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  • Organic Chemistry  (4,530)
  • nitrogen
  • Wiley-Blackwell  (4,531)
  • Springer  (227)
  • Institute of Physics (IOP)
  • Springer Nature
  • 2010-2014
  • 1990-1994  (4,758)
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  • Wiley-Blackwell  (4,531)
  • Springer  (227)
  • Institute of Physics (IOP)
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  • 1
    ISSN: 1573-0417
    Keywords: Great Basin ; climatic variations ; productivity ; organic matter ; nitrogen ; phosphorus ; hardwater lake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Sediment cores from the shallow and deep basins of Pyramid Lake, Nevada, revealed variations in composition with depth reflecting changes in lake level, river inflow, and lake productivity. Recent sediments from the period of historical record indicate: (1) CaCO3 and organic content of sediment in the shallow basin decrease at lower lake level, (2) CaCO3 content of deep basin sediments increases when lake level decreases rapidly, and (3) the inorganic P content of sediments increases with decreasing lake volume. Variations in sediment composition also indicate several periods for which productivity in Pyramid Lake may have been elevated over the past 1000 years. Our data provide strong evidence for increased productivity during the first half of the 20th Century, although the typical pattern for cultural eutrophication was not observed. The organic content of sediments also suggests periods of increased productivity in the lake prior to the discovery and development of the region by white settlers. Indeed, a broad peak in organic fractions during the 1800's originates as an increase starting around 1600. However, periods of changing organic content of sediments also correspond to periods when inflow to the lake was probably at extremes (e.g. drought or flood) indicating that fluctuations in river inflow may be an important factor affecting sediment composition in Pyramid Lake.
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  • 2
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    Nutrient cycling in agroecosystems 38 (1994), S. 53-59 
    ISSN: 1573-0867
    Keywords: controlled-release fertilizer ; gel ; iron ; manganese ; nitrogen ; polyacrylamide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Using diverse technological approaches, many types of delivery devices have been used to supply plant nutrients at a controlled rate in the soil. One new approach is the use of hydrophilic polymers as carriers of plant nutrients. These polymers may be generally classified as 1) natural polymers derived from polysaccharides, 2) semi-synthetic polymers (primarily cellulose derivatives), and 3) synthetic polymers. By controlling the reaction conditions when forming the polymers, various degrees of cross-linking, anionic charge, and cationic charge can be added, thereby changing their effectiveness as fertilizer carriers. When fertilizer-containing solutions are mixed with hydrophilic polymers to form a “gel” prior to application in the soil, the release of soluble nutrients can be substantially delayed compared with soluble fertilizer alone. The effectiveness of a specific controlled-release polymeric system is determined in part by its specific chemical and physical properties, its biodegradation rate, and the fertilizer source used. Addition of some polymers with nutrients has been shown to reduce N and K leaching from well-drained soils and to increase the plant recovery of added N, P, Fe, and Mn in some circumstances
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  • 3
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    Nutrient cycling in agroecosystems 40 (1994), S. 165-173 
    ISSN: 1573-0867
    Keywords: Animal manure ; eutrophication ; ground water ; nitrogen ; phosphorus ; surface runoff
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract With the rapid growth of the poultry industry in Oklahoma, U.S.A., more litter is applied to farm land. Thus, information is required on the impact of applications on regional soil and water resources. The effect of soil and poultry litter management on nitrogen (N) and phosphorus (P) loss in runoff and subsurface flow from four 16 m2 plots (Ruston fine sandy loam, 6 to 8% slope) was investigated under natural rainfall. Plots under Bermudagrass (Cynodon dactylon) received 11 Mg litter ha−1, which amounts to contributions of approximately 410 kg N and 140 kg P ha−1 yr−1. In spring, litter was broadcast on 3 of the plots; the upper half of one and total area of the other two. One of the total-area broadcast plots was tilled to 6 cm, the other remained as no till. The fourth plot served as a control. Relative to the control, litter application increased mean concentrations of total N and total P in runoff during the 16-week study for no-till (15.4 and 5.8 mg L−1) and tilled treatments (16.7 and 6.1 mg L−1). However, values for the half-area application (5.6 and 2.0 mg L−1) were similar to the control (5.7 and 1.3 mg L−1). Interflow (subsurface lateral flow at 70 cm depth) P was not affected by litter application; however, nitrate-N concentrations increased from 0.6 (control) to 2.9 mg L−1 (no till). In all cases, 〈 2 % litter N and P was lost in runoff and interflow, maintaining acceptable water quality concentrations. Although litter increased grass yield (8518 kg ha−1) compared to the control (3501 kg ha−1), yields were not affected by litter management. An 8-fold increase in the plant available P content of surface soil indicates long-term litter management and application rates will be critical to the environmentally sound use of this nutrient resource.
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  • 4
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    Nutrient cycling in agroecosystems 37 (1994), S. 107-113 
    ISSN: 1573-0867
    Keywords: Ensete ventricosum ; fertilizer response ; nitrogen ; phosphorus ; potassium ; sulphur ; starch
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Ensete (Ensete ventricosum W. Cheesm.) is a root crop which stores starch in the root and in the lower part of the stem. It is grown in the southwest of Ethiopia and due to its drought resistance, it is of outstanding importance for the supply of food to the local population. Until now virtually nothing is known about the response of Ensete to fertilizer application. Field trials carried out on three representative soils in Ethiopia showed that Ensete biomass yields were increased significantly on all three soils by nitrogen and phosphorus application. Potassium had only marginal effect on biomass growth but favourably influenced starch production. Sulfate application had no major impact on growth and starch yield. The yield response was well related to the level of available nutrients in the soil, as determined by electroultrafiltration (EUF). Leaf analysis provided preliminary evidence that optimum levels of N, P, and K may be 3.8%, 0.3%, and 4.8%, respectively.
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  • 5
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    Nutrient cycling in agroecosystems 37 (1994), S. 227-234 
    ISSN: 1573-0867
    Keywords: catch crop ; mineralization ; nitrogen ; plant species ; residual effects ; soil depletion ; winter hardiness
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Ten widely different plant species were compared for their ability to reduce soil mineral nitrogen levels in the autumn and their ability to improve the nitrogen nutrition of the succeeding crop. The species included monocots and dicots, crops that survived the winter (persistent) or were winter killed (non-persistent) as well as legumes and non legumes. Their ability to reduce soil mineral nitrogen content was dependent on both root depth and persistency of the crops in the autumn. For non-persistent catch crops most of the mineralization of plant nitrogen occurred during the winter, and for some of these so early as to allow leaching of some mineralized nitrogen. For persistent crops most of the mineralization occurred shortly after incorporation in the spring. The effect of the catch crops on nitrogen uptake by the succeeding barley crop varied from 13 to 66 kg N ha−1 and the differences between the crops could not be related to any single character, but to a combination of root depth, persistency, plant nitrate accumulation, and depletion of the soil mineral nitrogen pool in spring.
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  • 6
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    Nutrient cycling in agroecosystems 39 (1994), S. 223-228 
    ISSN: 1573-0867
    Keywords: drip-fertigation ; efficiency ; nitrogen ; sugar cane ; uptake ; yield
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Nitrogen (N) fertilizer use efficiency by sugar cane in Mauritius rarely exceeds 40%. Since drip-irrigation delivers water uniformly and directly to the root zone with little run-off, application of N via the drip-irrigation system could therefore provide a means of enhancing fertilizer N use by sugar cane. A study was initiated in Mauritius to determine what benefits would accrue from applying urea (120 kg N per ha) to sugar cane through the drip-irrigation network. The data obtained showed that the efficiency of fertilizer N when measured at harvest was nearly doubled by supplying the N daily over 10 to 20 weeks by fertigation. Increased yields of sugar or cane did not, however, accompany the improved N use efficiency. Furthermore, when N was applied through the drip-irrigation network, recovery of N at harvest did not accurately reflect N use efficiency.
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  • 7
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    Nutrient cycling in agroecosystems 39 (1994), S. 199-203 
    ISSN: 1573-0867
    Keywords: farmyard manure ; floodwater ; nitrogen ; Oryza sativa L. ; partial pressure of ammonia ; urea ; Vietnam
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Farmyard manure (FYM) applied to rice-growing soils can substitute for industrial fertilizers, but little is known about the influence of FYM on the effectiveness and optimal management for industrial N fertilizers. A field experiment was conducted in northern Vietnam on a degraded soil in the spring season (February to June) and summer season (July to November) to determine the effect of FYM on optimal timing for the first application of urea. The experimental design was a randomized complete block with two rates of basal incorporated FYM (0 or 6 Mg ha−1) in factorial combination with two timings of the first application of 30 kg urea-N ha−1 (basal incorporated before transplanting or delayed until 14 to 16 d after transplanting). The FYM was formed by composting pig manure with rice straw for 3 months. Basal incorporation of FYM, containing 23 kg N ha−1, increased rice grain yield in both seasons. The yield increase cannot be attributed to reduced ammonia loss of applied urea-N, because FYM did not reduce partial pressure of ammonia (pNH3) following urea application in either season. Basal and delayed applications of urea were equally effective in the absence of FYM, but when FYM was applied rice yields in both seasons were higher for delayed (mean = 3.2 Mg ha−1) than basal (mean = 2.9 Mg ha−1) application of urea. Results suggest that recommendations for urea timing in irrigated lowland rice should consider whether farmers apply FYM.
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  • 8
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    Aquatic sciences 56 (1994), S. 16-28 
    ISSN: 1420-9055
    Keywords: Chlorophyll-a ; phosphorus ; nitrogen ; lake ecosystem ; nutrient limitation ; regression analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Regression results based on data from 46 northern temperate lakes show that total phosphorus (TP) is the best predictor for phytoplankton (as chl-a) at lower trophic levels, TP 〈 200 mg · m−3. A regression including both TP and TN as regressors is the best predictor for lakes with TP 〉 200 mg · m−3. However, the good correlation is probably due to a high correlation between lake average chl-a (all years observed) and lake average TP and TN. Within single hypereutrophic lakes, TN alone is the best predictor. It was not possible to identify a medium trophic domain where TN and TP in combination was the best predictor for chl-a. The ratio TN:TP in the water decreases from about 40 to about 5 with increasing trophic level. Optimum TN:TP ratio for algal species with high abundance during late summer and autumn reflects this decreasing ratio, but within a lesser range, i.e., 20 to 5. In contrast, TN:TP ratios for species abundant during the early vernal period showed no, or an inverse, relation to the TN:TP ratio of the water.
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  • 9
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    Plasma chemistry and plasma processing 14 (1994), S. 451-490 
    ISSN: 1572-8986
    Keywords: Transport coefficients ; transport properties ; viscosity ; thermal conductivity ; electrical conductivity ; diffusion coefficient ; Chapman Enskog method ; argon ; nitrogen ; oxygen ; plasma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Calculated values of the viscosity, thermal conductivity, and electrical conductivity of argon, nitrogen, and oxygen plasmas, and mixtures of argon anti nitrogen and of argon anti oxygen, are presented. In addition, combined ordinary, pressure, and thermal diffusion coefficients are given for the gas mixtures. These three combined diffusion coefficients fully describe di fusion of the two gases, irrespective of their degree of dissociation or ionizati on. The calculations, which assume local thermodynamic equilibrium, are performed! for atmospheric-pressure plasmas in the temperature range /torn 300 to 30,000 K. A number of the collision integrals used in calculating the transport coefficients are significantly more accurate than values used in previous theoretical studies, resulting in more reliable values of the transport coefficients. The results are compared with those of published theoretical and experimental studies.
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  • 10
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    Aquatic ecology 28 (1994), S. 117-133 
    ISSN: 1573-5125
    Keywords: checklist ; diatoms ; The Netherlands ; pH ; salinity ; nitrogen ; oxygen ; saprobity ; trophic state ; moisture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract This first comprehensive checklist of the diatoms from fresh and weakly brackish water in The Netherlands comprises 948 taxa, belonging to 776 species in 56 genera. The generaNavicula, which has a very wide ecological amplitude, andNitzschia, which has many pollution tolerant species, are most numerous. Each taxon is identified with a unique eight-letter code, to facilitate computer processing of data. Ecological indicator values for pH, salinity, nitrogen uptake metabolism, oxygen, saprobity, trophic state and moisture are presented.
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  • 11
    ISSN: 1573-5036
    Keywords: nitrogen ; phosphorus ; revegetation ; silica ; succession ; shrubland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Fire is the principal means of stand renewal in big sagebrush-steppe communities of western North America. Plant growth following fire may be influenced by heat-induced changes in the nutrient status of the soil. Moreover, post-wildfire pioneer plant species may alter soil properties, and thereby, impact subsequent plant recruitment. Our study compared the growth and elemental content of big sagebrush (Artemisia tridentata), squirreltail (Elymus elymoides), cheatgrass (Bromus tectorum), and Indian ricegrass (Achnatherum hymenoides), grown under greenhouse conditions in post-wildfire and similar unburned soil. We also examined soil attributes following plant growth. Cheatgrass and squirreltail, grown in post-wildfire soil, had significantly (p≤0.05) greater aboveground mass than plants grown in unburned soil. As compared with unburned soil, post-wildfire soil engendered the following significant (p≤0.05) differences in leaf elemental content: 1) big sagebrush had higher levels of P and lower levels of Mn; 2) squirreltail accumulated more P and N; and 3) all grass species had higher SiO2 content. Following harvest of plants, post-wildfire soil generally contained significantly (p≤0.05) more KCl-extractable ortho-P, NH inf4 + , and SO 4 − , than unburned soil. Plant growth in both burned and unburned soils fostered a significant (p≤0.05) increase in the bicarbonate-extractable pool of P as compared with unplanted controls. Soil Kjeldahl-N was significantly (p≤0.05) greater after plant growth in burned treatments as compared with the control. This study demonstrates that post-wildfire soil can have a stimulatory effect on plant growth for some species. Squirreltail deserves consideration as a post-wildfire revegetation species. Furthermore, pioneer plant growth following wildfires can attenuate soil properties and therefore influence plant succession.
