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  • 1995-1999  (3,656)
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  • 1
    ISSN: 1573-5176
    Keywords: compression ; LiCl ; Porphyra ; seaweed ; tension
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The mechanical properties of various differentiated regions of thePorphyra perforata thallus and the effect of LiCl were studied by performing compression and tension tests. Among the various differentiated tissues, the holdfast area was high in its ‘compressive modulus of elasticity’ and ‘tensile modulus of elasticity’, possibly related to its thick matrix. Vegetative non-dividing tissue and vegetative dividing tissue were the most flexible and strong, showing the highest ‘percentage elongation at break’ and ‘tensile strength’. The patch area, which is a transition zone leading to sexually mature tissue, had moderate values of tensile properties. Meanwhile, sexually differentiated male and female tissues had the highest ‘compressive modulus of elasticity’ and lowest tensile properties. Thes tisues tended to crumble easily. Treatments in LiCl, as used for DNA extraction, resulted in a decrease in both ‘compressive modulus of elasticity’ (87%) and ‘tensile modulus of elasticity’ (54%). After treatment of tissue for chromosome staining in a method using LiCl, there was a marked decrease in ‘tensile modulus of elasticity’ (49%), while the ‘compressive modulus of elasticity’ remained unchanged. Such mechanical changes verify the softening effect of LiCl on the seaweedP. perforata tissue.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 321 (1996), S. 77-81 
    ISSN: 1573-5117
    Keywords: seaweed ; Durvillaea antarctica ; sulfated polysaccharides ; fucose ; anticoagulant activity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Durvillaea antarctica was extracted with hot water and a sulfate containing polymer was obtained after separation of laminaran and alginic acid with cetrimide and 2% calcium chloride solutions, respectively. Gel electrophoresis showed that the acidic polysaccharide (23.5% sulfate, 4.5% uronic acid) was not homogeneous. It was fractionated by anion-exchange chromatography on DEAE Sephadex with increasing concentrations of KC1 solutions affording seven fractions. All the fractions showed blood-anticoagulant activity. The fraction eluted with 1.2 M KC1 (34.85% sulfate, 1.4% uronic acid) showed the highest thrombin time. The plaque inhibition and the transcription assays of the whole acidic polysaccharide and the partial hydrolysis product against the infectious pancreatic necrosis virus showed a slight antiviral effect. The fucose-containing polymer from D. antarcica is a mixture of sulfated polysaccharides with a different content of sulfate groups and uronic acids. A correlation was observed between the anticoagulant effect uronic acids content.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 326-327 (1996), S. 371-379 
    ISSN: 1573-5117
    Keywords: Chile ; cultivation ; exploitation ; Gracilaria ; landings ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract In the last fourteen years the production of seaweeds in Chile has ranged from 74 000 to 229 000 wet metric tons per year and has included about twenty species belonging to Phaeophyta and Rhodophyta. The only source of this production has been the exploitation of natural beds, except for Gracilaria, which is the only case of commercial cultivation and contributes significant quantities to total production. Initially most of the raw material was exported but currently important quantities of Gracilaria and several carrageenophytes are being processed by local industry. Changes in production of the main resources are analyzed with consideration of potential demand, level of knowledge about natural beds, and the situation of total Gracilaria farming, in order to attempt predictions for the supply. Current possibilities of applying new technologies to cultivate other economically important Chilean seaweeds are also analyzed and discussed.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 326-327 (1996), S. 387-392 
    ISSN: 1573-5117
    Keywords: fusion ; histocompatibility ; Rhodophyta ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Fully developed thalli of Chondrus crispus, Gracilaria chilensis, Gymnogongrus furcellatus and Mazzaella laminarioides were used to assess tissue compatibility. The effect of thallus polarity on grafting and regeneration was also evaluated. Fusion did occur between fragments of the same life history phase in C. crispus, G. chilensis, G. furcellatus and M. laminarioides. Fusion between sporophytic and gametophytic tissue occurred in C. crispus, G. chilensis and M. laminarioides. Intergeneric fusion was observed between C. crispus and M. laminarioides, but not between G. chilensis and G. furcellatus. Outer cell wall, cortex and medulla were continuous at the contact face in compatible combinations. Medullary cells in the attached fragments were thinner and longer than normal cells, forming an interwoven scar plate. Thallus polarity did not modify fusion and regeneration.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 326-327 (1996), S. 429-436 
    ISSN: 1573-5117
    Keywords: codon usage ; Gracilaria verrucosa ; intron ; nuclear protein-coding genes ; poly(A) signal ; promoter ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Single-copy nuclear genes encoding cytosolic glyceraldehyde-3-phosphate dehydrogenase (GapC), triosephosphate isomerase (TPI1) and polyubiquitin (UBI6R), plastid-localized GAPDH (GapA), and mitochondrial aconitase (m-ACN), together with their corresponding cDNAs, have been cloned or PCR-amplified from Gracilaria verrucosa, sequenced, and characterized by genomic Southern hybridization. Three spliceosomal introns were found, one each near the 5′ end of GapA, GapC, and m-ACN. Codon usage is biased, with third-position A's underrepresented. Nucleotide compositions of the genes are balanced except in TPI1. Upstream promoter structure, downstream poly(A) processing signals, intron splice junctions, and one translation initiation site were analyzed. Poly(A) processing features of these red algal genes resemble those of green plants more than those of animals.
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  • 6
    ISSN: 1573-5117
    Keywords: antimicrobial activity ; Caribbean ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Antibacterial activity of lipid extracts from three species of Caribbean marine algae, Spyridia filamentosa, S. hypnoides and Wrangelia bicuspidata was evaluated monthly for one year. Activities were tested for whole plant extracts and TLC-separable zones. Whole plant extracts demonstrated monthly variability in activity with respect to both habitat and life history phase in addition to periods of similarity. No consistency was seen regarding activity against different microorganisms. TLC analyses of the extracts led to the identification of twenty-seven chromatographically distinct regions (TLC zones) each from both S. filamentosa and S. hypnoides and twenty-five from W. bicuspidata, which demonstrated antimicrobial activity. Between these species, twenty-one active TLC zones appeared to be shared based on their similar chromatographic characteristics. Individual TLC zones also demonstrated variable activity throughout the sampling period with respect to habitat and life history phase as well as periods of similarity. Algal antibiosis in these species is recognized as being highly complex, involving numerous chemical compounds, each of which is highly variable in terms of its presence and/or probable concentration.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 326-327 (1996), S. 491-495 
    ISSN: 1573-5117
    Keywords: acidic polysaccharide ; Leptosomia simplex ; Palmaria decipiens ; Rhodophyta ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Palmaria decipiens, one of the most abundant red seaweeds of the chilean Antarctic, was collected in King George Island. The hot water extract (26% yield) showed by acid hydrolysis to contain xylose, galactose and traces of glucose. Fractionation with cetrimide gave a soluble neutral xylan and an insoluble fraction. The insoluble fraction afforded an acidic polysaccharide that contained 4.8% of uronic acids, 2.8% of sulfate and 18.9% of protein. Polyacrylamide gel electrophoresis showed that it was homogeneous. The GLC and HPLC analysis of the total acidic hydrolysis products showed that the acidic polysaccharide was composed of the neutral sugars galactose and xylose in the molar ratio 8.2:1.0 and of galacturonic and glucuronic acid in the ratio 1.5:1.0. The second-derivative FT-IR spectrum showed the characteristic amide I, II and III bands of proteins. Alkaline cleavage with 0.1 M NaOH indicated the presence of a glycoprotein with O-glycosidic linkage. Results found in this work suggest that the acidic polysaccharide extracted from Palmaria decipiens is an acidic xylogalactan-protein complex.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 326-327 (1996), S. 401-406 
    ISSN: 1573-5117
    Keywords: CO22 ; HCO inf3 sup− ; light ; Lomentaria ; Palmaria ; seaweed ; sunflecks
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Palmaria palmata, which is able to use HCO inf3 sup− as a carbon source for photosynthesis, and Lomentaria articulata, which is dependent on diffusive uptake of dissolved CO2, were grown under constant light and light with sunflecks designed to model wave-induced fluctuations of near-shore underwater light. Both species exhibited significantly increased stable carbon isotope discrimination (more negative values of δ13C relative to PDB) when grown with sunflecks. More negative δ13C values were associated with decreased growth rate of P. palmata but not of L. articulata. The contrasting effects of sunflecks on the carbon-use characteristics of the two species are discussed in terms of the energetic cost of HCO inf3 sup− use and the susceptibility of CO2 diffusion-dependent species to photoinhibition.
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  • 9
    ISSN: 1573-5117
    Keywords: diatoxanthin ; Gracilaria ; photoinhibition ; phytoplankton ; seaweed ; xanthophyll-cycle ; zeaxanthin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Microalgae and macrophytes adapt their pigment content to the environment because excessive light could limit their photosynthetic rate by inducing photoinhibition. Carotenoids participate in the photoadaptative response especially through the operation of xanthophyll cycles (violaxanthin-zeaxanthin or diadinoxanthin-diatoxanthin). An increasing gradient of diatoxanthin in phytoplankton chromophytes is found from the inshore to the offshore waters, less turbid in relation to the different light penetration in seawater. In addition, a nyctemeral cycle is noted, with a suppression of diatoxanthin at night and its accumulation with the increase of the light. Similarly the vertical distribution, on the French Brittany coasts, of several Gracilaria and Gracilariopsis species corresponds to increasing zeaxanthin amounts in the seaweeds living at the upper zones, which are more resistant to photoinhibition as shown by fluorescence and oxygen evolution analysis. An operating xanthophyll cycle should be regarded as a regulatory mechanism involved in stress response for the dissipation of excessive excitation energy through deepoxidated xanthophylls such as zeaxanthin or diatoxanthin.
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  • 10
    ISSN: 1573-5117
    Keywords: agar ; agarophyte ; Gelidium ; phosphate ; Rhodophyta ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Phosphate concentration of the growth medium was found to affect the growth rate and agar yield of a clone of Gelidium robustum grown in the laboratory. To study differences in growth we used phosphate concentrations from 0 to 200 µM. To determine the effect of phosphate on agar yield and its properties we used concentrations from 0 to 20 µM. Growth rates generally increased with increasing phosphate concentration, with the highest growth rate (21% d−1) obtained at 150 µM. Agar yield as percentage of fresh weight was highest (10%) in the algae grown with low phosphate concentrations, but agar yield as percentage of dry weight was highest(43%) at 20 µM of phosphate. Gel strength increased with phosphate concentration with a maximum of 160 g m−2 for 0.75% gels for the cultures at 20 µM. Melting and gelling temperatures of the gels were also affected by phosphate concentration of the growth medium. Starch yield was highest in algae grown in low phosphate concentrations.
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  • 11
    ISSN: 1573-5117
    Keywords: airborne ; algorithm ; CASI ; intertidal ; imaging spectrometry ; seaweed ; Spectron
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The aim of this paper is to test the ability of imaging radiometers to describe the principal seaweed and seagrass beds along the coast of Brittany (France). In this work we used CASI, an instrument with programmable narrow bands. On the ground, regions of homogeneous vegetation cover were mapped using differential GPS positioning. Ground spectra were recorded with a field spectroradiometer (Spectron SE 590), for substratum and different species. Their analysis shows variations in relation to pigment characteristics, vegetation structure and environmental conditions. An algorithm sequence based on field work and according to the technical sensor characteristics, was developed to discriminate the dominant species. The classified CASI image was compared with ground data. The main results are the following P ] (a) the visible wavelengths allow good discrimination between green, red and brown algae. (b) the infrared wavelengths allow separation of two main types of brown species, seagrasses and the identification of floating seaweed.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 326-327 (1996), S. 191-197 
    ISSN: 1573-5117
    Keywords: epiphytes ; niche partitioning ; rocky shore ; seaweed ; temporal and spatial variation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Seasonal variation in a Fucus serratus assemblage was studied on the Isle of Man, UK over a 13-month period. Algal cover varied greatly, related to shedding reproductive fronds and winter storms. Peak reproduction was recorded in the autumn. There was little change in density of plants, the population was dominated by a bank of germlings (〈20 cm) and an adult mode between 50–70 cm. An indistinct third component of recruiting juveniles was present when gaps in the canopy formed. Seasonal variation in the algae was reflected in the population dynamics of the mobile epiphytes such as Littorina mariae and Lacuna pallidula, which exhibited annual life histories. Sessile species (such as bryozoans) utilized the algae year round, dominating the perennial stipes and lower fronds, which were not shed. Other species utilized the algae in a transient fashion: some feeding on the algae (e.g. Idotea), or other epiphytic animals (e.g. Nucella). Fucus serratus, therefore, provides a variety of spatially and temporally variable niches that explain the diversity of epiphytic animal species that exploit this alga.
