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  • Articles  (382)
  • phosphorus  (206)
  • Animals
  • Chemical Engineering
  • Electronic structure and strongly correlated systems
  • kinetics
  • Springer  (382)
  • 1990-1994  (382)
  • 1
    Electronic Resource
    Electronic Resource
    The kinetics of the solvolysis of chloropentacyanocobaltate(III) ions in water containing 2-methoxyethanol or diethylene glycol: A contrast with the effect of more hydrophobic cosolvents (1994)
    Springer
    Journal of solution chemistry 23 (1994), S. 1089-1100 
    Details
    ISSN: 1572-8927
    Keywords: Solvolysis ; kinetics ; aqueous solvent mixtures ; Co(III) complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the solvolysis of [Co(CN)5Cl]3− have been investigated in water +2-methoxyethanol and water + diethylene glycol mixtures. Although the addition of these linear hydrophilic cosolvent molecules to water produces curvature in the variation of log(rate constant) with the reciprocal of the dielectric constant, their effect on the enthalpy and entropy of activation is minimal, unlike the effect of hydrophobic cosolvents. The application of a Gibbs energy cycle to the solvolysis in water and in the mixtures using either solvent-sorting or TATB values for the Gibbs energy of transfer of the chloride ion between water and the mixture shows that the relative stability of the emergent solvated Co(III) ion in the transition state compared to that of Co(CN)5Cl3− in the initial state increases with increasing content of cosolvent in the mixture. By comparing the effects of other cosolvents on the solvolysis, this differential increase in the relative stabilities of the two species increases with the degree of hydrophobicity of the cosolvent.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00976258
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  • 2
    Electronic Resource
    Electronic Resource
    Thermodynamics of coupled reactions by the method of dynamic titration: the Nickel(II)-salicylate ion system (1994)
    Springer
    Journal of solution chemistry 23 (1994), S. 483-500 
    Details
    ISSN: 1572-8927
    Keywords: Thermodynamics ; kinetics ; chemical relaxation ; temperature-jump ; amplitudes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Amplitudes of chemical relaxation signals can provide useful information as to the thermodynamics of coupled chemical reactions. The temperature-jump technique has been used to investigate the thermodynamic behavior of the Nickel(II)-3,5-dinitrosalicylate system in buffer solution, where complex formation steps are coupled to proton transfer steps. The analysis of the relaxation curves is based on the transformation of a set of coupled elementary reactions into a set of uncoupled ‘normal reactions.’ By analogy with classical titrations, the experiments have been performed by changing the metal ion concentration at constant ligand concentration and pH. Each measured amplitude is associated in this way to a point of a ‘dynamic titration’ and a procedure is formulated by which the values of the equilibrium constants and enthalpies of the normal reactions are simultaneously obtained by simple linear plots. From the dependence of these parameters on suitable functions of the concentrations of the reactants the values of ΔG° and ΔH° of the individual steps are derived. It is shown that the addition of a buffer (instead of an indicator) influences the stoichiometric coefficients of the normal reaction in such a way that measurable amplitudes are produced in systems that, as the presently investigated, in unbuffered solution would remain insensitive to the external perturbation. The circumstances under which the dynamic method offers advantages over the classical techniques are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00972614
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  • 3
    Electronic Resource
    Electronic Resource
    Kinetics and mechanisms of the low-temperature degradation of cellulose (1994)
    Springer
    Cellulose 1 (1994), S. 26-56 
    Details
    ISSN: 1572-882X
    Keywords: low-temperature degradation ; kinetics ; mechanisms ; electrical insulation ; transformers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A critical review is given of the degradation of cellulose in the low-temperature region (below about 300°C) of power transformer operation. The large number of kinetic studies, under a variety of environmental conditions from Kraft paper in insulating oil, to cotton and paper in oxygen, are considered in terms of a first-order polymer chain scission model. In many cases, the data are replotted to suit the model. A common activation energy of 111±6 kjmol−1 is calculated and it is shown that the pre-exponential factor, rather than the activation energy, is sensitive to the oxidizing nature of the environment and the susceptibility to degradation of the material. The chemical mechanisms of degradation are reviewed, and conclusions and recommendations are made regarding chemical condition monitoring and life prediction of electrical insulation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00818797