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  • 12
    ISSN: 1573-5036
    Keywords: biological method ; chemical method ; mineralization potential ; nitrogen ; soil incubation ; temperate humid-zone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The potentially mineralizable organic N of 33 different soils was estimated by a chemical test (hot extraction with 2N KCl) and the values compared with those previously obtained by a biological method (aerobic incubation in the laboratory). On average, the organic N solubilized by the chemical procedure was significantly lower than that mineralized by a two weeks aerobic incubation for all the soils as a whole. The same was true for soils developed over acid rocks and over sediments. However, the values obtained for the soils developed over limestone and basic rocks were similar by both methods. The values obtained by both methods were not significantly correlated neither when considering all soils together nor when considering different groups according to soil management or parent material. Significant correlations between both methods were only found when the soils were separated into two groups according to their organic N content: soils with less than 400 mg N 100 g−1 soil and soils with more than 400 mg N 100 g−1 soil. The organic N solubilized by the chemical procedure was significantly correlated with the hexosamine-N content; however, it was not correlated with the factors that control the biological mineralization of the organic N, except with the soluble Al content. Therefore, the chemical extraction did not seem to address the biologically active N pool in a selective way.
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  • 13
    ISSN: 1573-5036
    Keywords: mineralization rate ; nitrogen ; stabilized organic matter ; crop rotation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract A simple model was developed to estimate the contribution of nitrogen (N) mineralization to the N supply of crops. In this model the soil organic matter is divided into active and passive pools. Annual soil mineralization of N is derived from the active pool. The active pool comprises stabilized and labile soil organic N. The stabilized N is built up from accumulated inputs of fresh organic N during a crop rotation but the labile N is a fraction of total N added, which mineralizes faster than the stabilized N. The passive pool is considered to have no participation in the mineralization process. Mineralization rates of labile and stabilized soil organic N from different crop residues decomposing in soil were derived from the literature and were described by the first-order rate equation dN/dt =-K*N, where N is the mineralizable organic N from crop residues andK is a constant. The data were groupedK 1 by short-term (0–1 year) andK 2 by long-term (0–10 years) incubation. Because the range of variation inK 2 was smaller than inK 1 we felt justified in using an average value to derive N mineralization from the stabilized pool. The use of a constant rate ofK 1 was avoided so net N mineralization during the first year after addition is derived directly from the labile N in the crop residues. The model was applied to four Chilean agro-ecosystems, using daily averages of soil temperature and moisture. The N losses by leaching were also calculated. The N mineralization varied between 30 and 130 kg N ha−1 yr−1 depending on organic N inputs. Nitrogen losses by leaching in a poorly structured soil were estimated to be about 10% of total N mineralized. The model could explain the large differences in N- mineralization as measured by the potential N mineralization at the four sites studied. However, when grassland was present in the crop rotation, the model underestimated the results obtained from potential mineralization.
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  • 14
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    Plant and soil 158 (1994), S. 129-134 
    ISSN: 1573-5036
    Keywords: Betula lenta L. ; black birch ; nitrogen ; root architecture ; soil heterogeneity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Inorganic soil nitrogen is often heterogeneously distributed, both spatially and in form (ammonium versus nitrate). Here we present information on the architecture of black birch (Betula lenta L.) root systems exposed to homogeneous and heterogeneous nitrogen environments. The major effects on root architecture were at the whole root system level in response to heterogeneity of nitrogen form rather than the effect of local of local nitrate or ammonium supply on local root growth. In the heterogeneous treatment, plant root systems had greater link lengths and more simple branching patterns. Root architectural responses to heterogeneous nitrogen, independent of localized responses to patches, suggest that in a seedling of B. lenta whole plant integration of its environment may override local control of root growth.
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  • 15
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    Plant and soil 165 (1994), S. 21-32 
    ISSN: 1573-5036
    Keywords: allocation ; CO2 ; image analysis ; loblolly pine ; nitrogen ; root morphology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract This paper examines how elevated CO2 and nitrogen (N) supply affect plant characteristics of loblolly pine (Pinus taeda L.) with an emphasis on root morphology. Seedlings were grown in greenhouses from seeds during one growing season at two atmospheric CO2 concentrations (375 and 710 μL L-1) and two N levels (High and Low). Root morphological characteristics were determined using a scanner and an image analysis program on a Macintosh computer. In the high N treatment, elevated CO2 increased total plant dry weight by 80% and did not modify root to shoot (R/S) dry weight ratio, and leaf and plant N concentration at the end of the growing season. In the low N treatment, elevated CO2 increased total dry weight by 60%. Plant and leaf N concentration declined and R/S ratio tended to increase. Nitrogen uptake rate on both a root length and a root dry weight basis was greater at elevated CO2 in the high N treatment and lower in the low N treatment. We argue that N stress resulting from short exposures to nutrients might help explain the lower N concentrations observed at high CO2 in other experiments; Nitrogen and CO2 levels modified root morphology. High N increased the number of secondary lateral roots per length of first order lateral root and high CO2 increased the length of secondary lateral roots per length of first order lateral root. Number and length of first order lateral roots were not modified by either treatment. Specific root length of main axis, and to a lower degree, of first order laterals, declined at high CO2, especially at high N. Basal stem diameter and first order root diameters increased at high CO2, especially at high N. Elevated CO2 increased the proportion of upper lateral roots within the root system.
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  • 16
    ISSN: 1573-5036
    Keywords: blue grama ; Bouteloua gracilis ; C4 grass ; CO2 enrichment ; mycorrhizae ; nitrogen ; phosphorus ; VAM ; water relations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract In order to better elucidate fixed-C partitioning, nutrient acquisition and water relations of prairie grasses under elevated [CO2], we grew the C4 grass Bouteloua gracilis (H.B.K.) lag ex Steud. from seed in soil-packed, column-lysimeters in two growth chambers maintained at current ambient [CO2] (350 μL L−1) and twice enriched [CO2] (700 μL L−1). Once established, plants were deficit irrigated; growth chamber conditions were maintained at day/night temperatures of 25/16°C, relative humidities of 35%/90% and a 14-hour photoperiod to simulate summer conditions on the shortgrass steppe in eastern Colorado. After 11 weeks of growth, plants grown under CO2 enrichment had produced 35% and 65% greater total and root biomass, respectively, and had twice the level of vesicular-arbuscular mycorrhizal (VAM) infection (19.8% versus 10.8%) as plants grown under current ambient [CO2]. The CO2-enriched plants also exhibited greater leaf water potentials and higher plant water use efficiencies. Plant N uptake was reduced by CO2 enrichment, while P uptake appeared little influenced by CO2 regime. Under the conditions of the experiment, CO2 enrichment increased root biomass and VAM infection via stimulated growth and adjustments in C partitioning below-ground.
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  • 17
    ISSN: 1573-5044
    Keywords: carbon ; elevated CO2 ; nitrogen ; suspension culture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A photoautotrophic soybean suspension culture (SB-P) was used to study CO2 assimilation while exposed to elevated or ambient CO2 levels. These studies showed that under elevated CO2 (5% v/v) malate is the dominant fixation product, strongly suggesting that phosphoenolpyruvate carboxylase (PEPCase) is the primary enzyme involved in carbon fixation in these cells under their normal growth conditions. Citrate and [aspartate + glutamate] were also significant fixation products during fifteen minutes of exposure to 14CO2. During the ten minute unlabeled CO2 chase however, 14C-malate continued to increase while citrate and [aspartate + glutamate] declined. Fixation of 14CO2 under ambient CO2 levels (0.037%) showed a very different product pattern as 3-phosphoglycerate was very high in the first one to two minutes followed by increases in [serine + glycine] and [aspartate + glutamate]. Hexose phosphates were also quite high initially but then declined relatively rapidly. Thus, the carbon fixation pattern at ambient CO2 levels resembles somewhat that seen in C3 leaf cells while that seen at elevated CO2 levels more closely resembles that of a C4 plant. The initial fixation product of C3 plants, 3-PGA, was never detectable under high CO2 conditions. These data suggest that an in vitro photoautotrophic system would be suitable for studying carbon fixation physiology during photosynthetic and non-photosynthetic growth.
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  • 18
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    Plant and soil 164 (1994), S. 187-193 
    ISSN: 1573-5036
    Keywords: apatite ; biotite ; forest soil ; mineralization ; nitrogen ; nutrient additions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The effects of slow (apatite, biotite) and fast-release nutrients (P, K, Mg) on C and N mineralization in acid forest soil were studied. These nutrients were applied alone or together with urea or urea and limestone. The production of CO2 in the soil samples taken one and three growing seasons after the application was lower in the soils treated with the fast-release nutrients than in the untreated soils. Similar reduction of microbial activity was not seen after the apatite and apatite+biotite treatments. In the first growing season, urea and urea+limestone enhanced CO2 production, but after three growing seasons, the opposite was true. Apatite and apatite+biotite added together with urea did not compensate for the decreasing effect of urea on the CO2 production. The addition of fast-release salts increased somewhat the concentration of NH inf4 sup+ in the soil and more NH4 + accumulated during laboratory incubation in the soil samples taken one growing season after the application. The urea addition immediately increased the concentrations of NH4 + and of NO3 − in the soil, but, three growing seasons after application, urea had only a slight increasing effect on mineral N content of the soil. Slow-release nutrients seem to have a more favourable effect than fast-release salts on nutrient turnover in acid forest soil.
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  • 19
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    Plant and soil 161 (1994), S. 241-250 
    ISSN: 1573-5036
    Keywords: carbon ; microorganisms ; nitrogen ; plant succession ; range grasses ; rhizosphere
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Nitrogen and rhizosphere microorganism effects on nitrogen and carbon dynamics of Sitanion hystrix (early successional species), Stipa comata and Poa secundu which are (mid-successional species), and Agropyron spicatum (late successional species) were evaluated in a growth chamber study. Rhizosphere inocula resulted in increased nitrogen in both root and shoot tissue, and also of water-extractable carbon in the rhizosphere. Plant species, rhizosphere inocula and nitrogen level showed a three-way significant interaction for total and plant-available nitrogen. Rhizosphere microbe presence resulted in higher plant-available nitrogen in the rhizosphere of S. hystrix and less with A. spicatum, suggesting nitrogen immobilization with the later successional grass. Higher nitrogen resulted in decreased active bacteria in the rhizosphere of all plants tested, and decreased fungal hyphal lengths in the rhizosphere of the later successional P. secunda and A. spicutum. Exudate carbon in the rhizosphere of the late successional species A. spicatum, was more recalcitrant, which also may contribute to nitrogen immobilization. These differential responses of early- and late-successional grasses may be important factors contributing to plant succession.
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  • 20
    ISSN: 1573-5036
    Keywords: ammonium sulphate ; fine roots ; needles ; nitrogen ; Norway spruce ; rhizosphere
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Rhizosphere, fine-root and needle chemistry were investigated in a 28 year old Norway spruce stand in SW Sweden. The uptake and allocation pattern of plant nutrients and aluminium in control plots (C) and plots repeatedly treated with ammonium sulphate (NS) were compared. Treatments started in 1988. Current year needles, one-year-old needles and cylindrical core samples of the LFH-layer and the mineral soil layers were sampled in 1988, 1989 and 1990. Compared to the control plots, pH decreased significantly in the rhizosphere soil in the NS plots in 1989 and 1990 while the SO4-S concentration increased significantly. Aluminium concentration in the rhizosphere soil was generally higher in the NS plots in all soil layers, except at 0–10 cm depths, both in 1989 and 1990. Calcium, Mg and K concentrations also increased after treatment with ammonium sulphate. Ammonium ions may have replaced these elements in the soil organic matter. The NS treatment significantly reduced Mg concentrations in fine roots in all layers in 1990. A similar trend was found in the needles. Ca concentrations in fine roots were significantly lower in the NS plots in the LFH layer in 1990 and the same pattern was found in the current needles. The N and S concentrations of both fine roots and needles were significantly higher in the NS plots. It was suggested that NS treatment resulted in displacement of Mg, Ca and K from exchange sites in the LFH layer leading to leaching of these cations to the mineral soil. Further application of ammonium sulphate may damage the fine roots and consequently adversely affect the water and nutrient uptake of root systems.
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  • 21
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    Plant and soil 163 (1994), S. 121-130 
    ISSN: 1573-5036
    Keywords: decomposition rates ; enriched CO2 ; lignin ; litter respiration ; microcosms ; nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Ash (Fraxinus excelsior L.), birch (Betula pubescens Ehrh.), sycamore (Acer pseudoplatanus L.) and Sitka spruce (Picea sitchensis (Bong.) Carr.) leaf litters were monitored for decomposition rates and nutrient release in a laboratory microcosm experiment. Litters were derived from solar domes where plants had been exposed to two different CO2 regimes: ambient (350 μL L-1 CO2) and enriched (600 μL L-1 CO2). Elevated CO2 significantly affected some of the major litter quality parameters, with lower N, higher lignin concentrations and higher ratios of C/N and lignin/N for litters derived from enriched CO2. Respiration rates of the deciduous species were significantly decreased for litters grown under elevated CO2, and reductions in mass loss at the end of the experiment were generally observed in litters derived from the 600 ppm CO2 treatment. Nutrient mineralization, dissolved organic carbon, and pH in microcosm leachates did not differ significantly between the two CO2 treatments for any of the species studied. Litter quality parameters were examined for correlations with cumulative respiration and decomposition rates: N concentration, C/N and lignin/N ratios showed the highest correlations, with differences between litter types. The results indicate that higher C storage will occur in soil as a consequence of litter quality changes resulting from higher atmospheric concentrations of CO2.
