativene and (±)-cis-SativenediolOur approach to (±)-sativene (7) and (±)-cis-sdtivenediol (9) involves: (a) reaction of 3-methylbutanoyl chloride with Et3N/cyclopentadiene to give the endo-isopropyl-ketone 1 (here improved to 71%), (b) NBS bromination of 1 to a 5:1 mixture (87%) of the bromo-ketones 2 and 3, (c) NFD-reaction sequence initiated by the attack of 1,2-butadienyl titanate (complex of 15, obtained from 2-butine) on 2/3 to afford 52% of the brexenone derivative 4 (along with 8% of its epimer 16), (d) addition of dibromomethane to 4 forming 63% of the diene-alcohol 5 (along with 13% of the diene-carbaldehyde 38), and (e) carbenoid ring-expansion with MeLi applied to 5 resulting in 41% the diene-ketone 6 (along with 15% of a 1:3 mixture of the diene-ketones 32 and 33). Wolff-Kishner reduction of 6 led to 81% of (±)-sativene (7), when enough O2 was present, but to 97% of the diene 8 in the strict absence of O2. (±)-cis-Sativenediol (9) was obrained (86%) by OsO4 hydroxylation of 8. The brexenone derivatives 4 and 16 (6:1, 50%) were also produced when the NFD-reaction sequence was applied to the isomeric bromo-ketone mixture 13/13 (1:3). The latter was obtained by NBS bromination of 10, which in turn was available by base epimerization of 1, followed by destructive removal of unreacted 1 by repeated gas-flow thermolysis. An analogous (less convenient) route to (±)-sativene (7) passed through a series of dihydro compounds (the ene series) it started with the methylidene-ketone 36, which was the product (97%) of a partial hydrogenation of 4. Addition of dibromomethane to 36 led t 62% of the methylidene-alcohol 39 (along with a little tetracyclic ether 40). Carbenoid ring expansion of 39 with MeLi afforded ca. 42% of the methylidene-ketone 41 (along with 7% of the methylidene-ketone 43 or, under slightly different condition, along with 9% of the methylidene-ketone 42 and 10% of the methylidene-carabaldehyde 44). The methylidene-alcohol 39 and the methylidene-ketone 43 were also obtained by partial hydrogenation of 5 and 33, respectively. Wolff-Kisher reduction converted 41 into (±)-sativene (7 99%); the same conditons applied to 42 afforded only ca. 8% 7 (along with three other hydrocarbons, one of them (ca. 21%) probably being (±)-copacamphene (45)). In the diene series, the two succeeding reactions (4→5 and 5→6) competed with the same side reaction, a rearrangement leading to the brendene-aldehyde 38. In the ene series, the corresponding dihydro-by-product 44 was found in the reacton 39→41, but not during 36→39. These side reactons could largely be suppressed by keeping the reaction temperature low. An explanation is proposed.
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  • 74
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    Helvetica Chimica Acta 71 (1988), S. 859-866 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of the bromo-substituted naphthalene 1 with the alkanethiolate anions 2a-b and arenethiolate 2c in tetraglyme gave the corresponding 1-naphythyl thio-ethers 3a-c. Thio-ethers 3a-c were oxidized to the corresponding sulfones 4a-c with m- chloroperoxybenzoic acid. The reaction of the dichloro-substituted anthracene 5a with 2b gave the disubstutution product 6a. The reaction of 9-bromoanthracene 5c with the alkanethiolate 2b gave 6b, whereas the reaction of 5c with the arenethiolate 2c gave a mixture of substitution product 6c and anthracene 7. The observation of the formation of both 6c and 7 is explained by the competition between substitution (SnAr) and electron-transfer (ET) mechanisms. Consistent with this interpretation, the reaction of the monochloro-substituted 5b, which has a higher-energy σ* orbital, with 2c gave 6c without the formation of 7. Zn/KOH in tetraglyme was shown to reduce the aryl halides 5b-c and thio-ether 6c to 7.
    Additional Material: 1 Tab.
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  • 75
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    Helvetica Chimica Acta 71 (1988), S. 876-880 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of Decarboxythamnolic AcidThe total synthesis of the meta-depside decarboxythamnolic ( = 3-[(3-formyl-2-4-dihydroxy-6-methyl-phenyl)oxy]-2-hydroxy-6-methoxy-4-methylbenzoic acid; 25) by the biomimetic condensation of the substituted β-orcinol units 9 and 22 is described.