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  • 13
    ISSN: 1573-5117
    Keywords: herbivory ; intra-population variability ; kelp ; Lessonia ; phenols ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Micropopulation differences in phenol content between intertidal and subtidal individuals of the kelp Lessonia nigrescens were found. Subtidal plants showed: (1) significantly higher phenol content than intertidal individuals, in vegetative and reproductive tissues, (2) intra-plant differences, with higher content in apical frond tissues, (3) higher resistance to consumption by herbivorous fishes. The microscopic progeny of subtidal plants showed the same trend as adult plants: (1) haploid spores from subtidal plants had higher phenol content than spores from intertidal individuals, and (2) the microscopic sporophytes derived from subtidal spores and gametophytes were less consumed by herbivorous snails (Tegula tridentata) than those derived from intertidal plant propagules. No increase in phenol content was detected after mechanical injury to experimental fronds, or after transplantation to the subtidal environment. In addition to the absence of inducible responses, the different phenol content between intertidal and subtidal individuals, in adult diploid plants and also in the haploid progeny, suggests that both environments differ someway enough to fix the mentioned features on the plants of Lessonia nigrescens. It is likely that the differences in herbivory between the two distributional extremes contributed to the observed pattern.
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 326-327 (1996), S. 29-34 
    ISSN: 1573-5117
    Keywords: Codium ; introduced species ; rDNA ; ITS ; RFLPs ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Analysis of DNA can help to distinguish those morphological characters indicative of species difference from those representing retained traits or parallel evolution. This can be of great value in detecting recent invaders. The choice of which DNA characters to examine not only dictates the methodology to be used but must also be appropriate for the detection level sought. Restriction endonuclease fragment comparisons of plastid DNA have been used to assess Codium species; the results show C. fragile subsp. tomentosoides from east and west coast North America to be identical while sympatric endemic Codium species each display their own unique set of fragments. For species of other algae, plastid DNA fragment patterns are not necessarily identical across a morphological species, e.g. Pandorina morum. Such repetitive element probes as M13 and the use of RAPDs are more appropriate for analysis of populations within species. DNA base sequence comparisons of nuclear rDNA genes often yield too few variant bases between closely related species for reliable identifications. Analysis of the more variable Internal Transcribed Spacer (ITS) region, lying between the small and large ribosomal subunit genes in nuclear DNA, yields more extensive base pair variation between species and relatively little within species; it may be an alternative choice for endonuclease restriction fragment analysis or for sequencing.
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  • 15
    ISSN: 1573-5117
    Keywords: biological interaction ; depth distribution ; Laminaria ; light ; seaweed ; Streblonema ; upper limit ; UV
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The kelp Laminaria saccharina dominates soft bottoms in 4–10 m depth in Kiel Bay. Experimental sporophytes transplanted to 2 and 5 m depth showed the typical annual growth pattern of Laminaria species. Surprisingly, 2 m plants died after the first resting phase, whereas 5 m plants survived and showed outgrowth of a new blade generation. Thalli at both depths were infected with the brown algal endophyte Streblonema aecidioides, with host deformations being significantly stronger in 2 m plants. Growth rates of infected sporophytes were reduced. Exclusion of UV light in 2 m depth resulted in less infected thalli. Discs excised from L. saccharina and cultivated in different photon fluence rates from 10–600 µmol m−2 s−1 did not differ in growth rate, photosynthesis or dark respiration. Hence, an exclusion of L. saccharina from shallow depths caused by high light cannot be concluded. We suggest the biological interaction with the endophyte S. aecidioides, amplified by UV light, to be most important for the exclusion of L. saccharina from shallow depths in the western Baltic.
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  • 16
    ISSN: 1573-5117
    Keywords: Ascophyllum nodosum ; Nova Scotia ; Canada ; population structure ; recruitment ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Changes in the structure of the Ascophyllum nodosum population at Pubnico, southwest Nova Scotia, Canada, at an experimental site subjected to mechanical harvest and at two control sites never subjected to mechanical harvest were monitored from 1991 to 1994. A bimodal population structure measured in terms of plant length was characteristic of all these sites before the experiment. The population structure of the experimental site became unimodal immediately after experimental harvest by machine and remained unimodal for the subsequent two years. However, a bimodal population structure began to appear in the third year. A bimodal population structure remained evident at the control site with bedrock as the substratum but was less evident at the other control site where the substratum is made up of boulders and cobbles. Movement of loose rocks with rockweeds still attached may have contributed to the less distinct modal structure of this control site. Other sites with different harvesting histories monitored in the summer of 1992 showed some interesting patterns. A unimodal population structure was evident in Argyle Sound and Pubnico Point South and at Charlesville, which had been harvested one and two years before, respectively. A bimodal population structure was more evident at Frenchman's Point, which had been harvested three years prior. The rate of change from a unimodal to a bimodal population structure may depend on the intensity of harvest. Extensive canopy removal in intensively harvested areas may be conducive to an influx of recruits and to regeneration from the holdfast. Hence, plant length modal structure may be a useful measure of the relative state of recovery of a harvested population.
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  • 17
    ISSN: 1573-5117
    Keywords: competition ; seaweed ; theoretical models
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The Lotka-Volterra competition model was used to represent the interaction between Laurencia obtusa and Hypnea spinella. A new model that considers effects of competition on algal carrying capacity is suggested. To test the models, data from field experiments conducted in an intertidal region at Cabo Frio Island, Rio de Janeiro, Brazil, were used. Both models showed that Hypnea was a stronger competitor than Laurencia. The model of interaction through the carrying capacity showed a stable coexistence between the algal populations and better represented the experimental data.
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  • 18
    ISSN: 1573-5117
    Keywords: ammonium ; competition ; eutrophication ; Gracilaria ; seaweed ; Ulva
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract In spring (August) 1993 a bloom of Ulva lactuca appeared for the first time in Saldanha Bay, South Africa, and persisted through summer. Ulva wash-ups contaminated the beach and part of the commercial Gracilaria beach-cast had to be discarded. The biomass and distribution of Gracilaria and Ulva are described in relation to the seasonal water chemistry of the bay. Gracilaria survives in deeper water in summer by the pulsing of nutrients on an approximately 6-day cycle of movement of the thermocline that separates nutrient-rich bottom water from warm oligotrophic surface water. Ammonium-rich fish-factory discharge into this surface layer in a sector of the bay provided localised conditions for Ulva to out-compete Gracilaria at depths of 2–5m, demonstrating the powerful disruptive effect of eutrophication in this strongly stratified system.
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  • 19
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 326-327 (1996), S. 305-310 
    ISSN: 1573-5117
    Keywords: Clyde ; environmental impact ; marine pollution ; metals ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The aim of this work is to describe changes in heavy metal concentrations in Ascophyllum nodosum from 1964 to 1994. Samples were collected from three sites in the Firth of Clyde and analysed for zinc, manganese, iron, copper, lead and nickel. The results were analysed using the multivariate technique Principal Components Analysis (PCA). At the Wemyss Bay site there was a trend towards increasing lead and nickel over the study period, which could not be accounted for by local industrial activity. At the Hunterston site, two groups were well separated by the PCA ordination, based on manganese and zinc concentrations, which corresponded to land reclamation activities in the area. The separation of samples at the Ardneil Bay site correlated well with copper concentration and this corresponded to the termination of industrial effluent with heavy copper loadings. Other changes in industrial effluent were also reflected in the Hunterston and Ardneil Bay site ordinations. The PCA technique highlighted the interplay between metals. The work demonstrated the potential for using multivariate analysis of seaweed metal concentrations in monitoring a posteriori the environmental impact of industrial change.
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  • 20
    ISSN: 1573-5117
    Keywords: Gracilaria ; morphotypes ; RAPD analysis ; RFLP analysis ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The extreme phenotypic variability recognized among the species of Gracilaria has highlighted the need for the application of refined methods to help solve taxa identifications. In Chile, there still exists uncertainty about the exact number of Gracilaria species. Our investigations are centered on DNA analyses of morphotypes collected from different geographical locations, namely Lenga and Isla Santa María, Region VIII (36°00′ S to 38°00′ S), and Maullín, Region X (39°30′ S to 43°40′ S). These two regions of Chile are considered as areas of confluence of G. chilensis, G. verrucosa, and a species of Gracilariopsis. In this study four morphotypes, from a natural bed located in Maullín, were analyzed for RFLP of plastid DNA and the results compared with data of four morphotypes from a bed in Lenga. The DNA banding patterns from each enzyme digest were identical irrespective of morphotypes and/or locations. In an attempt to unravel the nature of the morphological differences found among Lenga and Maullín morphotypes, RAPD analyses of nuclear DNA were also performed; however, no polymorphism has been found yet. Therefore, the data of this study, as well as concurrent data from preliminary interfertility tests, suggest that all morphotypes belong to a single taxon, Gracilaria chilensis.
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 326-327 (1996), S. 353-354 
    ISSN: 1573-5117
    Keywords: aquaculture ; biomass ; Gracilaria ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract This paper describes experiments to grow a local and still unidentified species of Gracilaria in shrimp hatcheries in Ecuador. The experiments used outdoor tanks of 1 and 18 m3 capacity, with continuous aeration and water renewal every two and five days, respectively. The sea water (salinity 34 ppt) was enriched with Guillard's f/2 medium; light and temperature were monitored but not controlled. One kg of fresh seaweed, inoculated into each tank, produced a biomass of ca. 3 kg in a period of 35 days in the 1 m3 tank and 18 kg in 43 days in the 18 m3 tank. We therefore believe that it is technically feasible to use the large infrastructure of existing shrimp hatcheries in Ecuador to produce Gracilaria.
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  • 22
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 326-327 (1996), S. 367-370 
    ISSN: 1573-5117
    Keywords: culture ; Gelidium rex ; re-attachment ; seaweed ; spores
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Research on the culture of Gelidium rex was approached from two points of view, growth of thalli from spores and growth from re-attachment. Mollusk shells, which are very easy to handle, were used in both systems. The results achieved by these methods showed that reattachment is the technique that obtains larger plants in a shorter time. This is the first stage in developing culture and cultivation techniques aimed at commercial exploitation of this species in Chile.
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  • 23
    ISSN: 1573-5117
    Keywords: agar ; Brazil ; Gelidiales ; Pterocladia ; Rhodophyta ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Pterocladia capillacea forms dense intertidal belts in southeastern Brazil, on moderately exposed rocky coasts. The studied population extends along a gradient of water exposure, where slightly different morphotypes can be recognized. Specimens were collected monthly from 3 points along the exposure gradient of its distribution (lower, medium and higher exposure), and analyzed for agar, sulfate and 3,6 anhydrogalactose content. Agar varied from 5–32% of dried seaweed with lower yields in the winter, and higher yields in late spring/early summer. Specimens from the surf side of the distribution had a consistently higher agar content throughout the year. Sulfate varied from 1–5%, and 3,6 AG from 27–48% of dried agar, without a clear variation among the sites.
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  • 24
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 326-327 (1996), S. 511-514 
    ISSN: 1573-5117
    Keywords: Delesseria ; seaweed ; sterol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract On Normandy coasts, the red alga Delesseria sanguinea perennates by its stipe; fronds grow in January and disappear in June. Seasonal variations in sterol composition in relation to the biology of D. sanguinea are reported. Sterols in cellular membranes are free or conjugated by esterification with fatty acids, heterosides or lipid complexes like phospholipids. Both kinds of sterols were analyzed by GC-MS. The major sterol (80%) found in fronds was cholesterol whereas in stipes, cholesterol was also the major sterol in spring, but in September, an important reduction in cholesterol yield was noted with proportional increase in sitosterol content. It appears that cholesterol is synthesized in fronds in spring, then transferred to the stipe, which loses an important amount of cholesterol with loss of the blades.