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  • 22
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    Plant and soil 160 (1994), S. 193-199 
    ISSN: 1573-5036
    Keywords: gaps ; ion uptake ; nitrogen ; nutrient acquisition ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Tree seedlings that colonize large treefall gaps are generally shade-intolerant species with high potential relative growth rates. Nutrient availability may be significantly elevated in disturbance-induced gaps, however, little is known about the role of differences in nutrient uptake capacities of different species in structuring the community response to gap openings in eastern North American deciduous forests. Seven tree species were grown from seed under both a high and a low nutrient regime, and uptake kinetics of phosphate, ammonium, and nitrate were studied. Yellow birch, a species with intermediate shade tolerance and relative growth rate, had the highest maximum rates of uptake of all ions, while tulip tree, a gap-colonizing species with high relative growth rate, had the lowest rate of phosphate uptake and intermediate rates of ammonium and nitrate uptake. Beech and hickory, which have low relative growth rates and are not gap-colonizing species, had intermediate levels of nutrient uptake. There was no evidence that species with the highest maximum uptake rates measured at high supply concentrations had relatively low uptake at low nutrient supply concentrations. Although birch increased phosphate absorption capacity when grown under a low nutrient regime, this pattern did not hold for nitrate or ammonium uptake, and other species showed no change in nutrient uptake capacity according to nutrient growth regime. Clearly, factors other than nutrient absorption capacity, such as nutrient use efficiency or allocation to root vs. shoot biomass, underlie differences in species' capacities to colonize and maintain a high relative growth rate in canopy gaps.
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  • 23
    ISSN: 1573-5036
    Keywords: CO2 ; gas exchange ; nitrogen ; Populus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Soil N availability may play an important role in regulating the long-term responses of plants to rising atmospheric CO2 partial pressure. To further examine the linkage between above- and belowground C and N cycles at elevated CO2, we grew clonally propagated cuttings of Populus grandidentata in the field at ambient and twice ambient CO2 in open bottom root boxes filled with organic matter poor native soil. Nitrogen was added to all root boxes at a rate equivalent to net N mineralization in local dry oak forests. Nitrogen added during August was enriched with 15N to trace the flux of N within the plant-soil system. Above-and belowground growth, CO2 assimilation, and leaf N content were measured non-destructively over 142 d. After final destructive harvest, roots, stems, and leaves were analyzed for total N and 15N. There was no CO2 treatment effect on leaf area, root length, or net assimilation prior to the completion of N addition. Following the N addition, leaf N content increased in both CO2 treatments, but net assimilation showed a sustained increase only in elevated CO2 grown plants. Root relative extension rate was greater at elevated CO2, both before and after the N addition. Although final root biomass was greater at elevated CO2, there was no CO2 effect on plant N uptake or allocation. While low soil N availability severely inhibited CO2 responses, high CO2 grown plants were more responsive to N. This differential behavior must be considered in light of the temporal and spatial heterogeneity of soil resources, particularly N which often limits plant growth in temperate forests.
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  • 24
    ISSN: 1573-5036
    Keywords: carbon dioxide ; nitrogen ; ponderosa pine ; soil respiration ; soil carbon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The purpose of this paper is to describe the effects of CO2 and N treatments on soil pCO2, calculated CO2 efflux, root biomass and soil carbon in open-top chambers planted with Pinus ponderosa seedlings. Based upon the literature, it was hypothesized that both elevated CO2 and N would cause increased root biomass which would in turn cause increases in both total soil CO2 efflux and microbial respiration. This hypothesis was only supported in part: both CO2 and N treatments caused significant increases in root biomass, soil pCO2, and calculated CO2 efflux, but there were no differences in soil microbial respiration measured in the laboratory. Both correlative and quantitative comparisons of CO2 efflux rates indicated that microbial respiration contributes little to total soil CO2 efflux in the field. Measurements of soil pCO2 and calculated CO2 efflux provided inexpensive, non-invasive, and relatively sensitive indices of belowground response to CO2 and N treatments.
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  • 25
    ISSN: 1573-5036
    Keywords: nitrogen ; precoditioning ; roots ; sycamore
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Acer pseudoplatanus L. trees were grown in sand culture for 2 years and, in 1988, supplied with either 1.0 mol N m-3 (low N) or 6.0 mol N m-3 (high N) to precondition their growth. In 1989, the same trees received either high or low nitrogen, producing four treatments; High N in 1988/High N in 1989; High N in 1988/Low N in 1989; Low N in 1988/Low N in 1989; and Low N in 1988/High N in 1989. Plant growth was affected by N supply in both years. In 1989 the Low N/High N treated trees had the same overall mass, leaf mass and stem girth as the High N/High N treatment. Early spring growth of foliage and roots was conditional on nitrogen supplied in the previous season. Later, the rapid increases in leaf, stem and root growth under high N was through root uptake. Internal partitioning of growth was affected, with the Low N/High N treatment producing more new leaves on axillary shoots, and more new white roots on existing structures, than the Low N/Low N treatment. Despite effects of the N preconditioning on the structure of both canopy and root system, nitrogen uptake was solely dependent on the current nitrogen supply.
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  • 26
    ISSN: 1573-5036
    Keywords: enzymes ; fine root vitality ; nitrogen ; Picea abies ; Pinus sylvestris ; triphenyltetrazolium chloride
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The present study is an attempt to investigate whether triphenyltetrazolium chloride (TTC), a chemical compound which measures dehydrogenase activity, could be used to study fine-root vitality from two different points of view: (i) in relation to ageing; (ii) as an indicator of environmental stress, in this case of excess nitrogen. The study was performed with excavated fine-roots from middle-aged Norway spruce and Scots pine stands. The ageing aspect was investigated by applying TTC to fine roots separated into different vitality classes, based on certain morphological characteristics. A significant difference in activity was demonstrated only in the case of roots that could be referred to as living and dead, respectively. The use of TTC on fine roots grown at different nitrogen supply levels indicates a possible increase in dehydrogenase activity with increasing nitrogen supply.
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  • 27
    ISSN: 1573-5044
    Keywords: Fatty acids ; hyoscyamine ; Hyoscyamus muticus ; nitrogen ; sucrose ; transformed root cultures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abatract The effect of carbon and nitrogen sources on two well-established hairy root clones, LBA1S and C58A, of Hyoscyamus muticus strain Cairo, were investigated. Both clones exhibited completely different patterns with regards to their growth rate, hyoscyamine accumulation, and fatty acid contents. Clone C58A grew faster and yielded more biomass (17.4 g l-1, in 21 days), but produced less hyoscyamine. The maximum hyoscyamine content (120 mg l-1) in clone LBA1S was reached in 28 days. Neither of the clones could use lactose or fructose as the sole carbon source, nor ammonium as the sole nitrogen source. The growth in the medium containing glucose was significantly reduced compared to that containing sucrose. Clone LBA1S was sensitive to the changes in sucrose concentration and an increase in ammonium in the culture medium, whereas C58A tolerated these changes better but was more sensitive to the increase in total nitrogen. Lipid synthesis was active in the exponential growth phase, and the total fatty acid content varied from 5 to 34 mg g-1 of dry root material. The major fatty acids were linoleic, palmitic and linolenic. There were considerable differences in the total amount of lipids and in their relative ratios when different nutrients were applied.
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  • 28
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    Hydrobiologia 275-276 (1994), S. 359-369 
    ISSN: 1573-5117
    Keywords: agriculture ; blue-green algae ; eutrophication ; internal loading ; nitrogen ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The impact of agriculture was estimated on two shallow, eutrophic lakes, Lake Kotojärvi and Lake Villikkalanjärvi in southern Finland. The main emphasis was on phosphorus and nitrogen budgets and on the phytoplankton dynamics. Special attention was paid to internal P loading and blue-green algal blooms. The mean Tot-P load from agricultural land was 1.2 kg ha-1 a-1 in both basins and Tot-N loads were 19 kg ha-1 a-1 in L. Villikkalanjärvi and 12 kg ha-1 a-1 in L. Kotojärvi. The Tot-P input to L. Kotojärvi was on an average 0.62 g m-2 a-1 (per lake surface area), and the Tot-N input 9.1 g m-2 a-1. The corresponding inputs to L. Villikkalanjärvi were 3.1 and 57 g m-2 a-1, respectively. The annual variation followed the runoff volumes. About half of the Tot-P and one third of the Tot-N load was retained in L. Kotojärvi. In L. Villikkalanjärvi the retention was only 24% for Tot-P and 19% for Tot-N. The difference was very probably due to a longer theoretical retention time in L. Kotojärvi. In L. Villikkalanjärvi the mean concentration of Tot-P was 120 µg 1-1 and that of Tot-N 1700 µg 1-1 and the corresponding figures in L. Kotojärvi 67 and 990 µg 1-1, respectively. The mean chlorophyll a concentration was, however, higher in L. Kotojärvi (26 µg 1-1) than in L. Villikkalanjärvi (20 µg 1-1). This was probably due to an internal P load in L. Kotojärvi: in 1988 the internal load of dissolved P was estimated to be as much as twofold the external load. In L. Villikkalanjärvi the internal dissolved P load was only up to 50% of the external input. In L. Kotojärvi the high internal P load coupled with a low DIN:DIP ratio resulted in a strong blue-green algal bloom in the summer of 1988. In L. Villikkalanjärvi blue-green algae were observed only in small amounts. Even in August 1990, when the DIN:DIP ratio was low enough to favor the occurrence of blue-green algae, they contributed only up to 10–15% of the total phytoplankton biomass.
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  • 29
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    Hydrobiologia 277 (1994), S. 17-39 
    ISSN: 1573-5117
    Keywords: carbon ; phosphorus ; nitrogen ; silica ; sedimentation ; mineralization ; meromixis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The dynamics of seston and dissolved elements in a meromictic lake with high concentrations of manganese and iron in the monimolimnion were studied through an annual cycle. This publication presents results for assimilation, sedimentation and recovery of nutrients (C, N, P, and Si) in the trophogenic zone. Phosphorus deficiency kept the productivity of the diatom dominated phytoplankton at an oligotrophic level. High concentrations of iron in influent streams and redistribution followed by precipitation of iron during periods of partial turnover removed phosphorus from the water. High concentrations of manganese and sulfate did not have the anticipated fertilizing effect, and recovery of nutrients from the depth of the lake was negligible. Mass balance calculations indicate that liberation of phosphorus from the sediments in the trophogenic zone was most important for the maintenance of primary production. 75% of carbon, 80% of nitrogen and 25% of phosphorus assimilated by the phytoplankton was mineralized in the trophogenic zone. Silica was effectively regenerated from the littoral zone during the decline of diatom blooms. Nitrogen and silica retention was 45% of the external load compared to 66% for phosphorus.
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  • 30
    ISSN: 1573-5117
    Keywords: eutrophication ; birds ; lake ; nitrogen ; phosphorus ; eutrophisation ; oiseaux ; lac ; azote ; phosphore
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Description / Table of Contents: Résumé Le plus grand lac de plaine français, Grand-Lieu, est actuellement largement eutrophisé. Le but de cette étude est d'estimer l'importation annuelle de N et P par les fientes des oiseaux qui s'alimentent à l'extérieur du lac, et de la comparer avec les apports des rivières alimentant le lac. Deux années sont comparées: 1981–82 et 1990–91. Les populations nicheuses (jusqu'à 956 couples de hérons cendrés et 136 couples de grands cormorans et 30 000 canards) et hivernantes (jusqu'à 17 000 canards, 1100 grands cormorans, 15 000 goélands et 2,4 millions d'étourneaux) ont respectivement importé 5800 kg de N total en 1981–82 et 7640 en 1990–91, soit 0,7% et 0,4% des entrées totales du système, et 2000 à 2530 kg de P total soit 2,4 et 6,6% des entrées. Les étourneaux sont responsables des trois quarts des apports d'azote par les oiseaux, et les canards de l'essentiel du reste, tandis que la part des étourneaux baisse pour le phosphore (36% en 1981–82 et 41% en 1990–91), au profit des Canards et des Hérons (respectivement 35% et 27% en 1981–82, 22% et 24% en 1990–91). Mais pendant la phase de croissance végétale (avril–septembre), la part des oiseaux monte jusqu'à 37% des entrées totales de phosphore. L'action localisée des colonies d'oiseaux piscivores est significative, avec une teneur de phosphore 42 fois plus grande dans l'eau sous la colonie qu'à l'extérieur des colonies. A l'échelle du l'ac, l'action actuelle globalement mineure des oiseaux sur les apports totaux d'azote et de phosphore est largement due à l'augmentation catastrophique des apports d'origine humaine (agriculture intensive et stations d'épuration). La teneur moyenne des rivières atteint désormais 10 mg l−1 de N (jusqu'à 23 mg en crue) et 394 mg m−3 de P (jusqu'à 468 mg en crue). Avant cette pollution généralisée, l'eau des rivières bretonnes ne contenait dans les années 1960 que 0,1 à 1,1 mg l−1 de N et 1 à 5 mg m−3 de P lors des périodes de débits maximum. A cette époque, les oiseaux représentaient probablement jusqu'à 36% des apports de N et 95% des apports de P dans les entrées du système lacustre.