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  • 76
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diets supplemented with astaxanthin and canthaxanthin, respectively, and a control diet without carotenoid additions, were fed to 1½-year-old Atlantic salmon (Salmo salar, L.) for one year. The integuments were investigated as to their quantitative and qualitative carotenoid composition. Astaxanthin and canthaxanthin deposited in the skin amounted to 20 and 14% of the total carotenoids only. Seventy % must be considered as metabolites of astaxanthin and canthaxanthin and 10% as basic xanthophylls also present in the control groups. Astaxanthin apparently underwent the following metabolic pathway: astaxanthin→idoxanthin→adonixanthin→zeaxanthin→zeaxanthin 5,6-epoxides. Reduction of the 4′-carbonyl group was stereospecific leading to the (4′R)-idoxanthin. Canthaxanthin was obviously converted to β,β-carotene via 4′-hydroxyechinenone, echinenone, and 4-hydroxy-β,β-carotene.
    Additional Material: 2 Ill.
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  • 77
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    Helvetica Chimica Acta 71 (1988), S. 1210-1219 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four highly oxygenated polyphenols 1-4, have been isolated from the stem bark of Cordia goetzei Gürke (Boraginaceae) and their structures elucidated by a combination of one- and two-dimensional (including COLOC) NMR spectroscopic techniques, mass spectroscopy, and chemical methods. The first new compound, cordigone (1), is a tetrahydrofuran derivative and the second one, cordigol (2), a furobenzopyran derivative. The benzofurans 3 and 4 are orange pigments, responsible for the coloration of the stem bark of the tree. All four polyphenols are fungicidal against cladosporium cucumerinum.
    Additional Material: 3 Tab.
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  • 78
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    Helvetica Chimica Acta 71 (1988), S. 1191-1198 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Base-modified octanucleotides derived from d(G1-G2-A-A-T-T-C-C-) (11) but containing 8-aza-7-deaza-2′-deoxyguanosine (2) instead of 2′-deoxyguanosine (1) have been prepared by solid-phase synthesis employing P(III) chemistry. Isobutyrylation of 2, followed by 4, 4′-dimethoxytritylation and subsequent phosphitylation yielded the methyl or the cyanoethyl phosphoramidites 6a or 6b, respectively. They were used as building blocks in automated DNA synthesis. The resulting octanucleotides 12-14 containing 2 showed increased Tm values compared to the parent oligomer 11. The oligomers 11-14 were employed as sequence-specific probes in endo-deoxyribonuclease Eco RI oligonucleotide recognition. Whereas displacement of dG-2 (enzymic cleavage site of 11) abolished phosphodiester hydrolysis, replacement of dG-1 enhanced the cleavage rate compared to 11.
    Additional Material: 2 Ill.
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  • 79
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title complexes have been derived from tricarbonyl [(1R,4S,5S,6R,)-C,5,6,C-η-(5,6-dimethylidenebicyclo[2.2.2]oct-2-ene)]iron (1.). The crystal structure and absoulte configuration of (+)-tricarbonyl (1S,2S,4R,5R,6S)-C,5,6,C,-η-(5,6-dimethylidenebicyclo[2.2.2]oct-2-yl p,-bromobenzoate)]iron ((+)-6) determined by X-ray diffrac-tion studies proved earlier attribution of the relative configuration (endo us. exo,) of the tricarbonyliron moieties in complexes 1 and 2 of 5,6-dimethylidenebicyclo[oct-2-ene. The structure of (+)-6 confirms the absolute configuration derived earlier from circular-dichroism spectra of 5,6-dimethylidenebicyclo[2.2.2]oct-2-yl esters and 5,6-dimethylidenebicyclo[2.2.2]octan-2-one.
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  • 80
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The [2 + 2] Photocycloaddition of 2-(trimethylsilyloxy)-1,3-butadiene to a number of 2-cycloalkenones proved to be quite a general reaction leading to good yields of the cycloadducts (Table). This finding is surprising since dienes, in general, are better known as quenchers of enone triplets rather than as photochemical reactants. Both the high substrate concentrations, which can be employed in these cycloadditions, and the remarkable regio and stereoselectivity of the processes qualify them as valuable for syntheses. In a first application, the photoproducts 1a, b were transformed in three steps into a viable precursor 4 of the pentalenolactone-G and -H antibiotics.