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  • 25
    ISSN: 1573-5117
    Keywords: alkali-soluble alginate ; block structure ; boiling water-soluble alginate ; brown alga ; Kjellmaniella crassifolia ; M:G ratio ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Kjellmaniella crassifolia, the edible macro-brown alga in Japan contained nearly 27% of alginates of which nearly 7% was extractable from the fronds with boiling water for 6 h and the residual alginates in the frond were almost exhaustively extracted with a dilute alkali at 60 °C for 6 h. The alginates dissolved in all these extracts with both boiling water and dilute alkali were purified by fractionation with MgCl2 and alcohol. The content of MM blocks in the boiling water-soluble alginate sample increased remarkably during heating for 6 h while that of GG blocks from the same sample decreased. In contrast, MM blocks in the alkali-soluble alginate sample decreased during 6 h heating while GG blocks continued to increase. Since the amounts of MG blocks showed slight fluctation, the M:G ratio of alginates extracted with boiling water increased towards the end of extraction whereas the reverse is true for the alkali-soluble alginates.
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  • 26
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    Hydrobiologia 326-327 (1996), S. 35-57 
    ISSN: 1573-5117
    Keywords: carrageenan ; Eucheuma ; filtered carrageenan ; Kappaphycus ; natural grade carrageenan ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Carrageenan has annual sales of over US$ 200 million, about 15% of the world use of food hydrocolloids. The market for carrageenan has grown exponentially at 5% per year for at least 25 years: 5 500 metric tons in 1970, and over 20 000 metric tons expected in 1995. The industry has become dominated by very large, multi-product companies with carrageenan factories in Europe and the US, but factories are now springing up in the Philippines and Chile, where red seaweeds grow in abundance. About 80 000 tons of dry red seaweeds are needed to produce 20 000 tons of carrageenan. About 40 000 tons comes from the Philippines, 15 000 tons from Indonesia, 15 000 tons from Chile, and 10 000 tons from elsewhere. Carrageenan growth depends on food fads like the McLean hamburger and food winners like processed pork and turkey. Carrageenan is a regulated food additive, and current health concerns focus on the minimum safe molecular weight for carrageenan when eaten. The most innovative development in carrageenans in recent years has been the introduction of a food grade version of lower cost natural grade carrageenan. Its acceptance, however, has been hampered by strong resistance from conventional carrageenan producers.
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  • 27
    ISSN: 1573-5117
    Keywords: biofilter ; floating enclosed systems ; integrated aquaculture ; mussels ; salmon ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A theoretical model linking the production of salmon, mussels and seaweed in floating, enclosed units is based on field data, laboratory tests and literature data. First step is the production of 300 metric tons of salmon in 12 production units of 500 m3 each and a total water flow of 60 m3 min−1. Using a standard high energy dry feed with a feed conversion factor of 1, a production of 300 metric tons of salmon is calculated to produce 15 metric tons of nitrogen (N) and 2.4 metric tons of phosphate (P), of which 13 metric tons of N and 0.7 metric tons of P are dissolved. Outlet water is transferred from the salmon units to 12 closed units (500 m3 each) with blue mussels. A standing stock of 112.5 metric tons of mussels (WW) is necessary to filtrate 60 m3 min−1. If all particles are filtrated through the mussels, 25% of the nitrogen is accumulated as increased biomass. 25–30% is released as faeces and 45–50% as dissolved matter. Particles are removed by a sedimentation trap. Outlet water from the 12 mussel filter units, containing 13.9 metric tons of dissolved N (0.9 metric tons from the mussels), is transferred to closed units (1000 m3) with seaweeds. Concentration of N is calculated to 0.44 g N m−3 and hydraulic retention time in the seaweed production unit is 4 hours. With a DW of 20% (4% N of DW) and an estimated growth rate of 10% d−1 during the production period, a standing stock of 45 metric tons (FW) of seaweed is theoretically needed to bind up all dissolved N from the salmon and mussel production.
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  • 28
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    Hydrobiologia 326-327 (1996), S. 145-148 
    ISSN: 1573-5117
    Keywords: algal taxonomy ; Brazil ; Gracilaria ; Gracilariopsis ; Rhodophyta ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Most of the agar production in the world now comes from terete species of Gracilariaceae, a notoriously difficult group with regard to species circumscription. We have studied different populations of such algae from Brazil and from abroad in order to ascertain their identity and relationship. We based our taxonomic concepts on traditional morphological markers and attempted crosses between putatively interspecific and geographically isolated intraspecific populations. Data from the crosses helped in the recognition of genera and species with convergent morphologies and between disjunct populations. Our results show that configuration of male reproductive structures and some features of cystocarp anatomy are reliable taxonomic characters whereas some morphological features, such as gross thallus morphology and branching pattern, are not.
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  • 29
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    Hydrobiologia 326-327 (1996), S. 173-178 
    ISSN: 1573-5117
    Keywords: diversity ; endemism ; global ; Phaeophyta ; seaweed ; upwelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Brown algal species diversity is compared in 100 km sections of the coastlines of four warm temperate regions: southern Australia, California, southwestern Africa, north-central Chile. The highest diversity (over 140 species per section) is found in southern Australia. California has a reasonable diversity (around 70 species per section), and both southern Australia and California have high regional endemism. Sections of north-central Chile and southwestern Africa have similar patterns, with low diversity (〈 30 species per 100 km section), low endemism, few or no fucoids, and up to 25% of the brown algal flora are environmentally tolerant species of Scytosiphonales. Species turnover between contiguous sections of coast is generally related to relative change in temperature regime. Thus the high diversity of southern Australia is due to high species diversity within the 100 km sections, with little turnover, except for a rapid reduction in eastern Victoria likely to be related to lack of rocky substatum. It is hypothesized that low diversity and endemism in Chile and southwestern Africa can be explained by the occurrence of major environmental perturbations (upwelling and El Nino effects) in these regions, producing variable inter-annual temperature conditions that select out tolerant species from the local floras.
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  • 30
    ISSN: 1573-5117
    Keywords: Fucus serratus ; Himanthalia elongata ; iteroparous ; reproductive allocation ; reproductive effort ; seaweed ; semelparous
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Reproductive allocation, the proportion of total dry weight allocated to receptacle tissue and reproductive effort, the proportion of reproductive carbon requirement contributed by receptacle photosynthesis, were measured in two fucoid algal species Fucus serratus and Himanthalia elongata at sites in NE Scotland. Reproductive development takes over ten months in H. elongata, a semelparous (single reproductive event) species, and reproductive allocation at receptacle maturity is over 98%. Following gamete release, the whole thallus dies. In contrast, reproductive development in F. serratus takes four months. Fucus serratus is iteroparous (capable of multiple reproductive events), reproductive allocation is 38.6% for the first reproductive event and 50.5% for the following year's event. In Fucus serratus, the receptacles appear to make a major contribution to their own carbon requirements after the first month of reproductive development. The receptacles of Himanthalia elongata contribute only a small proportion of the receptacle carbon requirements in the first four months of reproductive development, after which the contribution made through receptacle photosynthesis increases.
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  • 31
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    Hydrobiologia 326-327 (1996), S. 213-215 
    ISSN: 1573-5117
    Keywords: Argentina ; seaweed ; southwest Atlantic ; Undaria pinnatifida ; wakame
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract In December 1992, some sporophytes of the Asian kelp Undaria pinnatiftda were found growing subtidally at 6 m depth below ‘A. Storni’ Port, Puerto Madryn, Argentina. During the winter of 1994, the species expanded significantly from its original location. Sporelings appear in early autumn and attain their maximum size (1.65 ± 0.10 m) during winter and early spring, when most of them become fertile. The fronds are lost in summer, with only some holdfasts and sporophylls surviving, and these disappear by the end of summer. The occurrence of U. pinnatida in Golfo Nuevo is reportedly due to an accidental introduction by cargo ships or fishing vessels arriving from Asian ports.
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  • 32
    ISSN: 1573-5117
    Keywords: aliens ; Atlantic ; Laminariales ; seaweed ; Undaria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Since its first introduction into the Atlantic for farming purposes in 1983, the brown alga Undaria pinnatifida has been found at several sites along the European coasts. The present study deals with an ecological experiment that was performed at the island of Ushant (Brittany, France) in order to check the ability of Undaria to recruit to a rocky substratum in situ. On the one hand, the authors were unsuccessful in getting Undaria to colonize a previously denuded area of shore, which was subsequently colonized by other native species, a result that may speak for a competition between Undaria and the local kelps. On the other hand, evidence is presented that Undaria pinnatifida has become a member of the Atlantic flora for good. The sporophytes can be found growing from low water mark of neap tide (+1.5 m) down to at least −15 m below lower water mark of spring tide. Its propagation is thought to occur in at least two ways: either step by step from cultivation sites along the coasts, or from the hulls of ships sailing from harbour to harbour. The preference of Undaria for settlement is on artificial structures.
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  • 33
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    Hydrobiologia 326-327 (1996), S. 223-228 
    ISSN: 1573-5117
    Keywords: fecundity ; Gelidium sesquipedale ; Portugal ; reproduction ; seaweed ; size ; spore recruitment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Gelidium sesquipedale fecundity was quantified by counting tetrasporangial sori and cystocarps per meter squared and by estimating the number of spores contained inside them. These were obtained by regression on a size metric of reproductive structures. Tetrasporangial sori length and cystocarp thickness were the best estimators of spore number. To assess spore recruitment, 12 pottery tiles were fixed to the bottom, and the appearance of small fronds was monitored. No clear seasonal pattern of reproduction was found. Tetraspore production peaked in March 1990 with 10.4 × 106 spores m−2, whereas the carpospore peak was lower, 4.9 × 105 spores m−2 in July 1989. Recruitment followed tetraspore peaks. The probability of a G. sesquipedale tetraspore making the transition to a recruit was 4.7 × 10−5. Frond length was significantly related to tetrasporangial sori number, while cystocarp number was only related to frond branching order. Minimum size for reproduction was 6.9 cm for gametophytes and 5.4 cm for tetrasporophytes; very rarely were cystocarpic fronds smaller than 9 cm, while tetrasporic fronds were often longer than 15 cm. Cystocarpic fronds were significantly shorter and had more branches than tetrasporic fronds.
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  • 34
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    Hydrobiologia 326-327 (1996), S. 253-258 
    ISSN: 1573-5117
    Keywords: Gigartina skottsbergii ; management ; seasonal variation ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract This study reports the variations in biomass and reproductive phenology in a natural bed of Gigartina skottsbergii over a period of a year and correlates these variations with the abiotic factors solar radiation, number of daylight hours, water temperature and salinity. The results obtained show an annual production cycle with maximum biomass values in spring-summer, correlated with high solar radiation and to a lesser extent with salinity. Sexual reproduction was maximum in autumn-winter, correlated with low temperature and short-day conditions. The population showed a large gametophytic dominance according to size and biomass, which suggests that there is not ecological equivalence between the life history phases of the species. Finally, based on the results, a restriction of harvesting to spring-summer is suggested.
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  • 35
    ISSN: 1573-5117
    Keywords: Chile ; management ; Rhodophyta ; Sarcothalia ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The present paper describes growth dynamics in a natural bed of the resource ‘luga negra’ (Sarcothalia crispata) in Guapilinao, southern Chile (41°57′ S, 73°31′ W). This resource is currently harvested and exported as raw material for the production of carrageenan. Seasonal variation in biomass, frond size, density and phenology was determined by periodic sampling. Natural recruitment was evaluated on different substrata added to the field; at the same time, substrata were inoculated under greenhouse conditions. Results showed that ‘luga negra’ has seasonal growth: biomass increased from a minimum in spring to a maximum in mid to late summer. On the other hand, density was minimal in winter (200 ind. m−2) and increased to 2000 ind. m−2 in late spring. Peak abundance of mature tetrasporic fronds occurred in late summer, whereas that of cystocarpic fronds occurred in winter. Recruitment began in summer and extended into winter. Survival on different substrata were compared. Gametophytes had better survival rates on clam shells and 5 mm rope while tetrasporophytes had the best survival rate on clam shells and secondarily on boulders.