    Notes: Abstract The largest natural lake in France, Grand-Lieu, has suffered eutrophication. The objective of the study was to estimate the annual input of nutrients (N, P) resulting from avian excrement, deposited by birds feeding out of the lake and returning to its waters for breeding or roosting, as compared to the input by the rivers that enter in the lake. Two years are compared: 1981–82 and 1990–91. About 1600–2000 breeding herons and cormorants, 20 000–33 000 wintering ducks, gulls and cormorants and 1–2.4 million starlings deposited about 5800 kg total N in 1981–82 and 7640 kg in 1990–91. Respectively, 2000 and 2530 kg total P were deposited over the same time periods. These represent 0.7% and 0.4% of the total N input of the lake and 2.4 and 6.6% of the total P input in 1981–82 and 1990–91. Starlings account for 74% of the N and mallards most of the rest. P input by starlings (36% in 1981–82, 41% in 1990–91), and by mallards and herons (35% and 27% in 1981–82 and 22% and 24% in 1990–91 respectively) plays an appreciable role among birds. During the plant growing period (April–September), the contribution by birds can increase to 37% of total P input of the lake. Piscivorous bird colonies concentrate Phosphorus 42 times more within the colony than outside the colony. Overall, the role birds play in total N and P input is relatively small due to very high inputs from human sewage and agriculture run off. The monthly mean concentration of the water of the two rivers reaches currently 10 mg l−1 of N (to 23 mg during peak floods) and 394 mg m−3 of P (to 468 mg during peak floods). Earlier, for example in the 1960's, water in Brittany only contained 0.1 to 1.1 mg 1−1 of N and 1 to 5 mg m−3 of P during the maximum flow period. At this time, birds could probably have represented annually up to 37% of the N input and up to 95% of the P input to the lake.
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  • 31
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    Hydrobiologia 286 (1994), S. 155-165 
    ISSN: 1573-5117
    Keywords: decomposition ; marsh ; litter ; nitrogen ; Scolochloa festucacea
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The effect of seasonal inundation on the decomposition of emergent macrophyte litter (Scolochloa festucacea) was examined under experimental flooding regimes in a northern prairie marsh. Stem and leaf litter was subjected to six aboveground inundation treatments (ranging from never flooded to flooded April through October) and two belowground treatments (nonflooded and flooded April to August). Flooding increased the rate of mass loss from litter aboveground but retarded decay belowground. Aboveground, N concentration decreased and subsequently increased earlier in the longer flooded treatments, indicating that flooding decreased the time that litter remained in the leaching and immobilization phases of decay. Belowground, both flooded and nonflooded litter showed an initial rapid loss of N, but concentration and percent of original N remaining were greater in the nonflooded marsh throughout the first year. This suggested that more N was immobilized on litter under the nonflooded, more oxidizing soil conditions. Both N concentration and percent N remaining of belowground litter were greater in the flooded than the nonflooded marsh the second year, suggesting that N immobilization was enhanced after water-level drawdown. These results suggest different mechanisms by which flooding affects decomposition in different wetland environments. On the soil surface where oxygen is readily available, flooding accelerates decomposition by increasing moisture. Belowground, flooding creates anoxic conditions that slow decay. The typical hydrologic pattern in seasonally flooded prairie marshes of spring flooding followed by water-level drawdown in summer may maximize system decomposition rates by allowing rapid decomposition aboveground in standing water and by annually alleviating soil anoxia.
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  • 32
    ISSN: 1573-5095
    Keywords: foliage ; grafting ; nitrogen ; phosphorus ; Pinus caribaea ; rootstock ; scion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Both scion and rootstock clones significantly influenced scion elongation and concentrations of nitrogen and phosphorus in the scion foliage. Scion clone was the more important determinant. Scion clone × rootstock clone interactions were not significant. The ability of a clone to elongate as a scion was not correlated with its capacity to promote or retard scion elongation when used as a rootstock. Genetic differences in foliar nutrient concentrations appeared to reflect levels of nutrient demand, rather than the ability of roots to absorb nutrients. Nutrient demand of the rootstock can also explain negative correlations between nitrogen levels in rootstock clones and levels of both nitrogen and phosphorus in the scions. There was no significant relationship between scion elongation and foliar nitrogen concentrations of either rootstock or scion. The weak relationship between scion elongation and concentration of phosphorus in the rootstock apparently resulted from tissue dilution.
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  • 33
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    Biogeochemistry 25 (1994), S. 19-39 
    ISSN: 1573-515X
    Keywords: denitrification ; mineralization ; nitrification ; nitrogen ; riparian ; stream ; wetland ; New Jersey ; Pennsylvania ; Pinelands
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Denitrification (N2 production) and oxygen consumption rates were measured at ambient field nitrate concentrations during summer in sediments from eight wetlands (mixed hardwood swamps, cedar swamps, heath dominated shrub wetland, herbaceous peatland, and a wetland lacking live vegetation) and two streams. The study sites included wetlands in undisturbed watersheds and in watersheds with considerable agricultural and/or sewage treatment effluent input. Denitrification rates measured in intact cores of water-saturated sediment ranged from ≤ 20 to 260 μmol N m-2 h-1 among the three undisturbed wetlands and were less variable (180 to 260 μmol N M-2 h-1) among the four disturbed wetlands. Denitrification rates increased when nitrate concentrations in the overlying water were increased experimentally (1 up to 770 μM), indicating that nitrate was an important factor controlling denitrification rates. However, rates of nitrate uptake from the overlying water were not a good predictor of denitrification rates because nitrification in the sediments also supplied nitrate for denitrification. Regardless of the dominant vegetation, pH, or degree of disturbance, denitrification rates were best correlated with sediment oxygen consumption rates (r 2 = 0.912) indicating a relationship between denitrification and organic matter mineralization and/or sediment nitrification rates. Rates of denitrification in the wetland sediments were similar to those in adjacent stream sediments. Rates of denitrification in these wetlands were within the range of rates previously reported for water-saturated wetland sediments and flooded soils using whole core15N techniques that quantify coupled nitrification/denitrification, and were higher than rates reported from aerobic (non-saturated) wetland sediments using acetylene block methods.
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  • 34
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    Journal of aquatic ecosystem stress and recovery 3 (1994), S. 27-34 
    ISSN: 1573-5141
    Keywords: nutrient limitation ; critical tissue concentrations ; nitrogen ; phosphorus ; macroalgae ; biomonitoring
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Discs of the macroalga,Ulva lactuca L., were transplanted around an ocean outfall and at a reference site in Køge Bay, Denmark, to assess the influence of the outfall on the nutrient availability. At 2-wk intervals, samples were collected and analyzed for growth, nitrogen, and phosphorus content. The tissue concentrations of nitrogen and phosphorus decreased with distance to the outfall, showing that the tissue concentrations are suitable for monitoring nutrient availability in coastal areas and provide a time-integrated measure of the nutrient availability. The lowest tissue concentrations of nitrogen were recorded at the reference station, where the internal concentrations generally were below the critical concentration level, showing that nitrogen limited the growth. At the station located close to the outfall, the flux of nitrogen was sufficient to maintain the maximum growth rate. The tissue concentrations of phosphorus were only below the critical concentration level on one occasion, and the result showed a net uptake throughout the study period. It was concluded that in the Køge Bay, nitrogen was the main limiting factor for macroalgae growth during the summer. The applicability of tissue concentrations for assessment of nutrient availability is discussed and it is considered that the method, when evaluated against established critical concentrations, provides a valuable tool for assessing ecosystem health with regard to eutrophication.
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  • 35
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    World journal of microbiology and biotechnology 10 (1994), S. 477-478 
    ISSN: 1573-0972
    Keywords: Ethylenediamine ; glutamine synthetase ; nitrogen ; Nostoc ANTH
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Nostoc ANTH metabolizes ethylenediamine (EDA) as sole nitrogen source but not as a carbon source. EDA is assimilated by the glutamine synthetase-glutamate synthase pathway. EDA represses heterocyst formation and nitrogenase activity but this is reversed by l-methionine-dl-sulphoximine.
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  • 36
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    Nutrient cycling in agroecosystems 37 (1994), S. 93-105 
    ISSN: 1573-0867
    Keywords: Erosion/Productivity Impact Calculator (EPIC) model ; leaching ; lettuce ; net N mineralization ; nitrate ; nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Low N use efficiency and high nitrate (NO 3 - ) pollution potentials are problems in intensive vegetable production systems. The purpose of this study was to quantify N utilization by lettuce (Lactuca sativa L. cv Salinas), and identify periods of NO 3 - loss in an on-farm study in the Salinas Valley in coastal California. During autumn and winter, surface moisture remained low, and NO 3 - concentrations increased, reflecting high net mineralizable N, as determined by anaerobic incubation, and nitrification potential, as determined by the chlorate inhibition method. At the onset of a large winter storm, tracer levels of15NO 3 - were injected in the top 5 mm of soil in 30 cm-deep cylinders. After two weeks, most of the15N was present as15NO 3 - at 10–30 cm depth. By difference, losses to denitrification accounted for ~ 25% of the surface-applied15N. Leaching below 30 cm did not occur, since no15N enrichment of NO 3 - -N was measured in anion-exchange resin membranes placed at the base of each cylinder. During the crop period, NO 3 - losses were most pronounced after irrigation events. Uptake of N by two crops of lettuce (above- and belowground material) was approximately equal to fertilizer inputs, yet simulation of N fates by the Erosion/Productivity Impact Calculator (EPIC) model indicated losses of 14.6 g-N m−2 by leaching and 2.5 g-N m−2 by denitrification during the 6-month crop period. The large NO 3 - losses can be attributed to accumulation of soil NO 3 - during winter that was leached or denitrified during the irrigated crop period.
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  • 37
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    Nutrient cycling in agroecosystems 40 (1994), S. 105-108 
    ISSN: 1573-0867
    Keywords: annual ryegrass ; dry matter ; logistic ; model ; nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The logistic model has proven very useful in relating dry matter production of warm season perennial forage grasses to applied nitrogen. A recent extension of the model coupled dry matter and plant N accumulation through a common response coefficient c. The objective of this analysis was to apply the extended logistic model to cool season Gulf annual ryegrass (Lolium multiflorum Lam.) and to establish a common response coefficient c between accumulation of dry matter and plant N. Analysis of variance established the validity of this hypothesis. The model accurately described response of dry matter, plant N removal, and plant N concentration to applied N, with an overall correlation coefficient of 0.9954. Furthermore, the model closely described the relationship between yield and plant N removal, as well as between plant N concentration and plant N removal. The logistic equation is well-behaved and simple to use on a pocket calculator. It can be used to estimate yields and plant N removal in evaluation of agricultural production and environmental quality.
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  • 38
    ISSN: 1572-9680
    Keywords: Argania spinosa ; micro-elements ; nitrogen ; phosphorus ; V.A. mycorrhization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Description / Table of Contents: Résumé L'influence de la mycorhization V.A. sur la nutrition minérale de 2 clones d'Arganier (Argania spinosa) a été étudiée sur des plantules micropropagées in vitro poussant en conditions contrôlées. L'inoculation (qui augmentait la production de matière sèche d'un facteur 4,5) accroit également la teneur des plantes en phosphore, notamment dans les feuilles, et les plantes mycorhizées mobilisent 15 fois plus de phosphore que les plantes non inoculées. La teneur en azote est légèrement plus faible chez les plantes mycorhizées mais au total ces dernières exportent 3 fois plus d'azote. L'absorption des micro-éléments est aussi affectée par l'inoculation, qui accroit les teneurs des plantes en Fe, Zn et Cu. La nutrition minérale des deux clones étudiés semble affectée par le rapport racines/parties aériennes et d'autres caractéristiques génétiques, comme l'efficacité de translocation du fer. Ces résultats nous permettent de comprendre en quoi son système racinaire profond et mycorhizé permet à l'Arganier non seulement de pousser dans des zones arides aux sols pauvres, mais aussi d'améliorer la fertilité des couches supérieures du sol par l'effet litière.
    Notes: Abstract The influence of V.A. mycorrhization on mineral nutrition of 2 clones ofArgania spinosa was studied with in-vitro micropropagated plantlets grown in confined medium under controlled conditions. Inoculation, which increased dry matter production by a factor of 4.5, also increased P concentration in the plant, especially in the leaves, and the mycorrhizal plants mobilized 15 times more P than control plants. N concentration was slightly lower in mycorrhizal plants, but total N content was 3 times higher. Uptake of micro elements was also affected, inoculation increasing plant Fe, Zn and Cu content. Mineral nutrition in the test clones seemed affected by root/shoot ratio and other genetically-related characteristics, such as Fe translocation efficiency. These results help us to understand how its deep mycorrhizal root system might allowArgania spinosa not only to grow in infertile arid areas but also to improve top-soil fertility by a litter effect.
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  • 39
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    International journal of thermophysics 15 (1994), S. 1211-1219 
    ISSN: 1572-9567
    Keywords: binary system ; butane ; carbon dioxide ; nitrogen ; ternary system ; vapor-liquid equilibria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract The system studied was nitrogen + carbon dioxide +n-butane at 250 and 270 K and at pressures from 1.5 to 14 MPa. The Peng-Robinson equation was used to model the results, since it is the most widely accepted equation of state in the gas processing industry. In general, the predictions are most accurate at low and moderate pressures and poorest at high pressures, especially near the critical region.