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  • 81
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complexes trans-[PtXY(2] (X = H or Me; Y = OMe, OCHO, CO2H, and BH4; 2 = 2,11-bis{bis[3-(trifluoromethyl)phenyl]phosphinomethyl}benzo[c]phenanthrene) were prepared, and their decompositions to trans[PtHX(2)] were studied. Some binuclear hydrido-bridged complexes, e.g.[(2)HPt(μ-H)PtH(2)]+, were also obtained. The preparation of complexes trans-[PtHX(28)2] (X = H or Me, 28 = bis[3-(trifluoromethyl)phenyl]benzylphosphine) is also reported. The X-ray crystal structure of trans-[PtHCl1)] (1 = 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene) was carried out.
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  • 82
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 1005-1010 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The near-infrared luminescence of singlet oxygen (1O2) has been measured in order to determine the efficiency of 1O2 quenching by two carotenoid compounds, β-carotene and canthaxanthin. 1H-Phenalen-1-one and rose bengal have been used as photosensitizers in those steady-state luminescence experiments. Stern-Volmer analysis of the 1O2 luminescence in solutions of CCl4 and CD3OD, containing different concentrations of the carotenoids, has shown a very efficient quenching by canthaxanthin. The rate constants are about a factor of 2 below the diffusion limited values for the given solvents, confirming earlier results in benzene. In comparison, the efficiency of 1O2 quenching by β-carotene is slightly lower than that by canthaxanthin in non-polar solvents and is reduced by an order of magnitude in CD3OD, due to the aggregation of this quencher.
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  • 83
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    Helvetica Chimica Acta 71 (1988), S. 1035-1041 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of 3-azetidinones with different N-substituents and their transformation to 3-ethylideneazetidines has been studied in relation with a projected synthesis of 3-ethylideneazetidine-2-carboxylic acid (= polyoximic acid; 1). The stable crystalline 3-azetidinone hydrochloride (18), obtained by hydrogenolysis of the known 1-(diphenylmethyl)-3-azetidenone (4), is described for the first time, From this key intermediate, 3-oxoazetidine-derived amides, exemplified by benzamide 12,urethanes (e.g. 17), and ureas (e.g. 20) can be prepared in good yield (Scheme 3). The olefination of 3-azetidinones with alkylidene(triphenyl)phosphoranes is a perparatively useful process only for derivatives with a pyramidal N-atom, e.g. the diphenylmethyl derivative 4, and not for the amide 12 or the urethane 17 (Scheme 4). 3-Alkylidene-azetidines with an amide N-atom should, therefore, be prepared by exchange of the N-substituent after the introduction of the double bond.
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  • 84
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absorption spectra, luminescence spectra, and luminescence lifetimes of the isomeric [M(bph)(bpy)] and [M(phpy)2] complexes M = Pt(II) or Pd(II), bph2- = 1,1′-biphenyl-2,2′-diyl dianion, phpy- = 2-phenylpyridine-2′-yl anion, and bpy = 2,2′-bipyridine have been investigated and compared with those of [M(bpy)2]2+ complexes and of the free protonated ligands H2bph, Hbpy+, and Hphpy. In the absorption spectra, the region below 320 mm is dominated by ligand-centered (LC) transitions, whereas metal-to-ligand charge transfer (MLCT) transitions are responsible for the bands present in the near UV/VIS region. The MLCT bands move to higher energies on replacing Pt with Pd and in going from [M(bph)(bpy)] to the [M(phpy)2] isomer. For the mixed-ligand complexes, evidence for both M → bph2- (at higher energies) and M → bpy bands is found. The structured luminescence observed at 77 K shows lifetimes of 4.0 and 1.1 μs for [Pt(phpy)2] and [Pt(bph)(bpy)], respectively, and 480 and 250 μs for the analogous Pd complexes. On the basis of the energy and lifetime data, the luminescence of the Pt(II) complexes is assigned to the lowest triplet MLCT excited state, whereas for the Pd complexes the luminescent state is thought to result from a mixture of MLCT and LC triplet levels.