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  • 36
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    Hydrobiologia 326-327 (1996), S. 259-265 
    ISSN: 1573-5117
    Keywords: biomass-density relationship ; Gigartinaceae ; Mazzaella cornucopiae ; seaweed ; self-thinning
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The negative relationship between stand biomass and plant density observed in terrestrial plants was tested among fronds of a clonal red alga, Mazzaella cornucopiae. Stand biomass and frond density were estimated bimonthly for 1 year on 7 permanent quadrats. A positive linear correlation was found between biomass and density for the whole data set, suggesting the lack of self-thinning among fronds of this intertidal alga at natural densities. Higher frond densities could favor increased water retention among fronds, thus minimizing desiccation during low tides. In this way, stands could maintain higher production of biomass. Fronds may also be cushioned better against wave action at higher frond densities, thus decreasing the detachment of larger fronds. The temporal variation of the relationship between biomass and density was plotted separately for these 7 quadrats. Four quadrats showed positive linear correlation between both variables (the other three quadrats showed non-significant positive linear correlation). Their four slopes are statistically similar to that found for the entire data set. It is possible, then, that there is only one positive slope for the biomass-density relationship in this population. If this is true, standing biomass could be estimated from the density of fronds.
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  • 37
    ISSN: 1573-5117
    Keywords: Antarctica ; biomass ; Iridaea cordata ; Rhodophyta ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Results of a seasonal study on biomass in an infralittoral population of Iridaea cordata from Terra Nova Bay (Ross Sea, Antarctica) are reported. Thalli were collected during the IX Italian Antarctic Expedition (austral summer 1993–94). The population studied is that living at depths of 4 to 6 m, where the highest density of plants occurred. The highest value of biomass (wet weight 3440 g m−2) was found at the beginning of summer. In that period 72.5% of biomass was from 128 specimens belonging to weight classes 8 (〉16 to 32 g) to 10 (〉64 g), corresponding to 13.4% of the population in numbers. Small (〈1 g) and medium (1 to 8 g) specimens provided the remaining biomass of 5% and 22.5%, respectively. During the month of January, the number of heavy specimens decreased. At the end of that month biomass reached a minimum of 2225 g m−2. In February the biomass increased to 3169 g m −2, 72% of which was from 120 specimens belonging to weight classes 7 (〉8 to 16 g) to 9 (〉32 to 64 g), which numerically represented 18.5% of the population. Data showed that biomass depended mainly on the presence of large heavy specimens, even though they were always few in number. Moreover, the occurrence of such large thalli at the beginning of summer suggests that Iridaea cordata continues to grow during the long antarctic winter.
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  • 38
    ISSN: 1573-5117
    Keywords: Exxon Valdez ; Fucus ; intertidal ; oil spill ; pollution ; restoration ; rockweed ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The Exxon Valdez oil spill in March 1989 and subsequent cleanup caused injury to intertidal Fucus gardneri populations especially in the upper intertidal. A survey in 1994 in Prince William Sound, Alaska showed that the upper boundary of Fucus populations at oiled sites was still an average of 0.4 m lower than the upper boundary at unoiled sites. Restoration of severely damaged Fucus populations was started on a small-scale at a heavily oiled rocky site in Herring Bay, Prince William Sound. Experiments employed mats of biodegradable erosion control fabric to act as a substratum for Fucus germlings and to protect germlings from heat and desiccation stress. A series of plots was covered with mats made from a resilient coconut-fiber fabric in June 1993. Half of the mats were inoculated with Fucus zygotes. A series of uncovered control plots was also monitored. There was no enhancement of Fucus recruitment on the rock surfaces under the mats. Dense populations of Fucus developed on the surface of all of the mats by the summer of 1994. The natural rock surfaces in the control plots, both inoculated and not, were barren of macroscopic algal cover. By September 1994, the juvenile thalli on the mats were approximately 2 cm in length. Inoculating the mats had an effect only in the upper region of the intertidal. It is expected that the thalli will become fertile during the 1995 season. These thalli may serve as a source of embryos to enhance the recovery of new Fucus populations in this high intertidal area.
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  • 39
    ISSN: 1573-5117
    Keywords: biotest ; brackish ; Gracilaria ; growth inhibition ; marine ; photosynthesis ; Rhodophyta ; seaweed ; toxicity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A growth inhibition test method was developed using the macroalga Gracilaria tenuistipitata as the test organism. This alga was chosen because of its high laboratory growth rates, commonly 30–40% d−1, which are reached in salinities between 5 and 40‰, and its epiphyte resistance. The toxicity of a number of substances, including heavy metals, herbicides and complex wastewaters towards the alga was assayed. Anti-fouling paints were tested with a modification of the method. EC50 values for heavy metals varied between 0.05 and 17 mg l−1 and for herbicides between 0.002 and 0.02 mg l−l. The sensitivity to the toxicant was generally higher at low salinity. Omitting nitrogen and phosphorus additions to the test medium increased the sensitivity and a semi-static performance was possible with maintained or increased sensitivity. Preliminary tests done with a computerised photosynthesis inhibition method produced promising results. In conclusion, this is a simple, sensitive and reproducible test method for assessing the toxicity of substances, wastewaters and anti-fouling paints in brackish and marine environments.
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  • 40
    ISSN: 1573-5117
    Keywords: Chondrus crispus ; carbon demand ; pH regulation ; seaweed ; tank cultivation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The injection of exogenous carbon into intensively cultivated algal tanks is necessary to insure a maximum growth rate by stabilizing the dissolved inorganic carbon (DIC) pool, but represents the major part of the cultivation cost (ca. 73%). This study was conducted in paddle-wheel tanks ranging in size from 260 m2 to 1000 m2. Additional carbon was provided by carbon dioxide mixed into the incoming sea water through a tubular reactor. Production vs pH was analysed on 120 growth measurements covering two years of continuous cultivation. Whereas production peaked at pH 8.0–8.2, the economic optimum for pH regulation was in the range 8.4–8.5, where CO2 injection was greatly reduced (−29%) for only a slight decrease in production (−4%). Expressed as a function of pH level, the specific carbon injection (g c gdw−1 of Chondrus produced) showed an inverse exponential relationship, whereas gross photoconversion ratio (gdw mol photons−1) varied according to a second degree equation with a low amplitude. The photoconversion ratio was not improved when the culture was maintained at a DIC concentration higher than the natural equilibrium (0.64 ± 0.11 gdw mol photons−1 at 2.35 mM and 0.65 ± 0.15 gdw mol photons−1 at 3.19 MM). A complementary source of carbon was found in underground salt water with a high and stable DIC concentration (10.15 ± 0.25 mmole Cl−1). The mixing of the well water with natural sea water allowed another economy of CO2 (−20% at pH 8.5) and nutrients (−12%), the total unitary cost of production being cut by about 17%.
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  • 41
    ISSN: 1573-5117
    Keywords: Baltic ; disease ; endophyte ; Laminaria ; Phaeophyceae ; seaweed ; Streblonema
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The brown alga Laminaria saccharina is the dominant subtidal macroalga in Kiel Bay, western Baltic. It is infected by the microscopic brown alga, Streblonema aecidioides. Infected thalli may show symptoms of Streblonema disease, i.e. alterations of blade and stipe, ranging from dark spots to heavy deformations and completely crippled thalli. Samples taken from a single locality all year round show that (i) the host population is infected at a high rate of 87±13% (SD), but that (ii) a considerable proportion of thalli containing Streblonema does not show disease symptoms, and that (iii) juvenile hosts, which mainly appear in autumn, are infected at almost the same rate. Thus the infection seems to occur early in the host's life. Juveniles in nature show fewer symptoms of the disease than adults. Two months after infection, oxygen production and growth in laboratory-raised experimentally infected juvenile hosts was not different from uninfected controls. Experimental thalli showed more severe morphological alterations than uninfected controls only four months after infection. Both field and laboratory observations indicate that a lag phase exists between infection and outbreak of the disease.
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  • 42
    ISSN: 1573-5117
    Keywords: agar ; Gracilaria changii ; mariculture ; reproduction ; seasonality ; seaweed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Gracilaria changii, recorded from Malaysia and Thailand, is one of the more abundant agarophytic seaweeds found in Malaysia. A wild population of Gracilaria changii growing in mangroves was monitored for seasonal variation in agar content and gel strength as well as spore production. Agar yield and gel strength ranged from 12 to 25% dry weight and 294 to 563 g cm−2, respectively, over a 15-month period. Gel strength but not yield was positively correlated with amount of rainfall. Cystocarps were observed throughout the study, but use of sporetraps showed that spore release peaked around July–August and January–February after the two monsoon periods. Mariculture of Gracilaria changii in shallow ponds in the mangroves, in an irrrigation canal and in a shrimp farm pond was conducted. Average growth rate of cuttings tied to monofilament lines was 3.3 ± 1.7% d−1, 8.4 ± 1.8% d−1 and 3.6 ± 1.6% d−1 respectively. Cuttings were lost to siltation, wave action, predation and heavy epiphytisation. These studies show that Gracilaria changii has potential commercial application in the agar industry.
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  • 43
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    Hydrobiologia 326-327 (1996), S. 361-365 
    ISSN: 1573-5117
    Keywords: culture ; Gelidiaceae ; Gelidium sclerophyllum ; seaweed ; vegetative propagation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Results of the first phase of production of "seed" for a project of marine culture of species of Gelidiales are presented. Vegetative fragments of different sizes and from different parts of the thallus of Gelidium sclerophyllum from the Mexican tropical Pacific coast were cultured under nine treatments with different N and P concentrations. In treatments without N all fragments died; good vegetative growth was present in all remaining treatments. Growth in length and branch production were favored in medial fragments, and rhizoid production was favored in apices. Growth in length and biomass increase were stimulated by high N concentrations (2–3 mM), and branch and rhizoid production were stimulated by high P concentrations (100–150 µM).
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  • 44
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the way to the fullerene-acetylene hybrid carbon allotropes 2 and 6, the oxidative homocoupling of the 2-functionalized 1-ethynylated C60 derivatives 11, 12, 14, and 15 was investigated. Under Glaser-Hay conditions, the two soluble dumbbell-shaped bisfullerenes 17 and 18, with two C60 moieties linked by a buta-1,3-diynediyl bridge, were formed in 52 and 82% yield, respectively (Scheme 2). Cyclic-voltammetric measurements revealed that there is no significant electronic communication between the two fullerene spheres via the buta-1,3-diynediyl linker. Removal of the 3,4,5,6-tetrahydro-2H-pyran-2-yl (Thp) protecting groups in 18 gave in 80% yield the highly insoluble dumbbell 19 with methanol groups in the 2,2′-positions of the buta-1,3-diynediyl-bridged carbon spheres. Attempted conversion of 19 to the all-carbon dianion 6 (C1242-) via base-induced elimination of formaldehyde was not successful presumably due to exo-dig cyclization of the formed alkoxides. The occurrence of this cyclization under furan formation was proven for 2-[4-(trimethylsilyl)buta-1,3-diyn-1-yl][60]fullerene-1-methanol (21), a soluble model compound for 19 (Scheme 3). To compare the properties of ethynylated fullerene mono-adducts to those of corresponding higher adducts, hexakis-adducts 26 and 28 with an octahedral functionalization pattern resulting from all-e (equatorial) additions were prepared by the reversible-template method of Hirsch (Scheme 4). Reaction of the ethynylated mono-adducts 25 or 13 with diethyl 2-bromomalonate/1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in the presence of 1,9-dimethylanthracene (DMA) as reversible template led to 26 and 28 in 28 and 22% yield, respectively. Preliminary experiments indicated a significant change in reactivity and NMR spectral properties of the fullerene addends with increasing degree of functionalization.