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  • 40
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    Antonie van Leeuwenhoek 65 (1994), S. 179-182 
    ISSN: 1572-9699
    Keywords: Aspergillus ; fungus ; catabolism ; activation ; repression ; nitrogen ; carbon ; zinc fingers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract TheamdS gene codes for an acetamidase enzyme that hydrolyses acetamide to acetate and ammonium thus providingA. nidulans with a source of carbon and nitrogen. The exceptionally favourable genetics of this system combined with molecular analysis have enabled many regulatory circuits affectingamdS to be identified genetically. Characterization of the regulatory genes and the definition of the cis-acting sites involved have been done using bothin vivo andin vitro mutagenesis. Recent results on the analysis of the system are presented.
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  • 41
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    Hydrobiologia 278 (1994), S. 129-131 
    ISSN: 1573-5117
    Keywords: small rivers ; water contamination ; Tubificidae ; bacteria ; nitrogen ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Two small rivers, the Yerik and Nezhegolyok, were studied seasonally in 1979–1980. Increase in concentration of nitrogen and phosphorus compounds in the river water as well as proliferation of enterococci and enterobacilli favoured the abundance of Tubificidae while, at the same time, their numbers were reduced by chironomids and leeches.
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  • 42
    ISSN: 1573-5044
    Keywords: Fragaria x ananassa ; in vitro ; nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The uptake of 15NO3 - and 15NH4 + has been examined in 5-,10- and 28-day-old micropropagated strawberry (Fragaria x ananassa Duch. cv. Kent) shoots rooted in one-half strength Murashige and Skoog (MS) liquid medium on cellulose plugs (Sorbarods). The results indicated that the plantlets absorbed both NO3 - and NH4 + during the culture with a greater uptake of NH4 + at 5 days of culture. Furthermore, a pronounced reduction in NO3 - and NH4 + uptake at 10 and 28 days of culture was observed within 6 h of the short-term uptake study. This reduction could be explained by the low CO2 concentration in test tubes during the photoperiod, since no reduction in nitrogen uptake occurred in the CO2 enriched condition. The results are interpreted as an indication of the important role for photosynthetic CO2 fixation in the process of nitrogen uptake by the plantlets during the rooting stage.
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  • 43
    ISSN: 1573-5036
    Keywords: atmospheric deposition ; δ15N ; δ34S ; forest decline ; nitrogen ; Picea abies ; stable isotopes ; sulfur
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Concentrations and natural isotope abundance of total sulfur and nitrogen as well as sulfate and nitrate concentrations were measured in needles of different age classes and in soil samples of different horizons from a healthy and a declining Norway spruce (Picea abies (L.) Karst.) forest in the Fichtelgebirge (NE Bavaria, Germany), in order to study the fate of atmospheric depositions of sulfur and nitrogen compounds. The mean δ15N of the needles ranged between −3.7 and −2.1 ‰ and for δ34S a range between −0.4 and +0.9 ‰ was observed. δ34S and sulfur concentrations in the needles of both stands increased continuously with needle age and thus, were closely correlated. The δ15N values of the needles showed an initial decrease followed by an increase with needle age. The healthy stand showed more negative δ15N values in old needles than the declining stand. Nitrogen concentrations decreased with needle age. For soil samples at both sites the mean δ15N and δ34S values increased from −3 ‰ (δ15N) or +0.9 ‰ (δ34S) in the uppermost organic layer to about +4 ‰ (δ15N) or +4.5 ‰ (δ34S) in the mineral soil. This depth-dependent increase in abundance of 15N and 34S was accompanied by a decrease in total nitrogen and sulfur concentrations in the soil. δ15N values and nitrogen concentrations were closely correlated (slope −0.0061 ‰ δ15N per μmol eq N gdw −1), and δ34S values were linearly correlated with sulfur concentrations (slope −0.0576 ‰ δ34S per μmol eq S gdw −1). It follows that in the same soil samples sulfur concentrations were linearly correlated with the nitrogen concentrations (slope 0.0527), and δ34S values were linearly correlated with δ15N values (slope 0.459). A correlation of the sulfur and nitrogen isotope abundances on a Δ basis (which considers the different relative frequencies of 15N and 34S), however, revealed an isotope fractionation that was higher by a factor of 5 for sulfur than for nitrogen (slope 5.292). These correlations indicate a long term synchronous mineralization of organic nitrogen and sulfur compounds in the soil accompanied by element-specific isotope fractionations. Based on different sulfur isotope abundance of the soil (δ34S=0.9 ‰ for total sulfur of the organic layer was assumed to be equivalent to about −1.0 ‰ for soil sulfate) and of the atmospheric SO2 deposition (δ34S=2.0 ‰ at the healthy site and 2.3 ‰ at the declining site) the contribution of atmospheric SO2 to total sulfur of the needles was estimated. This contribution increased from about 20 % in current-year needles to more than 50 % in 3-year-old needles. The proportion of sulfur from atmospheric deposition was equivalent to the age dependent sulfate accumulation in the needles. In contrast to the accumulation of atmospheric sulfur compounds nitrogen compounds from atmospheric deposition were metabolized and were used for growth. The implications of both responses to atmospheric deposition are discussed.
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  • 44
    ISSN: 1573-5036
    Keywords: charcoal rot ; Macrophomina phaseolina ; nitrogen ; NH4NO3 ; Sorghum bicolor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Colonization of sorghum by Macrophomina phaseolina in field plots was determined at nitrogen fertilization rates of 0, 56, 112, and 168 kg ha-1 in 1988 and 0, 84, 168, and 256 kg ha-1 in 1989. Above ground plant tissue and roots were sampled monthly to determine total nitrogen and percent colonization of root segments by natural inoculum. Root infection was not affected by nitrogen treatment, but was affected by growth stage and environment. High root infection occurred before reproductive development (growth stage 3) in 1988 and was associated with hot, dry weather early in the growing season. In 1989, when the weather was cool and wet, root infection began after reproductive development (growth stage 4). The effect of nitrogen treatments on lesion length was determined in sorghum stalks artificially inoculated with M. phaseolina. Lesion lengths were significantly affected by both nitrogen treatments and growth stage. Lesions were significantly longer with all nitrogen treatments at growth stage 9 than with the no-nitrogen treatment, and lesions tended to increase with increased levels of nitrogen fertilization. Significant increases in lesion length occurred between growth stages 5, 7, and 9 in 1988 and between 7 and 9 in 1989. This study demonstrates that nitrogen fertilization affects colonization of sorghum stalks but not root infection by M. phaseolina.
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  • 45
    ISSN: 1573-5036
    Keywords: ammonification ; H+ production ; in-situ incubation ; liming ; mineralization ; nitrification ; nitrogen ; Pinus sylvestris
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract H+ production due to N uptake in a mature Scots pine stand subjected to high NH4 + deposition was previously estimated to amount to approx. 2.2 kmol ha-1 y-1. The question whether H+ transfers related to N mineralization (ammonification and nitrification) offset or corroborate this proton production is investigated in the present research. To determine N mineralization, soil cores were used of which both ends were closed with layers of ion exchange resin (IER) to prevent influx and efflux of ions. The effect of liming on N mineralization and the resulting H+ production was investigated in 7 incubation periods of each ca. 8 wk. Because of its high mobility NO3 accumulated in both IER layers at the expense of that in the incubated forest floor and mineral soil. Net N mineralization in the soil cores as a whole amounted to 40 and 77 kg N ha-1 in 384 d in the control and limed plots, respectively. In both treatments ca. 65% of mineralized N was nitrified. H+ production due to N mineralization amounted to approx. 1.2 kmol ha-1 y-1 in the control and limed plots. Liming reduced the amount of C in the forest floor, but not forest floor mass, because of an increased mixing with mineral particles.
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  • 46
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: β-Nitrostyrene derivatives of adenosine 5′-glutarates are potent and selective bisubstrate-type inhibitors of the epidermal growth factor receptor protein tyrosine kinase (EGF-R PTK). In an attempt to improve the inhibitory activity, this type of compounds was modified with alkyl spacers of varying length between the nitrostyrene and the glutaryl units. The spacers consisted of 1, 3, 4, and 5 atoms to give compounds of the benzyl, oxyethyl, oxypropyl, and oxybutyl series, respectively (Schemes 1 and 2). Adenosine 5′-esters were prepared in the benzyl and oxypropyl series only. Compared to the compounds in the parent series without spacer (IC50 = 0.7-12 μM), most of the modified compounds inhibited the EGF-R PTK only marginally or were inactive (IC50 ≥ 100 μM). The only exceptions were the free acids 19 and 20 with IC50 values of ca. 5 μM. It is noteworthy that esterification of these two hydrogen glutarates with either MeOH or adenosine yielded inactive compounds, which is in contrast to the corresponding substances without spacers.
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  • 47
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Characterization of the Furo and Thieno Analogues of the Triester of PQQWe report here the synthesis and properties of the furo and thieno analogues of 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-f]quinoline-2,7,9- tricarboxylic acid ( = PQQ), i.e. the furo- and thieno[2,3-f]quinoline-4,5-quinone (FQQ and TQQ, resp.) derivatives B and C, obtained as triesters. The triester of PQQ derivative A is much more stable than the triesters of B or C, and only the triester of A shows strong activity in nonenzymatic catalytic oxidations.
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  • 48
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    Helvetica Chimica Acta 77 (1994), S. 171-181 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conversion of the conformation of cyclosporin A (CsA) observed in CHCl3 to the receptor-bound state is investigated by two molecular-mechanics methods, template forcing and dynamic forcing. The conformations of CsA in CHCl3 and complexed with LiCl in THF as determined by NMR are used as starting structures. The transition starting from the CsA/CHCl3-derived conformation is hindered by steric interactions of two side chains (MeBmt1 and Val5). While starting with the CsA/LiCl-derived conformation, the conversion is facile. It is illustrated that these calculations, which are of artificial character, using only the starting and final structures of the observed conformational transition during the receptor-binding event, allow an insight into the interactions between the substrates and receptor in terms of an induced fit.
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  • 49
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    Helvetica Chimica Acta 77 (1994), S. 231-242 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transfer properties of the ionic species involved in the Williamson ether synthesis by phase-transfer catalysis were investigated using electrochemical techniques developed for the study of polarised liquid/liquid interfaces. This approach allows the measurement of the apparent partition coefficients of the transferring species. From these data, it is proposed that the role of the phase-transfer catalyst salt in the reaction mechanism is to establish a Galvani distribution potential difference between the two phases which in turn acts as the driving force for transferring the reactive aqueous ions to the organic phase.
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  • 50
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The (R)- and (S)-5-(hydroxymethyl)-3-isopropyloxazolidin-2-ones, ((R)- and (S)-2, resp.), pivotal intermediates in the preparation of optically active β-blockers, were synthesized using (R,E)-2-hydroxypent-3-enenitrile (1) as the chiral starting material. In the synthesis of (R)-2, a known cyclization/inversion step was applied.
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  • 51
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solutions (2 ml) of small linear and cyclic peptides (4-11), of a peptolide containing nine amino acids and a lactate moiety (12), of the cyclic undecapeptide cyclosporin A (CS, 1), and of the macrolides ascomycin, fujimycin, and rapamycin (13-15) in THF were added to excess LiCl, LiBr, or LiClO4 (up to 3000 equiv. in 40 ml THF) in a calorimeter (calorimetric titration). The enthalpies of interaction measured are in the range of ΔH = -8 to -37 kcal/mol. A similar experiment was carried out with one of the binding proteins of cyclosporin, the human cyclophilin A, to give the thermodynamic parameters for the complexation ΔH = -16, ΔG° = -10 kcal/mol, and ΔS° = -20 cal/mol·deg. at 25° which corresponds to an equilibrium constant K = 2·107 l/mol, in good agreement with the result of independent measurements using different methods. NMR Measurements of the macrolides in (D8)THF containing LiCl show strong down-field shifts of signals of the H-atoms next to C=O and C-OH groups in these molecules.
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  • 52
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 17O-NMR signals of four true C-nitroso compounds 1-4 appear at particularly low field (1550-1265 ppm), whereas the dimers (azodioxy type) resonate at ca. 400 ppm and the ‘isonitroso compounds’ ( = quinone-oximes; 5 and 6) at ca. 250 ppm. S-Nitroso compounds ( = thionitrites; 8 and 9) show shift values of ca. 1300 ppm, not far from C - NO; the NO+ ion is much stronger shielded (474 ppm). The results, together with those for higher-shielded nitroso compounds X - NO (X = RO, R2N, Cl, O-) are discussed in terms of (a) resonance stabilization through n-donation from X(π-bond order, approximated by the known barriers of rotation around the X - N bond) and of (b) electronic excitation energies ΔE. The latter are approximated by long-wave (symmetry-forbidden) UV/VIS absorptions and confirmed, where available, by the maxima of the curves of circular dichroism (CD); the CD curve of thionitrite 9 has been measured. It is found that the δ(17O) values of X - NO depend both on bond order and on ΔE, which could not be separated. The higher shielding of NO+ compared with X - N=O is explained on the basis of anisotropy effects, which differ between sp and sp2 systems.