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  • 85
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    Helvetica Chimica Acta 71 (1988), S. 1108-1115 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of tri-heteroleptic complex of Ru(II) with diimine ligands is describe. Ten compounds [Ru(R2bpy) (biq) (L)][PF6]2 (R = H, CH3); L = 2,2′-bipyridine (bpy), 4,4′-dimethyl-2,2′-bipyridine (Me2bpy), 2,2′-bipyrimidine (bpm), 2,2′-biisoquinoline (biiq), 1,10-phenanthroline (phen), dipyrido[3,2-c:2′,3′-e]pyridazine (taphen), 2,2′-biquinoline (biq), 6,7-dihydrodipyrido[2,3-b:3,2-j][1,10]-phenanthroline (dinapy), 2-(2[pyridyl)quinoline (pq), 1-(2-pyrimidyl)pyrazole] (pzpm), 2,2′-biimidazole (H2biim) are characterized by elemental analysis, electronic and 1H-NMR spectroscopy. The relative photosustitution rates of biq in MeCN are given at three temperatures.
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  • 86
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 1177-1190 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal Generation and Reactions of (Benzylthio)-and (Arylthio)-Substituted Nitrile YlidesThermolysis of 4-(benzylthio)- and 4-(arylthio)-1,3-oxazol-5(2H)-ones 6, at 110-155° in the presence of dipolarophiles with activated C≡C, C=C, C=O, C=S, and N=N bonds, led to 5-membered cyclo-adducts and CO2 (cf. Schemes 3, 5-7). Heating 6a and 6c in the presence of ethyl propiolate yielded ethyl quinoline-3-carboxylate (19) and ethyl pyridine-3-carboxylate(22), respectively (cf. Scheme 8). These results are rationalized on the basis of the intermediate formation of thio-substituted nitrile ylides of type 7 (cf. Scheme 2), which undergo regioselective 1,3-dipolar cycloadditions with reactive dipolarophiles. In the absence of such a dipolarophile, the nitrile ylides isomerize via a [1,4]-H shift to give 2-aza-1,3-butadienes of type 20. The latter are trapped in a Diels-Alder reaction with ethyl propiolate (cf. Scheme 8).
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  • 87
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 1220-1227 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tautomerisation between proxibarbal (I) and the two diastereoisomers of valofan, IIX and IIY, was investigated in aqueous solutions, and various rate and equilibrium caonstants were calculated by compartmental analysis. The proportion of I at equilibrium was found to increase with pH, and indeed, the two equilibrium constants are linear functions of pH. In contrast, the equilibrium-concentratio ratio of IIY/IIX was close to 63:37 and remained constant in the pH range investigated. The rate constants were also determined as a function of temperature, allowing calculation of the tehrmolynamic parameters. Under physiological conditions, the difference in free energy favouring I vs. IIX and IIY is 6.7 and 5.4KJ · mol-1, respectively.
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  • 88
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthess of 6,7,8,9-tetramethylidene-2-oxabicyclo[3.2.2]nonan-3-one (12), 6,7,8,9-tetramethylidene-2-azatricyclo[3.2.2]nonan-3-one (13), and (1RS,5SR,6RS,7SR)-6,7-bis(chloromethyl)-8,9-dimethylidene-2-oxabicyclo-[3.2.2]nonan-3-one (14) are presented. The rate constants of the two successive Diels-Alder additions of a given dienophile to 12 and 13 were nearly the same. Lewis-acid-catalyzed Diels-Alder addition of methyl vinyl ketone to 14 gave adduct 39 with high regio- and stereoselectivity. Lewis acids isomerized 39 into(1RS,5RS,6SR,7SR,11RS)-6,7-bis(chloromethyl)-3-oxo-2-oxatricyclo[7.4.0.01,5]tridec-8-en-11-yl methyl ketone (40) whose structure was determined by single-crystal X-ray crystallography. Heating 39 with CsF/Cs2CO3 in DMF/HMPT gave (1RS,5RS,11RS)-6,7-dimethylidene-3-oxo-2-oxatricycl. [7.4.0.01,5]tridec-8-en-11-yl methyl ketone (42). The exocyclic butadiene moiety of triene 42 added to methyl propynoate and 2,3-didehydroanisole with good regioselectivity giving polysubstituted anthracenyl and naphthacenyl derivatives, respectively.