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  • 45
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 137-150 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Supports consisting of a thin layer (2-10%) of polystyrene (PS) grafted onto a poly(tetrafluoroethylene) (PTFE) core are an interesting alternative to controlled pore glass (CPG) carriers in oligonucleotide synthesis. The beads are mechanically stable, do not show significant swelling, and allow effective removal of substrates by short washing steps with organic solvents. PTFE-PS as an organic polymer has generally more hydrophobic properties than inorganic polymer supports and, therefore, is well compatible with organic solvents such as anhydrous MeCN. We found PTFE with a content of 2-3% PS graft to be a very good support for the synthesis of oligonucleotides of extended length. In comparison, PTFE with 5-10% grafted PS is especially useful for large-scale syntheses. Functionalization procedures minimized in the extent of side reactions are described as well as examples for the use of the supports in syntheses of oligonucleotides both on large scale and of extended chain length.
    Additional Material: 7 Ill.
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  • 46
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of ‘Push-Pull’ Enynes with Acids. First Observation of a Rearrangement of 5-Chloro-5-(dialkylamino)pentadienals‘Push-pull’-enynes 7 react easily with HCl as well as with AcOH to give 5-amino-5-chloropentadienals 8 and 5-(acetoxy)-5-aminopentadienals 13 as well as the corresponding ketones. In view of a postulated rearrangement of compounds 8 and 13 (Scheme 2), both types of compounds have been treated with traces of acid. While no definite reaction is observed in case of 13, HCl-addition products 8 easily and quantitatively rearrange to give 2H-pyran-2-iminium chlorides 10 which are the postulated intermediates of the rearrangement 8→12 (Scheme 2).
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  • 47
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The self-assembly of alkaline folates in isotropic water solutions, with or without added salts, has been investigated by small-angle neutron-scattering, circular-dichroism, and NMR techniques. The assembled species are chiral, cylindrical aggregates of finite length, composed of stacked tetramers; each tetramer is formed by Hoogsteen-bonded folate residues. The assembly process is more efficient in the presence of an excess of NaI ions, leading to longer aggregates with stronger tetramer-tetramer-tetramer interaction. In pure water, the rods are shorter and the tetramer-tetramer interaction weaker. Association between folates can be detected by circular-dichroism spectroscopy starting from a concentration of 6· 10-4 mol l-1, well below the critical concentration for the formation of the cholesteric mesophase (ca. 0.5 mol l-1).
    Additional Material: 7 Ill.
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  • 48
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bromination of the monosilylated dialkynylated monomer 1a (Scheme 1), dimer 3 and tetramer 5 by N-bromosuccinimide (NBS) in the presence of CF3COOAg gave 2, 4, and 6, respectively, in over 93%. Similar conditions led to bromodesilylation. Either silyl group of the diprotected monomer 1c was selectively removed by bromolysis. On the one hand, bromodesilylation of 1c gave 2 in yields varying between 80 and 99%. On the other hand, bromodesilylation of 7, obtained from 1c by hydrolytic removal of the tetrahydro-2H-pyran-2-yl (Thp) group, yielded 91% of 8. Mechanistic considerations suggested that the deprotective bromination should be improved by replacing the Me3Si by a Me3Ge group. Indeed, bromodegermylation of 1b was quantitative and ca. 60 times faster than bromodesilylation of 1c. The Me3Si and Me3Ge groups can be used for an orthogonal protection/activation of dialkynes. This was shown by desilylating 12 to 11 (Scheme 2), while bromination yielded 13. Both reactions proceeded in high yields; 9 was isolated as a minor by-product of 13. The reactivity towards bromolysis decreases in the series H-DOPS 〉 Me3Ge ≈ H 〉 Me3Si 〉 Thp-DOPS (DOPS = [dimethyl(oxy)-p ropyl]dimethylsilyl). Orthogonal bromolysis of DOPS- and Me3Ge-substituted dialkynes is slightly more selective than the one of Me3Si- and Me3Ge-substituted analogues. Coupling of 7 with the bromoalkyne 2 gave the dimer 15 (76%), 14 (2%), and 16 (4%) (Scheme 3). The binomial synthesis was optimized so that each cycle, doubling the size of the precursor, requires the minimal number of transformations (Scheme 4). The orthogonally protected monomer 1b, dimer 19, and tetramer 22 were, on the one hand, hydrolyzed to the alcohols 18 (95%), 21 (91%), and 24(91%), respectively, and, on the other hand, bromodegermylated to 2 (99%), 4 (97%), and 6(93%). Cross-coupling of 18 with 2, 21 with 4, and 24 with 6 gave the orthogonally protected dimer 19 (73%), tetramer 22 (87%), and octamer 25 (83%), respectively.
    Additional Material: 1 Ill.
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  • 49
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of novel thiazole-containing complexing agents and their luminescence properties with EuIII and TbIII ions are reported. One of these terpyridine analogues was also tested as an EuIII labelling reagent, and its luminescence properties as an antibody conjugate were studied.
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  • 50
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 51
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    Helvetica Chimica Acta 79 (1996), S. 363-370 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemical screening of the secondary metabolites from Halenia corniculata L. (CORNAZ), by LC/UV,LC/TSP-MS (thermospray), and LC/ES-MS (electrospray) was used for the targeted isolation of corniculoside (1), a new biosidic ester secoiridoid. The structure was established as 7-β-[(E)-4′-O-(β-D-glucopyranosyl)caffeoyloxy]-sweroside by 1D- and 2D-NMR, LC/UV, LC/MS, and FAB-MS data, in combination with chemical reactions.
    Additional Material: 2 Ill.
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  • 52
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Addition reactions of organometallic reagents with 4,4-disubstituted 1,3-thiazole-5(4H)-thiones were studied. Whereas the reactions with alkyllithium and alkyl Grignard reagents occurred in the thiophilic manner, the carbophilic addition was observed with allyllithium and allyl Grignard reagents. A radical reaction mechanism is proposed for rationalizing these observations (Scheme 5). A radical cyclization of the prepared 5-allyl-4,5-dihydro-1,3-thiazole-5-thiol derivatives yielded 1,6-dithia-3-azaspiro[4.4]non-2-enes (Table 4).
    Additional Material: 4 Tab.
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  • 53
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The syntheses of various fluorocarbon/fluorocarbon and fluorocarbon/hydrocarbon rac-1,2- and 1,3-di-O-alk(en)ylglycerophosphocholines and rac-1,2-di-O-alkylglycerophosphoethanolamines (see Fig.2), which may be used as components for drug-carrier and delivery systems, are described together with some results concerning their biological tolerance. They were obtained by phosphorylation of perfluoroalkylated rac-di-O-alk(en)ylgly-cerols using POCl3, then condensation with choline tosylate or N-Boc-ethanolamine (2-[(tert-butoxy)carbonyl-amino]ethanol) followed by Boc-deportection (Schemes 6-8). The fluorcarbon/fluorocarbon 1,2-di-O-alkylgly-cerols were prepared by O-alkylation of rac-1-O-benzylglycerol using perfluoroalkylated mesylates, then hydrogenolysis for benzyl deprotection (Scheme 1). The two different hydrophobic chains in the mixed fluorocarbon/fluorocarbon and fluorocarbon/hydrocarbon 1,2-di-O-alk(en)ylglycerols were introduced starting from 1,2-O-iso-propylidene- then O-trityl-protected glycerols or from 1,3-O-benzylidene-glycerol (Schemes 3 and 4). The perfluoroalkylated O-alkenylglycerols were obtained by O-alkylation of a glycerol derivative using an ω-unsaturated alkenyl reagent, the perfluoroalkyl segment being connected onto the double bond in a subsequent step (Schemes 1) and 3. The perfluoroalkylated symmetrical and mixed 1,3-di-O-alkylglycerols were synthesized by displacement of the Cl-atom in epichlorohydrin by perfluoroalkylated alcohols, then catalytic (SnCl4) opening of the oxirane ring of the resulting alkyl glycidyl ethers in neat alcohols (Scheme 5). When injected intravenously into mice, acute maximum tolerated doses higher than 1500 and 2000 mg/kg body weight were observed for the fluorinated glycerophosphocholines, indicating a very promising in vivo tolerance.
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  • 54
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    Helvetica Chimica Acta 79 (1996), S. 449-453 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ten new α-diazo-β-oxoaldehydes were condensed with aniline, ammonia, hydroxylamine, and semicarbazide to yield new 4-acyl-(1-substituted)-1H-1,2,3-triazoles in moderate-to-good yields. The method is simple and regiospecific. The latter feature makes this method superior to the widely used acylacetylene + azide approach.
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  • 55
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    Helvetica Chimica Acta 79 (1996), S. 477-487 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of oligonucleotides containing N7-(2-deoxy-β-D-erythro-pentofuranosyl)guanine (N7Gd; 1) is described. Compound 1 was prepared by nucleobase-anion glycosylation of 2-amino-6-methoxypurine (5) with 2-deoxy-3,5-di-O-(4-toluoyl)-α-D-erythro-pentofuranosyl chloride (6) followed by detoluoylation and displacement of the MeO group (8→10→1). Upon base protection with the (dimethylamino)methylidene residue (→11) the 4,4-dimethoxytrityl group was introduced at OH—C(5′) (→12). The phosphonate 3 and the phosphoramidite 4 were prepared and used in solid-phase oligonucleotide synthesis. The self-complementary dodecamer d(N7G—C)6 shows sigmoidal melting. The Tm of the duplex is 40°. This demonstrates that guanine residues linked via N(7) of purine to the phosphodiester backbone are able to undergo base pairing with cytosine.
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  • 56
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    Helvetica Chimica Acta 79 (1996), S. 518-526 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Starting from the esters (2E,4S)-6 and (2E,4R)-6, bromo aldehydes (S)-9 and (R)-9 as well as bromo alcohols (S)-10 and (R)-10, respectively, were prepared. Bromo alcohol (R)-8 was converted to the diol (2E,4R)-16. Ozonolysis of the latter led to aldehyde (R)-17, which was transformed, by a Wittig reaction, to (2R,4E,6R)-18, corresponding to the C(7)-to-C(14) segment of phomenoic acid (1). Attempts to improve the yields by applying a Julia coupling of (R)-23, which was prepared from (2E,4R)-7, with (R)-24 were unsuccessful. Finally, the coupling of the iodo derivative (2E,4S)-28 with the lithiated derivative of 1,3-dithiane 30 by the Corey-Seebach ‘Umpolung’ led to (3S,4E)-32 which is a derivative of the C(7)-to-C(14) segment of 1, suitable for further transformations.
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  • 57
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monodisperse and polydisperse oligomers and polymers of 3-hydroxybutanoic acid (3-HB) containing 8, 16, ca. 28, 32, ca. 60, 64, 96, and ca. 3000 monomer units were incorporated into palmitoyl-oleoyl-phosphatidyl choline (POPC) planar bilayers. At concentrations of 0.1-5% of oligo(3-HB), the resulting phospholipid bilayers showed typical single-channel behavior for Rb+ and Ba2+ ions, using the patch clamp technique. Thus, channel-forming activity of a pure polyester has been demonstrated for the first time (Figs. 1, 3, and 6). Single-channel activity depends upon the following structural parameters of the 3-HB derivatives: unprotected OH and COOH groups on the chain ends; chain length ≥ 16 monomer units; no high-molecular-weight as in P(3-HB). The results are discussed in view of the Ca2+-specific channel formed with the P(3-HP)/Ca · PPi complex from genetically competent Escherichia coli and in view of the ubiquitous occurrence of low-molecular-weight P(3-HB) in prokaryotic and eukaryotic organisms. A simple model for the channel-causing structure is proposed, based on the proven tendency of oligo- and poly(3-HB) to form ca. 50-Å thick lamellar crystallites.
    Additional Material: 7 Ill.
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  • 58
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    Helvetica Chimica Acta 79 (1996), S. 568-570 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 59
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    Helvetica Chimica Acta 79 (1996), S. 548-559 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Synthesis of p-CumaroylspermidinesThe synthesis of three mono[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines, 10, 20, and 28, three bis[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines, 6, 16, and 25, and one tris[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]-spermidine is described.