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  • 4
    Electronic Resource
    Electronic Resource
    Oxidation of carbidic carbon on a rhodium surface (1994)
    Springer
    Catalysis letters 27 (1994), S. 79-90 
    Details
    ISSN: 1572-879X
    Keywords: kinetics ; carbon ; oxygen ; recombination ; rhodium ; surface characterisation ; XPS ; AES
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Different mechanisms of atomic carbon and oxygen recombination on a rhodium surface are studied with Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The kinetics of adsorbed carbidic carbon oxidation (carbon coverageθ c ≈ 0.1–0.3 ML) by gas-phase oxygen that proceeds by a Langmuir-Hinshelwood reaction mechanism, provides the value of the activation energy for recombination (E rec ⇂t ≈ 170±20 kJ/mol).E rec ⇂t depends slightly on the carbon coverage. An Eley-Rideal type of reaction was observed for adsorbed oxygen and atomic gas-phase carbon recombination which occurs in a dynamic regime. The low value found for the activation energy (near zero) is consistent with the mechanism that this exothermic reaction is too fast for energy dissipation into the substrate; the energy is mainly transferred into translational, vibrational and rotational energy of CO.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00806980
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  • 5
    Electronic Resource
    Electronic Resource
    Dynamics and self-organization of catalytic systems (1994)
    Springer
    Topics in catalysis 1 (1994), S. 305-314 
    Details
    ISSN: 1572-9028
    Keywords: non-Langmuir ; kinetics ; non-linear dynamics ; oscillations ; chaos ; self-organization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of a catalytic reaction is frequently formulated in terms of simple concepts of the Langmuir type. Apart from limitations arising from the non-uniformity of the catalyst's surface and from the coverage dependence of the rate “constants”, several other complications may come into play. These may arise on the “quantum level” where energy flow between the various degrees of freedom may cause failure of simple transition state theory, as well as on the “continuum level” where formulation of rate equations in terms of coupled non-linear differential equations may give rise to a rich scenario of spatio-temporal self-organization, including kinetic oscillations, chaos, and formation of concentration patterns. Several of these phenomena are illustrated by selected examples.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01492284
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  • 6
    Electronic Resource
    Electronic Resource
    The influence of sulfur dioxide on propane oxidation activity over supported platinum and palladium (1994)
    Springer
    Catalysis letters 30 (1994), S. 41-51 
    Details
    ISSN: 1572-879X
    Keywords: propane ; oxidation ; platinum ; palladium ; sulfur dioxide ; alumina ; zirconia ; activity ; acidity ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Earlier studies have shown that sulfur dioxide and metal-support interaction can strongly influence propane oxidation over platinum. In particular, oxidation activity is enhanced when platinum is supported on sulfated γ-alumina or zirconia compared to γ-alumina. Therefore, it is of interest to compare the performance of palladium under the same experimental conditions. Four model catalysts were examined: Pt/γ-alumina, Pt/zirconia, Pd/γ-alumina and Pd/zirconia. The metal loading was kept at or below 0.05 wt% to emphasize changes in activity attributable to metal-support interaction. Reaction rates were measured with and without sulfur dioxide. Surface sulfation was analyzed by measuring acid strength and evaluating spectra obtained by Fourier-transform infrared spectroscopy. In contrast to platinum, sulfation does not promote propane oxidation on Pd/γ-alumina, and Pd/zirconia is less active than Pd/γ-alumina.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00813671
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  • 7
    Electronic Resource
    Electronic Resource
    Spectrophotometric determination of mercury with 5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine by flow injection analysis (1994)
    Springer
    Microchimica acta 113 (1994), S. 81-89 
    Details
    ISSN: 1436-5073
    Keywords: flow injection analysis (FIA) ; mercury ; porphyrin ; kinetics ; spectro-photometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine (m-Cl-TPPS4) was synthesized and used for the Spectrophotometric determination of mercury by flow injection analysis. A pseudo-first-order reaction kinetic mechanism was proposed with a rate constant of 0.8 min−1 for Hg(II) withm-Cl-TPPS4 in the presence of 8-hydroxyquinoline in a medium of 1.0M acetic acid and sodium acetate buffer solution (pH 6.22). In the optimum conditions of reaction temperature (85 ° C), stopped-flow time (60 s) and sampling volume (100 μl), the method's relative standard deviation was 0.82% (n = 12) at 5.0 μg ml−1 mercury, with a linear range of 0–12.0 μg ml−1 and an analytical frequency of 60h−1. The detection limit (3σ) was 0.025 μg ml−1. Interference studies showed that most metal ions co-existing with Hg2+ could be tolerated at 100-fold excess levels, but Zn2+, Cu2+ and Mn2+ needed to be masked. The method has been applied to the analysis of water samples with satisfactory results.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01243140