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  • 89
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparative Chromatographic Resolution of Synthetically Useful Cyclic AcetalsRacemic cyclic acetals derived from aldehydes and glycine, glycolic acid, thioglycolic acid, formylacetic acid, and acetoacetic acid (oxazolidinones 4-13, dioxolanones 14, 15, oxathiolanone 16, dioxinones 17-23) are resolved by preparative high-pressure liquid chromatography on silica gel coated with the polymer from N-acryloylphenylalanine ethyl ester (Chiraspher®). The separation factors α range from1,1 to 2,4. Use of a Prepbar®-chromatography system allows injection of several grams at a time. The enantiomeric acetals thus obtained are fully characterized. First application to amino-acid synthesis are mentioned.
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  • 90
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the electron-transfer reaction between racemic or optically active [Co(bamap)H2O]+ and optically active Fe2+ complexes of the three new pentadentate ligands bamap, alamp, and valmp has been investigated. All the reacting species show C2 symmetry. With respect to aquo-Fe2+, the reaction rate for the Fe2+ complexes is enhanced by a factor of 104 to 105, and the observed kΔΛ/kΛΛ ratio is 1.0, 1,9, and 1.2, respectively. In all cases where stereoselectivity is observed, the reaction is faster between the complexes of opposite absolute configuration (ΔΛ or ΛΔ) than between species with the same configuration (ΛΛ or ΔΔ). The stereoselectivity effects are discussed of the basis of the structure of the transition state and the interatomic distances between the two metal centers at the moment of electron transfer.
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  • 91
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 92
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 1399-1405 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Epoxidation of (-)-(1R,2R,4R)-2-endo-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-exo-yl acetate ((-)-5) followed by saponification afforded (+)-(1R,4R,5R,6R)-5,6-exo-epoxy-7-oxabicyclo[2.2.1]heptan-2-one ((+)-7). Reduction of (+)-7 with diisobutylaluminium hydride (DIBAH) gave (+)-1,3:2,5-dianhydroviburnitol ( = (+)-(1R,2R,3S,4R,6S)-4,7-dioxatricyclo[3.2.1.03,6]octan-2-ol; (+)-3). Hydride reductions of (±)-7 were less exo-face selective than reductions of bicyclo[2.2.1]heptan-2-one and its derivatives with NaBH4, AlH3, and LiAlH4 probably because of smaller steric hindrance to endo-face hydride attack when C(5) and C(6) of the bicyclo-[2.2.1]heptan-2-one are part of an exo oxirane ring.
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  • 93
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    Helvetica Chimica Acta 71 (1988), S. 1483-1490 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new phenlypropanoid glycoside has been isolated from the methanolic extract of the aerial parts of Stachys lavandulifolia (Lamiaceae), lavandulifolioside (1). On the basis of chemical and spectral data the structure of the new compound 1 has been elucidated as β-(3,4-dihydroxyphenyl)ethyl O-α-L-arabinopyranosyl-(1→2)-α-L-rhamnopyranosyl-(1→3)-4-O-caffeoyl-β-D-glucopyranoside.
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  • 94
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    Helvetica Chimica Acta 71 (1988), S. 1498-1501 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radical cation of 2,3-diazabicyclo[2.2.2]oct-2-ene (1), generated by γ-rays in a CF2ClCFCl2 matrix, has been fully characterized by its hyperfine data with the use of ESR, ENDOR, and TRIPLE resonance spectroscopy. The isotropic coupling constants for \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\scriptstyle {{\relbar}\kern-4pt {.} }}$\end{document} are +3.14 mT for the two 14N Nuclei in the azo group, -0.336 mT for the two protons at the bridgehead C atoms, and +151 and +0.135 mT for the sets of four exo- and four endo-protons, respectively. MO calculations indicate that these values are consistent with an electron removal from an orbital represented by the antibonding combination (n_) of the lone-pair atomic orbitals at the two N atoms. The corresponding radical anion \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\scriptstyle {{\relbar}\kern-4pt {.} }}$\end{document} is persistent in fluid solution and its hyperfine data, combined with MO calculations, point to an electron uptake into the antibonding π orbital (π*) of the azo group. It is, thus, reasonable to classify \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\scriptstyle {{+}\kern-4pt {.} }}$\end{document} as a σ and \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\scriptstyle {{\relbar}\kern-4pt {.} }}$\end{document} as a π radical.