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  • 60
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four cyclotetrapeptides containing one (1, 2) or two (3, 4) chiral amino acids have been C-alkylated or C-hydroxyalkylated through Li+ or phosphazenium (P4 · H+) enolates. The reactions are completely diastereoselective (by NMR or HPLC analysis) with respect to the newly formed backbone stereogenic centres (Tables 2 and 3). The reactivity of the polylithiated species responsible for these alkylations is such that only highly reactive electrophiles (MeI, BnBr, primary allylic halides, aldehydes, CO2) can be employed. It is shown that the position, and thus the chirality sense, of the newly formed stereogenic centre in a given cyclotetrapeptide backbone is controlled by the positioning of N-methyl groups in the starting material (cf. cyclo(-MeLeu-Gly-D-Ala-Sar-) (3) and cyclo(-Leu-Sar-MeDAla-Gly-) (4) in Scheme 1). With Schwesinger's phosphazene P4-base, all NH groups are first benzylated and C-benzylation then takes place at a sarcosine, rather than an N-benzylglycine residue (Table 3). In contrast to open-chain N-benzyl peptides, the N-benzylated cyclotetrapeptides could not be debenzylated under dissolving-metal conditions (Na/NH3). Conformational analysis (NMR spectroscopy and X-ray diffraction) shows that the prevailing species have cis/trans/cis/trans(ctct) peptide bonds (zigzag conformation of Ci backbone symmetry, Figs. 2-4). However, a hitherto unknown conformation of cyclotetrapeptides has been found in CDCl3 solutions of the hydroxyalkylated products 18-21 (obtained with EtCHO and PhCHO as electrophiles; Fig.4). The new conformation has four trans peptide bonds and is believed to result mainly from intramolecular H-bond formation, involving the newly generated alkyl- or arylserine residue. This assumption has also been supported by modelling (TRIPOS force field, SYBYL, see Fig.5 and Table 6). The structure may be considered as a β-turn mimic.
    Additional Material: 5 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: The synthesis of functionalized 1,1,2,2-tetraethynylethanes (= 3,4-diethynylhexa-1,5-diynes) as synthons for tetraethynylethenes (3,4-diethynylhex-3-ene-1,5-diynes) and as building blocks for three-dimensional acetylenic molecular scaffolding targeting the synthesis of the molecular carbon belts 3 and 4 is reported (Scheme 1). Reaction of diethyl oxalate and (trialkylsilyl)ethynyl Grignard reagents afforded the silyl-protected 3,4-diethynylhexa-1,5-diyne-3,4- diols 7 and 8 which were transformed in high yields into the cyclic carbonate 9 and the cyclic orthoesters 10-13, respectively (Scheme 2). The solid-state structures of 9 and 10 were elucidated by X-ray crystallography. The alkyne protecting groups in 9, 10, and 12 were smoothly removed to give the free tetraynes 14-16 as relatively stable oils in nearly quantitative yields (Scheme 3). Orthoesters 15 and 16 underwent Pd-catalyzed cross-coupling with iodobenzene to give the tetraphenyl derivatives 17 and 18 (Scheme 4). Thermal acid-catalyzed elimination of the orthoester moieties in 12 and 13 produced the silyl-protected tetraethynylethenes 19 and 20 and concluded a novel, simple three-step synthesis of these fully two-dimensionally conjugated π-chromophores (Scheme 5).
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  • 62
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    Helvetica Chimica Acta 79 (1996), S. 702-709 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of new carbocyclic C-nucleosides with a cis-4′-(hydroxymethyl)cyclopent-2′-enyl sugar moiety and unnatural pyrimidine bases (2-6) were synthesized in racemic form in two steps starting from the easily accessible cyclic carbonate 1.
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  • 63
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    Helvetica Chimica Acta 79 (1996), S. 736-741 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and liquid-crystalline and thermal properties of a fullerene[60] functionalized by a framework containing two cholesterol derivatives through a methanofullerene structure are reported. The targeted fullerene derivative showed high thermal stability.
    Additional Material: 1 Ill.
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  • 64
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the thymine- and adenine-containing 5′-epi-bicyclodeoxynucleosides 7 and 8 as well as of the corresponding building blocks 13 and 14 for oligonucleotide syntheis according to the phosphoramidite methodology is described. A conformational analysis of 7 and 8 by 1H-NMR spectroscopy, refined by molecular modeling, shows the preferred conformation of the furanose unit in these nucleosides to be of the 1′-exo/2′-endo type. The 5′-OH group on the carbocyclic ring prefers to be axially oriented, thus placing torsion angle γ in the unusual -syn-clinal (-sc) range. These epi-bicyclodeoxynucleosides were successfully incorporated into DNA decamers. From UV/melting curves of such decamers with DNA and RNA complements, a duplex destabilization of -2 to -9° per residue was observed. An oligonucleotide built completely from 5′-epi-bicyclothymidine shows no detectable affinity to its DNA or RNA complement anymore. CD Spectra of duplexes containing 5′-epi-bicyclodeoxynucleotide units are very similar to the natural reference systems, indicating no major structural changes. A molecular-dynamics simulation of a heptamer duplex containing one 5′-epibicyclothymidine residue in the center reveals a conformational change of its carbocyclic unit placing torsion angle γ in the (for the free mononucleoside unfavorable) -anti-clinal (-ac) conformation in the duplex. The role of torsion angle γ on DNA duplex stability is discussed.
    Additional Material: 8 Ill.
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  • 65
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: L-Aspartic acid by tosylation, anhydride formation, and reduction with NaBH4 was converted into (3S)-3-(tosylamino)butan-4-olide (8; Scheme 1). Tretment of 8 with ethanolic trimethylsilyl iodide gave the N-protected deoxy-iodo-β-homoserine ethyl ester 9. The latter, on successive nucleophilic displacement with lithium dialkyl-cuprates ( → 10a-e), alkaline hydrolysis ( → 11a-e), and reductive removal of the tosyl group, produced the corresponding 4-substituted (3R)-3-aminobutanoic acids 12a-e (ee 〉 99%). Electrophilic hydroxylation of 8 ( → 19; Scheme 3), subsequent iodo-esterification ( → 21; Scheme 4), and nucleophilic alkylation and phenylation afforded, after saponification and deprotection, a series of 4-substituted (2S, 3R)-3-amino-2-hydroxybutanoic acids 24 including the N-terminal acids 24e ( =3) and 24f ( =4) of bestatin and microginin (de 〉 95%), respectively.
    Additional Material: 1 Tab.
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  • 66
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    Helvetica Chimica Acta 79 (1996), S. 1241-1248 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 67
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    Helvetica Chimica Acta 79 (1996), S. 1295-1304 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An asymmetric synthesis of the spermidine alkaloid (+)-cyclocelabenzine (1a) and its (-)-(13S)-epimer 1b is described using optically active (+)-(3S)-3-amino-3-phenylpropionic acid as the chiral building block. The isoquinolin-1-one fragment 15 was synthesized by a modified Bischler-Napieralski reaction. The relative configuration of the (-)-isomer was determined by an X-ray crystal-structure analysis, which enabled us to determine the absolute configuration of natural (+)-1a as (8S,13R).
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  • 68
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The methanolysis of the epimeric 7-chloro-7H-yohimbine derivatives 2 and 3 was reinvestigated. In case of the 7α-epimer 2, the reaction was uneventful and conformed with earlier observations, i.e., under sufficiently mild conditions, only the imino ether 4 (= imino ether A) was produced. Under the same conditions, the less reactive β-isomer 3 furnished a mixture of both imino ethers 4 and 5, accompanied by the elimination product 11, and by equal amounts of yohimbine (1) and 3,4,5,6-tetradehydroyohimbine (12), which are believed to arise through a disproportionation process of the putative intermediate 5,6-didehydroyhimbine (23). The nature of this divergent reactivity and of the ready equilibration of 4 and 5 was investigated by means of extensive force-field and semi-empirical calculations (AM1 and PM3) of various conformers of the compounds 2-5 and of some possible reaction intermediates.
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  • 69
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Alkynylcyclohex-2-enones 1a-c and 2a-c react with H2O2/NaOH in MeOH to afford 1-alkynyl-7-oxabicyclo[4.1.0]heptan-2-ones 3a-c and 4a-c, respectively. The 3-unsubstituted bicyclic epoxy ketones 3a, 3b, and 4a, 4b react further with H2O2/NaOH, undergoing ring contraction and (formal) decarbonylation to give 2-alkynylcy-clopent-2-enols 5a, 5b, and 6a, 6b, respectively. Epoxy ketones 3 are also obtained under neutral conditions on irradiation (λ = 350 nm) of cyclohexenones 1 in air-saturated benzene solution. Similarly, under neutral conditions oxo-cycloalkenecarbonitriles 8 react (thermally) with H2O2 in MeCN to give the oxabicyclic carbonitriles 9.
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  • 70
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    Helvetica Chimica Acta 79 (1996), S. 1451-1461 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oligonucleotides containing (2′-deoxy-β-D-xylofuranosyl)guanine have been prepared. For this purpose 2-aminoadenosine (5) was synthesized and converted to 2′-deoxy-β-D-xyloguanosine (1). The related 2′-deoxy-β-D-xyloisoguanosine (3) and 2′-deoxy-β-D-xyloxanthosine (4) were also synthesized. Compound 1 was converted to the phosphonate and phosphoramidite building blocks 10 and 11, respectively. The oligodeoxynucleotide (5′-3′)d(xG-xT-xA-xG-xA-xA-xT-xT-xC-xT-xA-xC-T) (18) formed a duplex with the same Tm as the parent (5′-3′)-(G-T-A-G-A-A-T-T-C-T-A-C) (19), but with an inverted CD spectrum.
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  • 71
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    Helvetica Chimica Acta 79 (1996) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 72
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Early steps in the biosynthesis of dedecano-4-lactone in ripening nectarines (Prunus persica var. nucipersica) and strawberries (Fragaria ananassa) were studied using cis-9,10-([18O]epoxy)heptadecanoic acid (5), instead of the natural C18-precursor epoxystearic acid 1. In nectarines, an epoxide hydrolase catalyzed, in a highly regio- and enantioselective reaction, the attack of H2O at C(9) of epoxy acid 5 yielding preferentially (9R,10R)-dihydroxyheptadecanoic acid 6a as an early intermediate and, after further metabolization, undecano-4-lactone 7a. In strawberries, the same transformation exhibited only a moderate regio- and enantioselectivity. Besides the previously established function of phytogenic epoxide hydrolases involved in generating oxygenated fatty-acid derivatives, which are used in cutin monomer production and plant defence, a new rǒle for these enzymes now emerges in the enantioselective production of aroma components of ripening fruits. The cis-9,10-([18O]epoxy)heptadecanoic acid (≥ 98% 18O; 5) was obtained in good overall yield (68%) from isopropyl (9Z)-heptadec-9-enoate using 18O2 gas in a free-radical chain reaction in the presence of 2-methylbutanal.
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  • 73
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of Trifluoromethyl-Substituted Sulfur Heterocycles Using 3,3,3-Trifluoropyruvic-Acid DerivativesThe reaction of methyl 3,3,3-trifluoropyruvate (1) with 2,5-dihydro-1,3,4-thiadiazoles 4a, b in benzene at 45° yielded the corresponding methyl 5-(trifluoromethyl)-1,3-oxathiolane-5-carboxylates 5a, b (Scheme 1) via a regioselective 1,3-dipolar cycloaddition of an intermediate ‘thiocarbonyl ylide’ of type 3. With methyl pyruvate, 4a reacted similarly to give 6 in good yield. Methyl 2-diazo-3,3,3-trifluoropropanoate (2) and thiobenzophenone (7a) in toluene underwent a reaction at 50°; the only product detected in the reaction mixture was thiirane 8a (Scheme 2). With the less reactive thiocarbonyl compounds 9H-xanthene-9-thione (7b) and 9H-thioxanthene-9-thione (7c) as well as with 1,3-thiazole-5(4H)-thione 12, diazo compound 2 reacted only in the presence of catalytic amounts of Rh2(OAc)4. In the cases of 7a and 7b, thiiranes 8b and 8c, respectively, were the sole products (Scheme 3). The crystal struture of 8c has been established by X-ray crystallography (Fig.). In the reaction with 12, desulfurization of the primarily formed thiirane 14 gave the methyl 3,3,3-trifluoro-2-(4,5-dihydro-1,3-thiazol-5-ylidene)propanoates (E)-and (Z)-15 (Scheme 4). A mechanism of the Rh-catalyzed reaction via a carbene addition to the thiocarbonyl S-atom is proposed in Scheme 5.