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  • 53
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    Helvetica Chimica Acta 77 (1994) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 54
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (1S,2R,6R,7R)-4-Phenyl-3,10-dioxa-5-azatricyclo[5.2.1.02,6]dec-4-en-9-one ((+)-5) obtained in 6 steps from the Diels-Alder adduct of furan to 1-cyanovinyl (1S)-camphanate ((+)-3) was reduced to the corresponding endo-alcohol (-)-6 the treatment of which with HBr/AcOH provided (-)-(3aS,4S,6R,7S,7aR)-4β-bromo-3aβ,4,5,6,7,7aβ-hexahydro-2-phenyl-1,3-benzoxazole-6β,7α-diyl diacetate ((-)-17). Elimination of HBr with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and acidic hydrolysis furnished (-)-(1R,2S,3R,4R)-4-aminocyclohex-5-ene-1,2,3-triol ( = (-)-conduramine C1;(-)-1).
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  • 55
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    Helvetica Chimica Acta 77 (1994), S. 10-22 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2′-5′ Adenylate trimers 41-44 carrying the (tert-butyl)dimethylsilyl (tbds) group at the 3′-OH position of various sugar moieties were synthesized via the phosphoramidite method. The use of the (tert-butyloxy)carbonyl (boc) and 2-(4-nitrophenyl)ethylsulfonyl (npes) groups for 2′-OH protection in neighbourhood to the 3′-O-tbds residue was compared during the synthesis of the target trimers. For other functional positions, the use of the 2-(4-nitrophenyl)ethyl (npe) and 2-(4-nitrophenyl)ethoxycarbonyl (npeoc) blocking groups were favoured.
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  • 56
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new and generally applicable synthetic path for the preparation of heteroditopic bis-macrocycles using tri-N-protected tetraazacycloalkanes as building blocks and bromoacetyl bromide as bridging reagent is described. In the first step, bromoacetyl bromide is used as acylating agent for one of the macrocycles, whereas in the second step it is used as alkylating agent for the second macrocycle, thus giving protected bis-macrocyclic amides (e.g. 6). After reduction of the amide moiety and deprotection, bis-azamacrocycles with an ethylene bridge are obtained (e.g. 8). The corresponding homoditopic bis-macrocycles 16 and 17 are also prepared for comparison purpose. Spectrophotometric studies indicate that bis-macrocycle 8, which consists of a 12- and a 14-membered ring, binds two metal ions with equal affinity, whereas compound 13, in which an unsubstituted (cyclam) and a trimethyl-substituted tetraazacyclotetradecane unit (Me3cyclam) are bridged, shows selective metal-ion binding. The first metal ion is always incorporated into the cyclam unit, whereas the second one binds to the Me3cyclam macrocycle. Thus, by sequential addition of two different metal ions, heterobinuclear complexes can easily be prepared. The electrochemistry of the binuclear Ni2+ complexes, studied by CV and DPV, as well as the EPR spectra of the binuclear Cu2+ complexes clearly indicate metal-metal interactions.
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  • 57
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Flash-vacuum thermolysis of the four diastereoisomeric 5,6-epoxy-5,6-dihydro-caryophyllenes 1-4 at 500-550°/0.1-0.7 Torr leads to the hitherto unreported enantiomers of (6RS,7RS)- and (6RS,7SR)-6,7-epoxy-6,7-dihydro-β-farnesenes ((±)-5 and (±)-6, resp.). In particular, (+)-5 is formed in 45% yield (ca. 90% ee) and is, thus, an attractive chiral building block for natural-product synthesis.
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  • 58
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of ceramides, called oceanapins A-F (2-7), which are unique for branching at both the sphingosine and fatty-acid chains, have been isolated as pure compounds from the haplosclerid sponge Oceanapia cf. tenuis of the Coral Sea. Following acid hydrolysis, both the fatty-acid and the sphingosine portions were obtained separately, which allowed their unequivocal structural definition. The absolute configuration was secured via protection of C(1′)-OH and Mosher's esterification at C(3′)-OH of the oceanapins.
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  • 59
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The one-electron transfer to large π-delocalized hydrocarbons provides an interesting possibility to crystallize solvent-separated ion-pair salts containing optimally solvated cations. Accordingly, the reduction of 9,10-diphenylanthracene in aprotic THF solution at a sodium metal mirror allows to grow dark-blue prismatic crystals of its radical anion and sixfold THF-solvated sodium cation. The structure of the radical anion is very similar to that recently published for the neutral molecule. According to AM1 hypersurface calculations based on the structural data, the phenyl twist angles obviously must be determined by lattice packing, and the negative charge is delocalized predominantly within the anthracene π system. The counter cation [Na⊕(THF)6], reported ordered for the first time, shows nearly octahedral coordination within a rather densily packed solvent shell. Due to the strong repulsions between the solvent molecules, its isodesmically calculated solvation enthalpy is smaller than that of the analogous dimethoxyethane complex [Na⊕(DME)3].
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  • 60
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    Helvetica Chimica Acta 77 (1994), S. 86-91 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 14N- and 1H-Coupling constants, determined by ESR, ENDOR, and general-TRIPLE-resonance spectroscopy, are reported for the radical cations of tetrazinodi(heteroarenes) 1-8. The results comply with the expectation that donor properties of these compounds are mainly due to the electron-rich dihydrotetrazine ring.
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  • 61
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    Helvetica Chimica Acta 77 (1994), S. 70-85 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The biphenyl-containing pseudo-amino acids 2′-(aminomethyl)biphenyl-2-carboxylic acid (Abc; 1) and 2′-(aminomethyl)biphenyl-2-acetic acid (Aba; 2) are used as rigid spacers in the backbone of the cyclic peptides cyclo (-Abc-Ala-Phe-Gly-)2 (5), cyclo(-Abc-Ala-Val-Gly-)2 (6), cyclo(-Aba-Gly-Phe-Ala-)2 (7), and cyclo(-Aba-Ala-Phe-Gly-)2(8). Three different interconverting diastereoisomers are found in solutions of each of these cyclopeptides due to the atropisomerism of the biphenyl units. NMR Techniques and molecular-dynamics calculations allow to conclude that the major diastereoisomer of 5 (and 6) in (D6)DMSO adopts a β-sheet conformation. It is proposed that the pseudo-amino acid 1 of (R)-chirality forms, with attached L-amino acids, a H-bonding pattern comparable to a β-turn (see D in Fig. 4 and F).
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  • 62
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    Helvetica Chimica Acta 77 (1994), S. 92-99 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vitamin-B12-Catalyzed C, C-Bond Formation: Synthesis of Jasmonates via Sequential Radical ReactionThe Cbl-catalyzed electroreduction of 3-(2′-bromo-1′-ethoxyethoxy)cyclopenten (1a) in presence of 1-cyanovinyl-acetate (8) gave, in a sequential radical reaction (5-exo-trig-cyclization of 1a followed by addition to 8), 1-cyano-2-(2′-ethoxy-hexahydro-2′H-cyclopenta[b] furan-4′-yl)ethyl acetate (10a). This intermediate was transformed to methyl jasmonate (7; four steps) and epituberolide (9; three steps) in 20 and 31% yield, respectively, from cyclopent-2-en-l-ol.
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  • 63
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    Helvetica Chimica Acta 77 (1994), S. 111-120 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Synthesis of Azaisomers of the Triester of PQQ: 3H-Pyrrolo[3,2-f]-, 1H-Pyrrolo[3,2-h]-, and 7H-Pyrrolo[2,3-h]quinolinequinone DerivativesWe describe here the synthesis of the title compounds 3-5, starting from highly substituted aminoindoles. The annelated pyridine rings were built up in each case with dimethyl 4-oxoglutaconate according to Corey's procedure. All three o-quinone derivatives 3-5 are stable compounds, comparable to PQQ-triester. The azaisomers vary in biological activity from practically inactive to strong inhibition of the α-amidating enzyme or the ornithin decarboxylase.
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  • 64
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    Helvetica Chimica Acta 77 (1994), S. 608-614 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of 2-(1-phenylvinyl)aniline and 4-chloro-2-(1-phenylvinyl)aniline with acetophenone derivatives, 1-(naphthalen-1-yl)ethanone and 1-(furan-2-yl)ethanone in toluene at 110-115° with toluene-4-sulfonic acid as a catalyst leads in good-to-excellent yields to the 2,2-disubstituted 1,2-dihydro-4-phenyl-quinolines 1-18 (Scheme 1, Table). The structure of the new racemic 1,2-dihydroquinolines 1-18 is determined by NMR spectroscopy. A reaction mechanism proceeding via a 6π-electrocyclic rearrangement of 2-(1-phenylvinyl)anils 19 as the key step is proposed for the formation of these compounds (Scheme 1). The scope and limitations of the novel methods are discussed (Scheme 2).
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  • 65
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    Helvetica Chimica Acta 77 (1994), S. 622-630 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 2′-deoxyisoguanosine (1) was synthesized by a two-step procedure from 2′-deoxyguanosine (5). Amination of silylated 2′-deoxyguanosine yielded 2-amino-2′-deoxyadenosine (6) which was subjected to selective deamination of the 2-NH2 group resulting in compound 1. Also 2′,3′-dideoxyisoguanosine (2) was prepared employing the photo-substitution of the 2-substituent of 2-chloro-2′,3′-dideoxyadenosine (4). The latter was synthesized by Barton deoxygenation from 2-chloro-2′-deoxyadenosine (3) or via glycosylation of 2,6-dichloropurine (12) with the lactol 13. Compound 1 was less stable at the N-glycosylic bond than 2′-deoxyguanosine (5). The dideoxynucleoside 2 was deaminated by adenosine deaminase affording 2′,3′-dideoxyxanthosine (17).
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  • 66
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A crude hydrate 6 and a crystalline hemiacetal 7 of glyoxylamide 4 were prepared from crotonamide 5 (Scheme 2). Particularly hemiacetal 7, but also 6 and the ‘dimer’ 8 (obtained from 7) may serve as homochiral auxiliaries. The structure of 8 was determined by X-ray analysis. By arenesulfonyl halides, tryptimines 12-14 of 4 were diastereoselectively transformed into spirotricycles 15-17 and 19.
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  • 67
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of 2′-benzamido-2′-deoxyadenosine analogues were synthesized in an effort to find new lead structures for the treatment of sleeping sickness. The 2′-deoxy-2′-(3-methoxybenzamido)adenosine (1h) was proved to be a selective inhibitor of the parasite glyceraldehyde 3-phosphate dehydrogenase which confirms the modeling studies. The solution-state conformation of 2′-(thiophene-2-carboxamido) analogue 1d demonstrates a 2′-endo conformation, an orientation of the thiophene ring under the ribose moiety, and the base part occupying a ‘syn’/‘anti’ equilibrium.
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  • 68
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    Helvetica Chimica Acta 77 (1994), S. 645-654 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of cyclohexyl diazoacetate (5a) in the presence of the chiral [Rh2{(2S)-mepy}4] catalyst leads to a 3:1 cis/trans mixture of bicyclic lactone 6a with an enantiomeric excess of 95-97% (cis) and 90% (trans). The conformationally rigid tert-butyl derivatives 5b and 5c afford, in the presence of the same catalyst, 6b and 6c, respectively, via insertion into the equatorial C—H bonds exclusively, with ee's of ca. 95%. A remarkable degree of induction (92-95%) results in the lactone 6g upon decomposition of 1-isopropyl-2-methylpropyl diazoacetate (5g). The diazoacetates derived from 1-methylcyclohexanol, cyclopentanol and 1-methylcyclopentanol (5d-f) afford under similar conditions insertion products with higher diastereoselectivity, but significantly lower enantioselectivity. Other dirhodium catalysts are less efficient.
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  • 69
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    Helvetica Chimica Acta 77 (1994), S. 661-667 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first synthesis of (Z)-neomanoalide (4) and an improved synthesis of its (E)-isomer 3 was accomplished in a concise, regiocontrolled manner by exploiting 2-[(tert-butyl)dimethylsiloxy]-4{[(tert-butyl)dimethylsiloxy]-methyl}furan (6) as the key reagent. Lithiation of 6 and subsequent reaction with the (2Z)- or (2E)-isomer of (6E)-3-{[(tert-butyl)dimethylsiloxy]methyl}-7-methyl-9-(2′,6′,6′-trimethylcyclohex-1′-enyl)nona-2,6-dienyl bromide (5), followed by hydrolysis, afforded the corresponding neomanoalide.
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  • 70
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 2,4-bis-functionalized phenol 1 is dehydrogenated regioselectivity with potassium ferricyanide, affording the corresponding p-quinonemethide 2. Hydrolysis of 2 affords a mixture of dithioacetal 5a and benzaldehyde 6; 1,6-addition of thiols to 2 gives the dithioacetals 5 of benzaldehyde 6; reaction of 2 with 2,2′-azobis(isobutyronitrile) (= 2,2′-dimethyl-2,2′-azobis(propanenitrile)) leads to 9a, 9b, and 10, addition products of the 1-cyano-1-methylethyl radical. The structures of all products are confirmed mainly by 1H- and 13C-NMR spectroscopy, and the mode of their formation is discussed.
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  • 71
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational space of the trisaccharide α-L-Fuc-(1→2)-β- D-Gal-(1→3)-β -D-GalNAc-1-OPr (2) and of its component disaccharide moieties α -L-Fuc-(1→2)-β -D-Gal-1-OMe (3) and β -D-Gal-(1→3)-β- D-GalNAc-1-OPr (4) was investigated with the aid of molecular-mechanics energy minimizations and molecular-dynamics simulations. These calculations suggested the occurrence of two conformations for each compound characterized by different φ and Ψ glycosidic angles. However, 1H-NMR investigation of D2O solutions of 2-4 indicated a sure preference for one of the two conformers with a contribution of the other one ranging from negligible to low.