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  • 8
    Electronic Resource
    Electronic Resource
    Historical changes in sediments of Pyramid Lake, Nevada, USA: consequences of changes in the water balance of a terminal desert lake (1994)
    Springer
    Journal of paleolimnology 12 (1994), S. 87-101 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00678089
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  • 9
    Electronic Resource
    Electronic Resource
    Environmental impact of fertilizing soils by using sewage and animal wastes (1994)
    Springer
    Nutrient cycling in agroecosystems 37 (1994), S. 1-22 
    Details
    ISSN: 1573-0867
    Keywords: animal slurries and manures ; applications to soils ; carbon- ; nitrogen- ; phosphorus ; contamination ; crop production ; dissemination ; hazardous organics ; heavy metals ; inputs ; macro- and micronutrients ; pathogens ; sewage sludges ; survival- ; transfer- ; transport and adsorption rates in soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The European Community is producing annually about 300 × 106 tons of sewage sludges as well as about 150, 950,160 and 200 tons of domestic, agricultural, industrial and other wastes (street litter, dead leaves etc.). About 20–25% of the German sewage sludges, which contain in average about 3.8,1.6, 0.4, 0.6, 5.3% DM−1 N, P, K, Mg and Ca, 202, 5, 131, 349, 53, 3 and 1446 mg kg−1 DM Pb, Cd, Cr, Cu, Ni, Hg, Zn as well as ca. 37 and 5 mg kg−1 Dm polychlorinated hydrocarbons and biphenyls, are recycled annually as fertilizer. In addition environmental impacts on the arable land of Germany may derive from 76,19.2, 64.7, 33.6, 7.8 and 0.1 kg ha−1 a−1 of N, P, K, Ca, Mg and Cu added as animal manures. Besides heavy metals and hazardous organics pathogens are disseminated with organic wastes. Crop production and soil fertility generally profit from the considerable amounts of plant nutrients and carbon in sewage sludges, animal slurries and manures, but the physicochemical soil properties, the composition of microbial, faunal and plant communities as well as the metabolic processes in the soil-, rhizo- and phyllosphere are changed by organic manuring. Consequences for the soil carbon-, nitrogen-and phosphorus-cycle are discussed. Impacts of heavy metals and hazardous organics on the soil biomass and its habitat as well as on transport mechanisms and surival times of disseminated pathogens in soils are reviewed with emphasis on the German situation. A proposal for future strategies (landscape recycling) is made.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00750669
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  • 10
    Electronic Resource
    Electronic Resource
    Land application of poultry litter and water quality in Oklahoma, U.S.A. (1994)
    Springer
    Nutrient cycling in agroecosystems 40 (1994), S. 165-173 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00750462
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  • 11
    Electronic Resource
    Electronic Resource
    Response of ensete (Ensete ventricosum W.) to mineral fertilizers in southwest Ethiopia (1994)
    Springer
    Nutrient cycling in agroecosystems 37 (1994), S. 107-113 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00748551
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  • 12
    Electronic Resource
    Electronic Resource
    Slow release rate: Individual granules and population behaviour (1994)
    Springer
    Nutrient cycling in agroecosystems 39 (1994), S. 39-42 
    Details
    ISSN: 1573-0867
    Keywords: Controlled release fertilizers ; kinetics ; mechanism ; nutrient supply ; rate of release ; slow release fertilizers (SRF)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Individual granules within a given granule population of a slow-release fertilizer (SRF) have a different release pattern. The populations studied differed both in relation to the time delay before the start of the release process and to the duration of the release. An association between a short delay period and a rapid release was found. The random reease distribution can be approximated using first-order rate equations. In cases, a term describing a “lag” period should be added. The distribution of release timing among the fertilizer granules may allow a long-lasting nutrient supply to the plant, as long as there are enough granules within the root zone to allow a uniform supply pattern.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00750155
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  • 13