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  • 74
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    Helvetica Chimica Acta 79 (1996), S. 1549-1558 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oligonucleotide building blocks, the phosphonates 1a, b and the phosphoramidites 2a, b derived from 7-iodo- and 7-bromo-7-deaza-2′-deoxyguanosines 3a, b were prepared. They were employed in solid-phase oligonucleotide synthesis of the alternating octamers d(Br7c7G-C)4 (8) and d(I7c7G-C)4 (9) as well as the homo-oligonucleotides d[(Br7c7G)5-G] (11) and d[(I7c7G)5-G] (12). The melting profiles and CD spectra of oligonucleotide duplexes were measured. The Tm values as well as the thermodynamic data were determined and correlated to the major-groove modification of this DNA. The self-complementary octamers 8 and 9 form more stable duplexes compared to the parent oligomer d(G-C)4. The heteroduplex of d[(I7c7G)5-G] (12) with d(C6) is slightly destabilized (ΔTm = -12°) over that of d[(c7G)5-G] with d(C6). However, the complex of 12 with poly(C) is more stable than that of d[(c7G5-G)] with poly(C).
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  • 75
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular structure of the two complex ions [Co(tmen)3]3+ and [Co(tmen)3]2+ (tmen = 2,3-dimethylbutane-2,3-diamine) have been determined at 100 K. They show a strong trigonal distortion of the octahedral CoN6 core. The twist angle is 26.2(2.8)° for CoII and 43.9(9)° for CoIII. Average Co—N distances are 2.193(13) Å (CoII) and 1.997(2) Å (CoIII), 0.02 Å longer than for the main body of CoIII amines.
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  • 76
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    Helvetica Chimica Acta 79 (1996), S. 1967-1979 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Guanidinium compounds imitating the bis(arginine) structural motif of staphylococcal nuclease (e.g. 3) are known to be powerful catalysts for phosphoryl transfer reactions in dipolar aprotic solvents. Compound 3 also accelerates the hydrolysis of RNA (H2O, pH 7). However, due to diminished substrate affinity in H2O, the rate effects are less pronounced in aqueous than in aprotic solution. To test if a synthetic ribonuclease may be derived from the bis(guanidinium) moiety of 3 by the addition of RNA-binding substructures, the TAR sequence of HIV-1 was chosen as a target. The arginine residue of compound 4 serves as an extremely simplified mimic of tat, a protein responsible for boosting the viral transcription by complex formation with TAR. Here, we present the synthesis of 4 and its ability to bind and to cleave efficiently the truncated TAR sequence 1. In addition, the synthesis of an acridine arginine conjugate, 19, is reported in preliminary form. Compound 19 associates with 1 and completely blocks the cleavage induced by 4.
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  • 77
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    Helvetica Chimica Acta 79 (1996), S. 2023-2034 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies on post-angioplastic restenosis have shown the implication of angiotensin II (Ang) as a myoproliferative mediator. The antiproliferative efficacy of non-peptide Ang antagonists on the rat carotid model is of 50%, whereas a continuously infused peptide antagonist at low doses totally blocks neointimal growth. To explore the feasibility of depot forms of Ang that may be introduced during angioplasty and thus prevent restenois, lipid-masked Ang analogues of the following general structure were prepared: [Xxx°, Yyy1]Ang with Xxx = decanoyl or palmitoyl and Yyy = Ser, Cys, Asp, β-lactoyl, 3-mercaptopropanoyl or succinyl. All fatty acylated peptides [Xxx°, Yyy1]Ang were practically inactive, and O- or S-esterified Ser and Cys peptides underwent intramolecular transcylation giving inactive Nx-acylated peptides. O-Acylated [β-mercaptopropanoyl1]Ang were easily hydrolyzed into their biologically active[Yyy1]Ang forms, either by mild saponification or by lipase activity.
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  • 78
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nortopsentin D (5), a bis(indole) alkaloid unique for bearing a 2-amino-methylimidazole appendage at the central 1H-imidazol-5(4H)-one nucleus, was isolated in abundance, besides the putative biogenetic precursor 6 of its appendage, from the deep-water axinellid sponge Dragmacidon sp. Structural elucidation of 5 by NMR and MS methods heavily relied on its N-methyl derivatives 8-11. Unusually for topsentin-type structures, natural 5 and semisynthetic methyl derivatives 8 and 10 proved inactive on KB tumoural cells, while introduction of the last three methyl groups, amazingly led to highly cytotoxic 11.
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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 interaction between a vitamin B12 derivative containing a peripheral C18 alkyl chain (see 1a) and a (methyl)thiomalonate substrate bearing alkyl chains of various length at the thioester group (see 5) was investigated. A catalytic cycle was established for the methylmalonyl→succinyl rearrangement by using electrochemistry and photolysis (see Scheme 3). Increased yields of the succinate relative to the reduction product were obtained (2:3 ratio), when the reaction was run in MeOH/H2O, and when both the substrate and the catalyst had an octadecyl substituent capable of hydrophobic interactions.
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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 electrospray tandem mass spectra (ESI-MS/MS) of the three N,N′-bis[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines 1-3 displayed the same fragment-ion signals. These isomers could not be differentiated by ESI-MS/MS, since their fragmentation patterns are similar. (E,E)-N-(3-[15N]Aminopropyl)-3,3′-bis(4- hydroxyphenyl)-N,N′-(butane-1,4-diyl)bis[prop-2-enamide] ([15N(1)])-(1) was synthesized in order to get further information about the fragmentation mechanisms. The comparison of the ESI-MS/MS of 1 and [15N(1)]-1 revealed a transamidation, the Zip reaction, under mass-spectral conditions of the [1 + H]+ ions. Because of this reaction, the three isomers 1-3 could not be distinguished.
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  • 81
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    Helvetica Chimica Acta 79 (1996), S. 2219-2234 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A total synthesis of cyclothialidine (1), a new DNA gyrase inhibitor isolated from Streptomyces filipinensis, is described. The synthetic concept was tested by preparing the lactone 13 (Scheme 2) which contains the characteristic bicyclic core entity of 1. Key features of the synthesis of 1 are: preparation of 3,5-dihydroxy-2,6-dimethylbenzoic acid (23) from 3,5-dihydroxybenzoic acid (19) by two consecutive Mannich aminomethylation/hydrogenation sequences; benzylic N-bromosuccinimide bromination of an ester derivative 25 thereof and its subsequent coupling with Boc-Ser-Cys-OMe (11); cyclization of the ω-hydroxy acid 29 29 to the 12-membered lactone 30 using preferably Mitsunobu conditions; completion of the peptidic side chains of 1 using Boc strategy (Scheme 4). Optically pure cis-N-(tert-butoxycarbonyl)-3-hydroxy-L-proline ((-)-14) was obtained by resolution of the racemate via an efficient reaction sequence containing a lipase-catalyzed enantiospecific acetate hydrolysis (Scheme 3). The structure of natural 1 was confirmed by comparison with the synthetic material. The synthetic route described provides also easy access to analogues of 1, e.g., via the intermediate 30.
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  • 82
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A comprehensive series of tetraethynylethenes (= 3,4-diethynylhex-3-ene-1,5-diynes, TEEs) bearing electrondonating (p-methoxyphenyl or p-aminophenyl) and/or electron-accepting (p-nitrophenyl) groups was prepared via [Pd]-catalyzed Sonogashira cross-coupling reactions. The electronic and photonic properties of these molecules were investigated with a special emphasis on the effects caused by degree and pattern of donor/acceptor substitution around the central TEE core. This analysis showed that intramolecular donor-acceptor interactions, as evidenced by a long-wavelength charge-transfer band, are considerably more effective in TEEs 44 and 46, with trans and cis, linearly-conjugated electronic pathways between donor and acceptor, than in 11, with a geminal, cross-conjugated electronic pathway. UV/VIS Spectroscopy revealed a steady bathochromic shift of the longest-wavelength absorption band (λmax) as the number of donor-acceptor conjugation paths increased upon changing from bis-arylated (11, 44, and 46) to tetrakis-arylated (14, 31, and 35) TEEs. The position of the longest-wavelength absorption was also found to be strongly dependent on the nature of the N-substituents in the R2NC6H4-donor groups. Electronic emission spectroscopic investigations demonstrated a considerable solvent dependency of the fluorescence of donor-acceptor-substituted TEEs such as 11 or 44, in agreement with the presence of highly polarized excited states in these molecules. Correspondingly, fluorescence spectra of TEEs bearing only donor or acceptor substituents showed little solvent dependency. The large majority of the donor/acceptor-substituted TEEs are thermally and environmentally stable molecules. They can be stored for months as solids in the air at room temperature, and many decompose only upon heating to temperatures above 200°. X-Ray analysis showed the conjugated C-atom scaffolds of 44, 46, and 67 to be essentially planar, whereas the aryl substituents in 28 and 30 are rotated out of the plane of the TEE core by varying degrees.
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  • 83
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    Helvetica Chimica Acta 79 (1996), S. 913-913 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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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 β-hexapeptide (H-β-HVal-β-HAla-β-HLeu)2-OH (2) was prepared from the component L-β-amino acids by conventional peptide synthesis, including fragment coupling. A cyclo-β-tri- and a cyclo-β-hexapeptide were also prepared. The β-amino acids were obtained from α-amino acids by Arndt-Eistert homologation. All reactions leading to the β-peptides occur smoothly and in high yields. The β-peptides were characterized by their CD and NMR spectra (COSY, ROESY, TOCSY, and NOE-restricted modelling), and by an X-ray crystal-structure analysis. β-Sheet-type structures (in the solid state) and a compact, left-handed or (M) 31 helix of 5-Å pitch (in solution) were discovered. Comparison with the analogous secondary structures of α-peptides shows fundamental differences, the most surprising one at this point being the greater stability of β-peptide helices. There are structural relationships of β-peptides with oligomers of β-hydroxyalkanoic acids, and dissimilarities between the two classes of compounds are a demonstration of the power of H-bonding. The β-hexapeptide 2 is stable to cleavage by pepsin at pH 2 in H2O for at least 60 h at 37°, while the corresponding α-peptide H-(Val-Ala-Leu)2-OH is cleaved instantaneously under these conditions. The implication of the described results are discussed.
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  • 85
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cholic-acid-type 3-keto steroids 1-8, all isolated from Deltocyathus magnificus (2-8 after CH2N2 treatment), are the first secondary metabolites obtained from a deep-water scleractinian. Steroids 1-3, 5, and 7 are new, their main structural oddities being loss of C(24) (see 5) or hydroxylation in the side chain (see 3 and 7). Steroids 4, 6, and 8, from the same coral, were previously known from other marine organisms.
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  • 86
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    Helvetica Chimica Acta 79 (1996), S. 989-998 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rearrangement of 5α- and 5β-cholesta-6,8(14)-dienes (13a and 13b, resp.) in the presence of anhydrous toluene-4-sulfonic acid in acetic acid leads to 5α- and 5β-12(13 → 14)-abeo-cholesta-8,13(17)-dienes (15a and 15b, resp.) via 5α- and 5β-cholesta-8,14-dienes (14a and 14b, resp.), respectively. Epimerization at C(20) of the spirosteradienes 15a and 15b occurs with increasing reaction time. Molecular-mechanics calculation of the relative stabilities of these compounds and of congeners thereof is in agreement with the observed reaction pathway.
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  • 87
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    Helvetica Chimica Acta 79 (1996), S. 1085-1094 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The total syntheses of the spermidine alkaloids (-)-mayfoline (11) and (+)-N(1)-acetyl-N(1)-deoxymayfoline (12) are described. These macrocyclic lactams belong to the most interesting conjugates of the polyamine derivatives very commonly found in nature. The enantioselective syntheses were achieved through resolution of the methyl 3-amino-3-phenylpropanoate (2) by recrystallization of its (+)-L-tartrate salt. Construction of the 13-membered ring ensued through condensation, reductive ring expansion (internal bond cleavage), and finally a transamidation reaction involving a second ring expansion.