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  • 72
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis on solid phase of a new derivative of the anticoagulant protein hirudin is described (see Scheme and Fig.1, I). The henicosapeptide is a bivalent conjugate of the C-terminus of hirudin and of the active-site-binding tetrapeptide D-Phe-Pro-Arg-Pro linked via a tetraglycine spacer. The peptide, for which the name hirufos was coined, incorporates a stable phosphono derivative of L-phenylalanine which, combined with the other structural modifications, leads to a potent anticoagulant agent. Synthesis was readily achieved by the (9H-fluoren-9-yl)-methoxycarbonyl (Fmoc) strategy followed by acidolytic cleavage from the resin and deprotection, including the liberation of the crucial phosphonic group on L-phenylalanine.
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  • 73
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    Helvetica Chimica Acta 77 (1994), S. 691-708 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tri-o-thymotide (TOT) clathrates are enantiomorphous and enantioselective (chiral cages). It was shown that an external molecular reactant can diffuse into the TOT host crystal lattice and reacts with the included molecule (guest) in characteristic ways, differing from those occurring in liquid solutions. Several aspects of the action of hydrogen halides (HCl, HBr) on the chemical behavior of included oxiranes were investigated for solid-gas and solid-liquid (aqueous) systems. Under well established experimental conditions, these reactions gave regiospecifically one target product and were asymmetric. The included substrate underwent first an acid-catalyzed allylic isomerization that is cage-specific and mostly quantitative. In sheer contrast, strong basic conditions were required to promote, in reduced yield, the analogous transformation in solution. The regiospecificity and enantioselectivity of several intra-crystalline conversions allowed the accurate determination of the absolute configuration of several guest molecules. Kinetic measurements were achieved that disclosed some striking features of this new type of heterogeneous reactions. Tentative models for the cage stereoselective mechanisms are briefly discussed.
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  • 74
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complex formation by Co2+, Ni2+, Cu2+, Zn2+, and Cd2+ with tris[2-(dimethylamino)ethyl]amine (N(CH2CH2NMe2)3, Me6tren) was investigated at 25° and at an ionic strength of 1, using VIS spectroscopy and potentiometric measurements. The stability constants of these complexes are compared with those of tris(2-aminoethyl)amine (N(CH2CH2NH2)3, tren), obtained under the same conditions. The values of the constants for Me6tren are much lower than those for tren, due to the bulky Me substituents. The values of the constants can be correlated with the ability of the individual metal ions to adopt coordination number 5. This appears to be easier for Cu2+ and Co2+ than for Cd2+ and Zn2+ and is very difficult for Ni2+. The 1:1 complexes [ML(H2O)]2+ are monoprotonic acids whose pKs values are similar or lower than those of the corresponding aquametal ions. The X-ray crystal structure of the copper(II) complex [Cu(SO4)(Me6tren)] · 8H2O reveals pentacoordination at the central ion. The UV/VIS spectra of the aqueous solutions of the Co2+, Ni2+, and Cu2+ 1:1 complexes confirm that the same coordination number is present also in these complexes.
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  • 75
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    Helvetica Chimica Acta 77 (1994), S. 1768-1772 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of peregrine (1), a norditerpenoid alkaloid isolated from Delphinium peregrinum var. elongatum BOISS., was revised on the basis of the 1H-COSY, HMQC, HMBC, and ROESY NMR spectra and of the X-ray analysis of its parent alcohol 2. Some of the 13C-NMR resonances of 1 and the related alkaloids peregrine alcohol (2), 14-O-acetylperegrine (3), bicoloridine (4), bicoloridine alcohol (5), 6-O-acetylbicolorine (6), bicolorine (7), and 14-O-acetylbicolorine (8), were also reassigned.
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  • 76
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The antivirally active 3′-deoxyadenylyl-(2′-5′)-3′-deoxyadenylyl-(2′-5′)-3′-deoxyadenosine (cordycepin trimer core) was modified at the 2′- or 5′-terminus, by attachment of cholesterol via a carbonate bond (→ 15) or a succinate linker (→ 16 and 27) to improve cell permeability. The corresponding monomeric conjugates 4, 7, and 21 of cordycepin were prepared as model substances to study the applicability of the anticipated protecting groups - the monomethoxytrityl (MeOTr), the (tert-butyl)dimethylsilyl (tbds), and the β -eliminating 2-(4-nitrophenyl)ethyl (npe) and 2-(4-nitrophenyl)ethoxycarbonyl (npeoc) groups - for the final deblocking steps without harming the ester bonds of the conjugate trimers. The syntheses were performed in solution using phosphoramidite chemistry. The fully protected trimer conjugates 13, 14, and 26 as well as all intermediates were characterized by elemental analyses, UV and 1H-NMR spectra. The deblocked conjugates 15, 16, and 27 were pure according to HPLC and showed the correct compositions by mass spectra. Comparative biological studies indicated that cordycepincholesterol conjugate trimers 16 and 27 were 333- and 1000-fold, respectively, more potent inhibitors of HIV-1-induced syncytia formation than cordycepin trimer core.
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  • 77
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrophosphoric-acid-analogue phosphonoformic acid (pfa) and the amino-acid-analogue (aminomethyl)phosphonic acid (ampa) both form, in the deprotonated state, i.e., as -OOC-PO32- and H2N—CH2—PO32-, respectively, five-membered chelate rings with metal ions. pfa inhibits both phosphate transport and virus replication, while ampa is a metabolic product of the common herbicide glyphosate ( = N-(phosphonomethyl)glycine). The acidity constants of H2pfa- and H2ampa± as well as the stability constants of the [M(Hpfa)], [M(pfa)]-, [M(Hampa)]+, and [M(ampa)] complexes, where M2+ = Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Co2+, Ni2+, Cu2+, Cu(2,2′-bipyridyl)2+, Cu(1,10-phenanthroline)2+, Zn2+, or Cd2+, have been determined by potentiometric pH titrations in aqueous solution at 25° and I = 0.1M (NaNO3). The structures of isomeric complexes and the connected intramolecular equilibria are deduced and evaluated based on the equilibrium constants measured and those calculated via the pKa values of the above mentioned ligands and previously established log K vs. pKa straight-line plots (H. Sigel et al., Helv. Chim. Acta 1992, 75, 2634) for a simple phosphonate-M2+ coordination. pfa forms stronger complexes than ampa with all the above mentioned metal ions, with the single exception of [Cu(ampa)] which is slightly more stable than [Cu(pfa)]-. In neutral solutions, more precisely at pH of ca. 6, pfa complexes of alkaline-earth-metal ions retain one phosphonate-bound proton, [M(Hpfa)], while those of the transition-metal ions chelate with the trianionic ligand, pfa3-. In accord with increasing ligand-basicity, the stability-constant order for all metal-ion complexes is oxalate 〉 pfa 〉 pyrophosphate but, owing to proton competition in pyrophosphate, in neutral solutions metal-ion complexation of pfa3- competes with P2O74-. With ampa alkaline-earth-metal ions interact only with the phosphonate group of even the dianionic ligand (though Mg2+ appears to form a low fraction of a [Mg(ampa)] chelate) while transition-metal ions form chelates which are comparable in stability to those of glycinate.
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  • 78
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    Helvetica Chimica Acta 77 (1994), S. 1773-1780 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of the Sb2F11 salt of the 2-phenyladamant-2-yl cation, 1 · Sb2F11, was determined at 183 K (P21/c, R1 = 0.0652, σ(C—C) = 0.02 Å), because earlier published results indicated a charge delocalization from the cationic C(2) into the σ framework (C—C hyperconjugation) and a bending of the C(2) bridge. In the structure of 1, a displacement of the C(2) bridge by 7.8(12)° from the symmetrical position and C—C bond-length deviations from expectation values were found which are in agreement with preferential C—C hyperconjugation on one face of C(2). The interactions of 1 with two Sb2F11 counterions nearest to C(2) also indicate different behaviour of the two faces of C(2). The benzylic resonance in 1 is confirmed.
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  • 79
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bicyclic monoselenoacetal 7, easily obtained from (±)-7-oxabicyclo[2.2.1]hept-5-en-2-one (6) via a radical addition-acyl migration sequence, was converted to racemic 12-epiprostaglandins 3 and 4. The key intermediate was the all-cis-formyllactone 2b related to Corey lactone (see 12; Scheme 1). The presence of a (tert-butyl)-dimethylsilyl protective group for the 11-OH substituent (prostaglandin numbering) was found to be crucial in avoidingβ -elimination and epimerization during the Wittig-Horner reaction (Scheme 2). Epimerization at C(12) at the formyllactone stage (see 2b) was also possible and gave the known precursor 1b of naturally occurring prostaglandins and analogs.
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  • 80
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: While trialkylamines and dialkyl(phenyl)amines do not react with CS2 in the sense of an addition reaction, the analogous phosphines react smoothly. Attempts to interpret the reaction course on the basis of semiempirical, HF, MP2, and MP4 calculations of energy changes failed completely. To understand why Me3P or Me2PhP react so vigorously (liquid phase, 300 K) with CS2, CASSCF and MRSDCI calculations must be carried out.
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  • 81
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 0The bipyridyl-armed tetra-p-(tert-butyl)calix[4]arenes 1-5 were synthesized from tetra-p-(tert-butyl)-calix[4]arene A and 6-(bromomethyl)-6′-methyl-2,2′-bipyridine (B) by direct base-strength-driven regioselective O-alkylation or by stepwise procedures. Preliminary complexation studies of the ligands 1-3 with CuI affording the complexes 6-8 are described.
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  • 82
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Hydroxymethyl)bilane synthase (HMBS) catalyses the conversion of porphobilinogen (2) into the (hydroxymethyl)bilane derivative 3, a linear tetrapyrrolic intermediate in the biosynthesis of haem, chlorophyll, and related pigments. The conversion involves the sequential formation of four intermediate covalent enzyme-substrate complexes, before the product is released. We analysed the pre-steady-state kinetics of the formation of the complexes, taking advantage of their remarkable chemical stability allowing chromatographic separation. The experimental approach involved the generation of the complexes while HMBS was immobilised on an anion-exchange column. A solution being 0.2 Km in substrate was pumped through the column during a time interval which was varied to sample the pre-steady-state period. Then, the enzyme and enzyme-substrate complexes were eluted and their proportions evaluated. A computer simulation of the pre-steady-state time course, in combination with a χ2 fitting to the experimental data, allowed the specificity constants kcat/Km for the individual steps of the process to be derived. By repeating the analysis with variants of HMBS in which specific amino acids were replaced by others, we demonstrated that it is possible to trace the consequences of amino-acid replacements down to the individual steps of the reaction sequence. Since the positions of the amino acids concerned in the three-dimensional structure were known, detailed structure-function relationships become evident in this way.
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  • 83
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclic oligomers of (R)-3-hydroxyvaleric acid (3-HV) are prepared from the monomer by three different methods, giving various ratios of the oligomers. The macrocycles containing three to twelve 3-HV units (12- to 48-membered rings) are isolated in pure form by chromatography. The triolide 3 can be separated by distillation and isolated on large scale. Biopol, the copolymer of (R)-3-hydroxybutanoic acid (3-HB) and (R)-3-hydroxyvaleric acid (3-HV), is degraded to mixtures of Me- and Et-substituted triolides (‘mixolides’) with high crystallization tendency. The X-ray crystal structures of the tetrolide 4, pentolide 5, hexolide 6, heptolide 7, and of two ‘mixolides’ (with inclusions of solvent) have been determined (Figs. 3-7, 10, and 11) and are compared with those of the corresponding 3-HB derivatives reported previously. From the structural data, a 31 and a 21 helix of 3-HV can be modelled, and the latter one compared with helix structures of P9(3-HB) and P(3-HV) derived from stretch-fibre X-ray scattering. Crystals of a water-containing NaSCN complex of the triethyl triolide 3 were obtained in good quality for X-ray analysis. The structure (Figs. 12, 13, and Table 6) contains an interesting array of C=O and H2O O-atoms around the Na+ ions along a channel-type tube (a-axis of the crystal) which may be relevant to the role of P(3-HB) and P(3-HV) as components of cellular ion channels.
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  • 84
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By conventional peptide-coupling methods (C to N direction; mixed anhydride, bis(2)-oxooxazolidin-3-yl)phosphinoyl chloride (Bop-Cl), or dicyclohexylcarbodiimide (DCC), 2-amino-2-methyl-3-(methylamino)-propionic acid and 2-amino-2-ethyl-3-(methylamino)propionic acid ( = 2-amino-2-[(methylamino)methyl]butanoic acid) are incorporated in the central position of tri-, penta-, and heptapeptides (see 3-7, 21, and 22). The fragment coupling of the β -amino group of the diamino-acid moiety in a tetrapeptide led to partial epimerization, and thus, two epimeric heptapeptide derivatives were actually obtained (7 and epi-7). The final deprotection to the free heptapeptide (involving a Me3SiI cleavage of BocNH and MeOCONH, a saponification with NaOH, and HPLC purification) gave both the desired product (isopeptide 21), with the β -amino group inside the peptide backbone, and a product (peptide 22) of transpeptidation, with the α-amino group of the diamino acid incorporated and a (methylamino)methyl group as the side chain. Peptide 22 is completely converted to the isopeptide 21 by prolonged treatment with base. The heptapeptide 21 was analyzed by elaborate 2QF-COSY and NOESY NMR measurements in H2O/CD3OD at -5° (Table, Fig.); there is no indication for β -sheet or helical structures, a fact which was also confirmed by CD measurements.