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  • 95
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An efficient synthesis of chiral semicorrin ligands is described (see 6-9, Schemes 2 and 3). Both enantiomers are readily obtained in enantiomerically pure form starting either from D-or L-pyroglutamic acid (1). Semicorrins of this type possess several features that make them attractive ligands for enantioselective control of metal-catalyzed reactions. Their structure is characterized by C2 symmetry, a conformationally rigid ligand system, and two stereogenic centers adjacent to the coordination sphere. In a metal complex, the two substituents at the stereogenic centers shield the metal atom from two opposite directions and, therefore, are expected to have a pronounced effect on the stereochemical course of a reaction occurring in the coordination sphere. The structure of these two substituents can be easily modified in a variety of ways. A series of (semicorrinato)copper(II) complexes (see 10-14, Scheme 4) has been prepared, and in one case (14), the three-dimensional structure has been determined by X-ray analysis (Fig. 1).
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  • 96
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solid-liquid phase-transfer glycosylation (KOH, tris[2-(2-methoxyethoxy)ethye]amine ( = TDA-1), MeCN) of pyrrolo[2,3-d]pyrimidines such as 3a and 3b with an equimolar amount of 5-O-[(1,1 -dimethylethyl)dimethylsilyl]-2,3-O-(1-methylethylidene)-α-D-ribofuranosyl chloride (1) [6] gave the protected β-D-nucleosides 4a and 4b, respectively, stereoselectively (Scheme). The β-D-anomer 2 [6] yielded the corresponding α-D-nucleosides 5a and 5b with traces of the β-D-compounds. The 6-substituted 7-deazapurine nucleosides 6a, 7a, and 8 were converted into tubercidin (10) or its α-D-anomer (11). Spin-lattice relaxation measurements of anomeric ribonucleosides revealed that T1 values of H—C(8) in the α-D-series are significantly increased compared to H—C(8) in the β-D-series while the opposite is true for T1 of H—C(1′). 15N-NMR data of 6-substituted 7-deazapurine D-ribofuranosides were assigned and compared with those of 2′-deoxy compounds. Furthermore, it was shown that 7-deaza-2′deoxyadenosine ( = 2′-deoxytubercidin; 12) is protonated at N(1), whereas the protonation site of 7-deaza-2′-deoxyguanosine (20) is N(3).
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  • 97
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 98
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 1616-1621 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Group-IV-A phthalocyanines with four crown ether substituents have been prepared from 4′,5′-dicyanobenzo(15-crown-5), 4′,5′-diiminoisoindolino(15-crown-5), or metal-free phthalocyanine and the corresponding metal salts. The axial ligands of dichloro[tetra(15-crown-5)phthalocyaninato]silicon or -tin have been converted into dihydroxy derivatives by hydrolysis in aqueous Et3N. The catalytic effect of H2O-free CaC12 in quinoline is used for the polycondensation of dihydroxysilicon-phthalocyanine to cofacially arrayed polymers. The thermal stability of group-IV-A-metal phthalocyanines is confirmed by the higher initial decomposition points (290-440°) compared to those of the corresponding transition-metal phthalocyanines.
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  • 99
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 1659-1660 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: O-Labelled carbon monoxide was prepared on the gram scale from enriched water and acetals of norborn-2-en-7-one(= bicyclo[2.2.1]hept-2-en-7-one) in almost quantitative yields and without isotopic dilution.
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  • 100
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dimethyl acetals 4 of (E)-2,4-pentadienal and of (E,E)- and (E,Z)-2,4-hexadienals undergo regio- and stereospecific cycloaddition reactions with in-situ-generated acylnitroso dienophiles 5a and 5b, leading thereby to the corresponding dihydrooxazines 7a-d and 8c-d. cis-Glycolization of these latter adducts stereospecifically gave the dihydro derivatives 9a-d and 10d which, after sequential hydrogenolysis, deacetalization, and instant cyclization, led to the aminodeoxyribose derivatives 17a, 17f, and 18, and to the amino-dideoxyallose compounds 17c and 17h. These piperidino-deoxysugar derivatives exhibit a strong anomeric effect, i.e. OH—C(1) is always axial, which is explained in terms of a nN(π)-σ*(C—OH) orbital compression, as compared to the less pronounced one in the more classical pyranose series.
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