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  • 88
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of natural polyphenols (chlorogenic acid (9), cordigol (11), cordigone (12), danthrone (1), 1,5-dihydroxy-3-methoxyxanthone (2), eriosematin (7), flemichin D (8), frutinone A (6), mangiferin (4), quercetin (5), 1,3,6,7-tetrahydroxyxanthone (3) and verbascoside (10)) were investigated for their redox properties using cyclic voltammetry. The antioxidant properties of these compounds were also examined in two models, namely lipid peroxidation in rat synaptosomes and AAPH-mediated oxidation of serum albumin. Compounds with a catechol group (9, 4, 5, 3 and 10) were oxidized below 0.4 V and inhibited lipid peroxidation with IC50 values between 2 and 8 μM. Compounds having one or more isolated phenolic groups and showing an oxidation potential between 0.45 and 0.8 V (11, 12 and 8) inhibited lipid peroxidation with IC50 between 7 and 9 μM, except 2 (0.45 V), danthrone (0.96 V) and eriosematin which showed no or modest antioxidant activity. Some of the investigated compounds also protected albumin from oxidation, but no structure-activity relationship was apparent, suggesting that other factors beside redox potential influence this activity.
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  • 89
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To demonstrate the relevance of the kinetic acidity of individual OH groups for the regioselectivity of glycosylation by glycosylidene carbenes, we compared the glycosylation by 1 of the known triol 2 with the glycosylation of the diol D-3 and the fluorodiol L-4. Deoxygenation with Bu3SnH of the phenoxythiocarbonyl derivative of 5 (Scheme 1) or the carbonothioate 6 gave the racemic alcohol (±)-7. The enantiomers were separated via the allophanates 9a and 9b, and desilylated to the deoxydiols D- and L-3, respectively. The assignment of their absolute configuration is based upon the CD spectra of the bis(4-bromobenzoates) D- and L-10. The (+)-(R)-1-phenylethylcarbamates 13a and 13b (Scheme 2) were prepared from the fluoroinositol (±)-11 via (±)-4 and the silyl ether (±)-12 and separated by chromatography. The absolute configuration of 13a was established by X-ray analysis. Decarbamoylation of 13a ( → L-12) and desilylation afforded the fluorodiol L-4. The H-bonds of D-3 and L-4 in chlorinated solvents and in dioxane were studied by IR and 1H-NMR spectroscopy (Fig. 2). In both diols, HO—C(2) forms an intramolecular, bifurcated H-bond. There is an intramolecular H-bond between HO—C(6) and F in solutions of L-4 in CH2Cl2, but not in 1,4-dioxane; the solubility of L-4 in CH2Cl2 is too low to permit a meaningful glycosidation in this solvent. Glycosidation of D-3 in dioxane by the carbene derived from 1 (Scheme 3) followed by acetylation gave predominantly the pseudodisaccharides 18/19 (38%), derived from glycosidation of the axial OH group besides the pseudodisaccharides 16/17 (13%) and the epoxides 20/21 (7%), derived from protonation of the carbene by the equatorial OH group. Similarly, the reaction of L-4 with 1 (Scheme 4) led to the pseudodisaccharides 28/29 (46%) and 26/27 (14%), derived from deprotonation of the axial and equatorial OH groups, respectively. Formation of the epoxides involved deprotonation of the intramolecularly H-bonded tautomer, followed by intramolecular alkylation, elimination, and substitution (Scheme 4). The regio- and diastereoselectivities of the glycosidation correlate with the H-bonds in the starting diols.
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  • 90
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    Helvetica Chimica Acta 79 (1996), S. 1217-1221 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the chiral triazolium salt 1 as catalyst, a novel asymmetric variant of the benzoin reaction is reported. For the first time, the scope of the method is extended to a broader range of aromatic aldehydes 2, affording the acyloins 3a-h in yields of 22-72% and enantiomeric excesses up to 86%.
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  • 91
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    Helvetica Chimica Acta 79 (1996), S. 1239-1239 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 92
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    Helvetica Chimica Acta 79 (1996), S. 1260-1278 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ninety years ago, chemical methods were used in solving biological problems. In our days, methods of evolutionary biology are going to be used in solving problems of synthetic chemistry.
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  • 93
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cellobiose-derived dialkynes 14 and 15 were prepared by glycosidation of the acceptor 9 with the thioglycosides 12(82%) and 13(85%), respectively. The acceptor 9 was prepared from the known alcohol 2 via the lactone 7 in five steps (48% overall), and the donors 12 and 13 were prepared from the alkynylated anhydroglucose derivative 10 (60% overall). Acetolytic debenzylation of 14 and 15 (→16 and 17, resp.) followed by deacylation of 16 yielded 60% of the cellobiose-derived dialkyne 18. Deacylation of 14 (→19), methoxymethylation (→20) and trimethylgermylation led to the orthogonally protected dialkyne 21 (69% overall). Protodesilylation of 21 with K2CO3/MeOH gave 22 (90%), while the Me3Ge group was selectively removed with CuBr (19 mol-%) in THF/MeOH to give 20 (95%). Treatment of 21 with aqueous HCl solution led to 19 (80%). Bromodegermylation of 21 (NBS/AgOOCCF3) led to a mixture of 23 (85%) and 24 (11%). Similar conditions using CuBr instead of AgOOCCF3 gave exclusively the bromoalkyne 23 (93%). The temperature dependence of the δ values of the OH resonances of 18 in (D6)DMSO evidence a strong intramolecular H-bond between C(5′)—O…HO—C(5).
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  • 94
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cinchona alkaloid analogs (+)- and (-)-5 with a quinuclidine-2-methanol residue attached to C(2) of a 9,9′-spirobifluorene moiety were prepared as a racemic mixture by reacting lithiated 2-bromo-9,9′-spirobifluorene 7 with (2-ethoxycarbonyl)quinuclidine (±)-6 to give ketone (±)-8, followed by diastereoselective reduction with diisobutylaluminum hydride (DIBAL-H). The absolute configuration at C(9) and C(8), i.e., at the methanol bridge and the adjacent quinuclidine C-atom, in the two enantiomers of 5 is identical to the configuration at the corresponding centers in (-)-quinine (1) and (+)-quinidine (2), respectively. For the optical resolution of (±)-5, a chiral stationary phase for HPLC was prepared by covalently bonding quinine via a thiol spacer to a silica-gel surface. The enantiomer separation was accomplished at an α value of 1.61 with (±)-5 being eluted last, in agreement with 1H-NMR studies in CDCl3 which showed that (+)-5 underwent a more stable host-guest association with quinine than (-)-5. 1H{1H} Nuclear Overhauser effect (NOE) difference spectroscopical analysis of the host-guest associations with quinine in CDCl3, combined with computer-model examinations, allowed the assignment of the absolute configurations as (+)-(8R,9S)-5 and (-)-(8S,9R)-5. A detailed conformational analysis displayed excellent agreement between the results of computational methods (Monte Carlo multiple minimum simulations, analyses of the total energy as a function of the flexible dihedral angles in the molecule) and 1H{1H}-NOE difference spectroscopical data. It was found that (-)-5 and (+)-5 differ significantly in their conformational preference from their natural counterparts quinine (1) and quinidine (2). Whereas the natural alkaloids prefer the ‘open’ conformation, with the quinuclidine N-atom pointing away from the quinoline ring, analog (±)-5 adopts preferentially (by ca. 4 kcal mol-1) a ‘closed’ conformation, in which the quinuclidine N-atom points into the cleft of the 9,9′-spirobifluorene moiety. Since the basic quinuclidine N-atom in the ‘closed’ conformation is sterically shielded from forming strong H-bonds, the new Cinchona alkaloid analogs form less stable host-guest associations via H-bonding than quinine or quinidine.
    Additional Material: 10 Ill.
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  • 95
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acidic condensation of 2,4-dimethylfuran with acetaldehyde provided 2,2′-ethylidenebis[3,5-dimethylfuran] (7) which added 1 equiv. of methyl bromopropynoate to give a major adduct 8. Regio- and stereoselective hydroboration of the latter 7-oxanorbornadiene derivative followed by alcohol protection and methanolysis of its β-bromoacrylate moiety gave (1RS,2RS,4RS,5SR,6SR,1′RS)-methyl 4-[1′-(3″,5″-dimethylfuran-2″-yl)ethyl]-3,3-dimethoxy-6-exo-[(2-methoxy)ethoxy]-1,5-endo-dimethyl-7-oxabicyclo[2.2.1]heptane-2-endo-carboxylate (24) (Schemes 2 and 3). Reduction of 24 with LiAlH4, followed by H2O and MeOH elimination gave the 3-methyl-idene-7-oxanorbornan-2-one derivative 26 which underwent 7-oxa ring opening through a SN2′ type of reaction with Me2CuLi (Scheme 4). Stereoselective hydrogenation and ketone reduction provided (1RS, 2SR,3RS,4RS,5RS,6RS,1′SR)-1- [1″-(3 ″,5″-dimethylfuran-2″-yl)]-c-3-ethyl-c-5-[(2-methoxyethoxy)m e-c-ethyl-c-c-5-(2-methoxyethoxy)methoxy]-t-4,t-6-dimethyl-cyclohexane-r-1,c-2-diol (32), the oxidative cleavage of which with Pb(OAc)4 generated a 6-oxo-aldehyde 33 (Schemes 4 and 5). Chemoselective protection of 33 and chemo- and stereoselective reductions generated (2RS,3RS,4SR,5SR,6SR,7RS)-7-(3′,5″-dimethylfuran-2′-yl)-2-ethyl-6-hydroxy-4-[(2-methoxyethoxy)methoxy]-3,5-dimethyloct-1-yl pivaloate (36) and its 4-hydroxy 6-epimer 40 (12 and 13 steps, resp., from adduct 8; Scheme 5). Oxidation of the furan ring of 36 led to a (2RS,3SR,4RS,5SR,6RS,7RS)-7-ethyl-3,5,8-trihydroxy-2,4,6-trimethyl-octanoic acid derivative 44, a polypropionate fragment with six contiguous stereogenic centres (Scheme 6).
    Additional Material: 2 Ill.
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  • 96
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isomerization of (all-E)-Cycloviolaxanthin. Preparation and Characterization of (9Z)- and (13Z)-CycloviolaxanthinFrom (all-E)-cycloviolaxanthin (ex Capsicum annuum), (9Z)- and (13Z)-cycloviolaxanthin were prepared in a highly pure state. The configuration of both isomers was determined by means of UV/VIS, NMR, and CD spectroscopy.
    Additional Material: 3 Ill.
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  • 97
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1518-1518 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 98
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclohexa-1,3-dienes 7-10 with a 1,5,6-substitution pattern were prepared in a one-pot reaction sequence by sequential addition of MeLi and propargyl bromides to the tricarbonylchromium complex 1a. These products were subjected to radical cyclization procedures. Vinyl radical generation by Bu3Sn addition to the propargyl group in 7-10 was followed by regio- and diastereoselective intramolecular ring closure. Two different 5-exo-trig cyclizations are possible via different vinyl radical intermediates and cyclization to one or the other of the termini of the cyclohexadiene moiety. Internal alkynes reacted to yield exclusively the cis-fused hexahydroindene products 12-14, whereas the terminal alkyne yielded bicyclo[3.2.1]octenes 11 as sole products.
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  • 99
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1899-1902 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first asymmetric intramolecular Stetter reaction is reported, using the chiral triazolium salt 1 as catalyst. Starting from the easily accessible 4-(2-formylphenoxy)but-2-enoates 2, this protocol opens up an enantioselective pathway to the benzo-annulated pyran-4-ones (chroman-4-ones) 3a-h with good yields and enantiomeric excesses of up to 74%.
    Additional Material: 1 Ill.
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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 3-(2-propenylidene)-β-lactams 1a-c react as semicyclic dienes with the dihydrotriazole-diones 2 in a stereoselective fashion leading to the cycloadducts 3. The 3′,3′-disubstituted derivative 4 gives no [4 + 2]-cycloaddition products but forms the adducts 5 and 6. Sterochemistry and reaction pathways are discussed.
    Type of Medium: Electronic Resource
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