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  • 85
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    Helvetica Chimica Acta 77 (1994) 
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    Keywords: Chemistry ; Organic Chemistry
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    Topics: Chemistry and Pharmacology
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  • 86
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    Helvetica Chimica Acta 77 (1994), S. 2070-2070 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 87
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The triphenylstannyl β-D-glucopyranoside 4 was synthesized in one step from the 1,2-anhydro-α-D-glucopyranose 3 with (triphenylstannyl)lithium (Scheme 1). Transmetallation of 4 with excess BuLi, followed by quenching the dianion 7 with CD3OD gave (1S)-1,5-anhydro-3,4,6-tri-O-benzyl-[1-2H]-D- glucitol (8) in 81% yield (Scheme 2). Trapping of 7 with benzaldehyde, isobutyraldehyde, or acroleine gave the expected β-D-configurated products 11, 12, and 13 in good yields. Preparation of C-acyl glycosides from acid chlorides, such as acetyl or benzoyl chloride was not practicable, but addition of benzonitrile to 7 yielded 84% of the benzoylated product 14. Treatment of 7 with MeI led to 15 (30%) along with 40% of 18, C-alkylation being accompanied by halogen-metal exchange. Prior addition of lithium 2-thienylcyanocuprate increased the yield of 15 to 50% and using dimethyl sulfate instead of MeI led to 77% of 15. No α-D-anomers could be detected, except with allyl bromide as the electrophile, which yielded in a 1:1 mixture of the anomers 16 and 17.
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  • 88
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantiomerically pure C2-symmetric 1,4-diols embodying bicyclic C-frameworks were synthesized by means of asymmetric carbo-Diels-Alder reactions as key steps (Scheme 1). They were investigated as chiral ligands in the enantioselective addition of ZnEt2 to aromatic aldehydes. In the presence of 20-40 mol-% of the titanates formed from these diols and [Ti(i-PrO)4] at -78°, the respective 1-arylpropanols were obtained with enantiomer ratios up to 93:7 (Scheme 2, Table).
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  • 89
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidative transformation of synthetic (+)-aristoteline ((+)-6) into other metabolites which had been isolated from Aristotelia species was investigated. Thus, treatment of (+)-6 with I2 as the single oxidant furnished the naturally occurring indole alkaloids (+)-makonine ((+)-9),(+)-aristotelinone ((+)-11), or (+)-11, 12-didehydroaristoteline ((+)-7) in good yields, the selectivity of the oxidation process depending on the chosen reaction conditions.
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  • 90
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparation and screening of twenty new ligands, all analogs of α,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL), for the Ti-catalyzed asymmetric addition of methyltri(isopropoxy)titanium and diethylzinc to benzaldehyde are described. These ligands have the dioxolane ring of the TADDOL's replaced by cyclobutane, cyclopentane, cyclohexene, cyclohexane, bicyclo[2.2.1]heptene and -heptane and bicyclo[2.2.2]octene and -octane moieties; several have H-atoms or alkyl groups in place of the aryl groups, and nine of them have C2 symmetry. X-Ray crystallography and molecular mechanics are used to analyze the structure of the ligands, and two structural features appear to correlate with selectivity: (i) the torsion angle for the chelating O-atom and the ortho-C-atom of the axial Ph group (a small, ca. 19°, angle is optimum, Fig.8) and (ii) the “degree of perpendicularity” of the axial Ph group (Fig. 9). Competition experiments indicate that TADDOL 1a catalyzes both the methyltitanium and diethylzinc additions ≥ 50 times faster than the related dioxolane analogs 12a, 12c, and 12e (Scheme 7), indicating that both axial and equatorial aryl groups (see Footnote 6) are necessary for ligand-accelerated catalysis of these reactions. A refined mechanistic hypothesis is presented (Fig. 10) to explain the selectivities observed for these new ligands. Our analysis suggests that a combination of structural features appear necessary for good catalytic efficiency and high selectivity. These features, especially the rather subtle conformational effects, appear to be optimized (among the ligands tested) in the TADDOL's.
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  • 91
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 77 (1994), S. 2117-2124 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a theoretical investigation of the structure and reactivity of indole derivatives of tricarbonylchromium(0), we have used two different semi-empirical quantum chemical models derived from the extended Hückel molecular-orbital (EHMO) formalism. The first one, based on the atom-superposition and electron-delocalization (ASED) method, is used to optimize the geometry of the systems; it is shown to lead to results in satisfactory agreement with experiment in the case of the complex for which X-ray structural data are available, the average errors being 0.03-0.05 Å for bond distances and 5° for bond angles. The second one consists of a local reactivity index, made of the intermolecular interaction energy between the organometallic substrate and a model reactant. It is seen that this procedure is able to reproduce the experimental trends as to the most reactive regions of the systems investigated towards nucleophilic and electrophilic addition reactions.
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  • 92
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 77 (1994), S. 2133-2141 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Thiazole-5(4H)-thione oxides 2 were prepared by oxidation of the corresponding 1,3-thiazole-5(4H)-thiones 1 with m-chloroperbenzoic acid (Table 1). Addition reactions of 2 with organolithium and Grignard reagents yielded 4,5-dihydro-4,4-dimethyl-1,3-thiazol-5-yl methyl sulfoxides of type 4 via thiophilic attack (Table 2). Whereas the reaction with the organolithium compounds proceeded with fair-to-excellent yields, the Grignard reagents reacted only very sluggishly. The sulfoxides 4 could also be prepared via oxidation of 4,5-dihydro-4,4-dimethyl-5-(methylthio)-1,3-thiazoles of type 3 with m-chloroperbenzoic acid, together with the corresponding sulfones 5 (Scheme 1).
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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 α-D-allo-diol 9 possesses an intramolecular H-bond (HO—C(3) to O—C(1)) in solution and in the solid state (Fig. 2). In solution, it exists as a mixture of the tautomers 9a and 9b (Fig. 3), which possess a bifurcated H-bond, connecting HO—C(2) with both O—C(1) and O—C(3). In addition, 9a possesses the same intramolecular H-bond as in the solid state, while 9b is characterized by an intramolecular H-bond between HO—C(3) and O—C(4). In solution, the β-D-anomer 12 is also a mixture of tautomers, 12a and presumably a dimer. The H-bonding in 9 and 12 is evidenced by their IR and 1H-NMR spectra and by a comparison with those of 3-8, 10, and 11. The expected regioselectivity of glycosidation of 9 and 12 by the diazirine 1 or the trichloroacetimidate 2 is discussed on the basis of the relative degree of acidity/nucleophilicity of individual OH groups, as governed by H-bonding. Additional factors determining the regioselectivity of glycosidation by 1 are the direction of carbene approach/proton transfer by H-bonded OH groups, and the stereoelectronic control of both the proton transfer to the alkoxy-alkyl carbene (in the σ-plane) and the combination of the thereby formed ions (π-plane of the oxycarbenium ion). Glycosidation of 9 by the diazirine 1 or the trichloroacetimidate 2 proceeded in good yields (75-94%) and with high regioselectivity. Glycosidation of 9 and 12 by 1 or 2 gave mixtures of the disaccharides 14-17 and 18-21, respectively (Scheme 2). As expected, glycosidation of 12 by 1 or by 2 gave a nearly 1:1 mixture of regioisomers and a slight preference for the β-D-anomers (Table 4). Glycosidation of the α-D-anomer 9 gave mostly the 1,3-linked disaccharides 16 and 17 (α-D β-D) along with the 1,2-linked disaccharides 14 and 15 (α-D 〈 β-D, 1,2-/1,3-linked glycosides ca. 1:4), except in THF and at low temperature, where the β-D-configurated 1,2-linked disaccharide 15 is predominantly formed. Similarly, glycosidation of 9 with 2 yielded mainly the 1,3-linked disaccharides (1,2-/1,3-linked products ca. 1:3 and α-D/β-D ca. 1:4). Yields and selectivity depend upon the solvent and the temperature. The regioselectivity and the unexpected stereoselectivity of the glycosidation of 9 by 1 evidences the combined effect of the above mentioned factors, which also explain the lack of regio-complementarity in the glycosidation of 9 by 1 and by 2 (Scheme 3). THF solvates the intermediate oxycarbenium ion, as evidenced by the strong influence of this solvent on the regio- and stereoselectivity, particularly at low temperatures, where kinetic control leads to a stereoelectronically preferred axial attack of THF on the oxycarbenium ion.
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  • 94
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Condensation of 3,4-dihydro-6,7-dimethoxyisoquinoline (4) with 4-methylnicotinoyl chloride (12) in refluxing pyridine gives 5,6,13,13a-tetrahydro-2,3-dimethoxy-8H-isoquino[2,1-b][2,7] naphthyridin-8-one (11), along with some of its 13,13a-didehydro derivative 7. A similar reaction of 4 with 4-(chloromethyl)nicotinoyl chloride (14) affords, in addition to 7, the isomeric product 10,11-dihydro-7,8-dimethoxy-13H-pyrido[4′,3′:3,4]pyrrolo[2,1- b][3]benzazepin-13-one (3). Analogous pairs of products are obtained from 3,4-dihydro-6,7-(methylenedioxy)- and 3,4-dihydro-6,7,8-trimethoxy-isoquinolines (15 and 18, resp.). The structure of 3 was established by extensive NMR data and confirmed by single-crystal X-ray studies. Structure 7 has the ring system of the Alangium alkaloids like alangimarinc (1), while the isomeric ring system 3 is predicted to be present in nature on biogenetic reasoning.
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  • 95
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 77 (1994), S. 182-193 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe the synthesis of short double-stranded DNA fragments (see 4 and 13) which are capped on both ends by an optimally designed linker molecule. The new structures are stable with respect to hybrid dissociation and should have implications in physical studies involving double-stranded DNA as well as in the antisense area for the specific modulation of gene expressions.
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  • 96
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nucleophilic substitution of 6β-chloro-7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan (1) and 8α-bromo-6,7-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan (2) with lithium cyano(methyl)- and (aryl)cyanocuprates(I) (5a-c) was accompanied by allylic rearrangement with both change and retention of orientation of the substituting group (Scheme 1, Table 1). Nucleophilic substitution in 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan-6α-yl methanesulfonate (3) and 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan-6β-yl methanesulfonate (4) proceeded without allylic rearrangement with both change and retention of the orientation of the substituting group (Scheme 2, Table 1). X-Ray diffraction studies of the products 6,7-didehydro-4,5α-epoxy-3-methoxy-17-methyl-8α-phenylmorphinan (6b) and 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methyl-6β-phenylmorphinan (7b) were carried out (Figs. 1 and 2).
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  • 97
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 77 (1994), S. 194-202 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various 2-substituted purine and pyrrolo[2,3-d]pyrimidine 2′-deoxyribonucleosides with methylthio (13a), chloro (13b), methoxy (9b), and oxo (2, 3) substituents at C(2) are prepared. They are obtained either via stereoselective nucleobase-anion glycosylation or by base transformation. A three-step synthesis of the unknown 2′-deoxyisoinosine (2) from 2′-deoxyguanosine (15) is described. Compound 2 as well as its 7-deazapurine derivative 3 exhibit strong fluorescence.
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  • 98
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Use of the 2-dansylethoxycarbonyl ( = 2-{[5-(dimethylamino)naphthalen-1-yl]sulfonyl}ethoxycarbonyl; Dnseoc) group as an intermediate 5′-OH protecting group in oligodeoxyribonucleotide synthesis using the automated phosphoramidite approach is described in a model study to an alternative strategy in RNA synthesis.
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  • 99
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of (-)-corycavinium (+)-10-camphorsulfonate has been investigated by X-ray analysis. The structure of (-)-corycavinium ion ( = (-)-(7S,13S,14R)-5,6,13,13a-tetrahydro-13a-hydroxy-7-methyl-2,3;9,10-bis(methylenedioxy)-8H-dibenzo[a,g]quinolizinium), has been determined. The conformation with B/C-cis-conjunction, a twisted half-chair of ring B, and a half-chair of ring C, as well as α-oriented substituted groups N…Me, C…Me, and C…OH is revealed. Feeding experiments with cell suspension cultures of Corydalis incisa (Papaveraceae) defined the intermediacy of (-)-corycavinium in the route from protoberberine-type to hexahydrobenzo[c]phenanthridine-type of alkaloids. On the basis of the present crystal conformation, the stereospecificity of the relating enzyme is biogenetically considered.
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  • 100
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Symmetrical Azopyridinone Dyes: Synthesis, Spectrophotometrical and Acidobasic Properties, Metal-Complex Formation and Kinetical Investigation of the Azo-Dye FormationThe 13 substituted symmetrical azopyridinone dyes 2a-n were synthesized and their VIS spectra measured. The pK*a values of some dyes and of pyridinone coupling components were determined in MeOH/H2O 64:36. The metal-complex formation of the dyes with Cd2+, Zn2+, Co2+, Ni2+, and Cu2+ was investigated, and complex-formation constants of the 1:1 complexes were determined in H2O for 2k (Table 2) and in dimethylformamide/H2O 1:1 for some other azopyridinone dyes (Table 3). The mechanism of the azo-dye formation was investigated and found to be much more complicated than expected. A mechanism of the coupling reaction was developed (see Scheme 4) and fitted by least-squares calculations.
    Notes: NO ABSTRACT.
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