    Electronic Resource
    Electronic Resource
    Effect of phosphate on the sorption, desorption and plant-availability of selenium in soil (1994)
    Springer
    Nutrient cycling in agroecosystems 39 (1994), S. 189-197 
    Details
    ISSN: 1573-0867
    Keywords: interaction ; isotopic exchange ; phosphorus ; plant-availability ; selenium ; soil
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Phosphate, applied at 5µg P cm−3, decreased selenite sorption by from 30–70% in three soils studied. Both maximum sorption (Xm) and the binding-energy of sorption as indicated by the binding-energy related constant (k) or the molar free energy (ΔG) of the sorption reaction derived from the Langmuir equation were considerably decreased. On the other hand, phosphate sorption was decreased by increasing concentration of selenite from 0.2µg Se cm−3 to 1.0µg Se cm−3 in the initial solution. The competitive sorption of phosphate with selenite was likely the main mechanism involved in the P-Se interactions. The competitively sorbed selenite exhibited much larger desorption in 0.01M CaCl2 solution, more readily extractable to 0.5M NaHCO3 and significantly higher isotopic exchangeability compared to that sorbed without the competing anion. Results from pot trial using ryegrass indicated that phosphate application increased more efficiently the plant-availability of applied fertilizer Se than that of indegeneous Se in soil.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00750246
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  • 14
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    Phosphorus and nitrogen limitation of algal biomass across trophic gradients (1994)
    Springer
    Aquatic sciences 56 (1994), S. 16-28 
    Details
    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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    URL: http://dx.doi.org/10.1007/BF00877432
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  • 15
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    Contribution of nitrogen and phosphorus by precipitation in the drainage basin of the Santillana Reservoir (Madrid) (1994)
    Springer
    Environmental geology 23 (1994), S. 99-104 
    Details
    ISSN: 1432-0495
    Keywords: Nitrogen ; phosphorus ; Precipitation collector ; Nutrients rates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract The contribution of nitrogen and phosphorus due to precipitation constitutes the second most important route after superficial runoff. The sampling carried out during a two-year period by means of a precipitation collector allows us to determine the contribution of this route both qualitatively and quantitatively. Nitrogen is mainly supplied in an inorganic form, while phosphorus is principally supplied as orthophosphate. During the period of this study (March 1986–February 1988) it was found that in the Santillana Reservoir Watershed the level of nitrogen supplied by precipitation constitutes an average of 4.87% and the level of phosphorus constitutes 8.01%. The contribution of nitrogen varies in inverse ratio to precipitation and the contribution of phosphorus varies in direct ratio.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00766982
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  • 16
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    Comparative studies on species-specific reactivity between renin and angiotensinogen (1994)
    Springer
    Molecular and cellular biochemistry 131 (1994), S. 43-47 
    Details
    ISSN: 1573-4919
    Keywords: angiotensinogen ; kinetics ; recombinant protein ; renin ; species specificity ; transgenic mouse
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The renin-angiotensin system (RAS) is the most important regulator of electrolyte homeostasis and blood pressure. Our recently generated transgenic mice carrying either the human renin (hREN) or human angiotensinogen (hANG) genes did not develop hypertension but dual gene strains obtained by cross-mating separate lines of mice exhibited a chronically sustained increase in blood pressure, suggesting the presence of species-specific reactivity between renin and angiotensinogen. In order to examine this specificity, the present study was designed to perform a strictly comparative study on hydrolysis of hANG by hREN and mouse submandibular renin (mREN)in vitro by using pure proteins. The recombinant hANG (rhANG) and the synthetic human-type tridecapeptide (hTDP), Asp-Arg-Val-Tyr-Ile-His-Pro-Phe-His-Leu-Val-Ile-His, corresponding to the N-terminal sequences of hANG, were used to determine the species specificity of recombinant hREN (rhREN) and mREN. While hTDP was cleaved by both rhREN with similar Km and with the same order of kcat, rhANG was cleaved by mREN with 16.7-fold higher Km and with 28.2-fold lower kcat than by rhREN. These results showed that kcat/Km value of mREN for rhANG was 468-fold lower than that for rhREN acting on rhANG.
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    URL: http://dx.doi.org/10.1007/BF01075723
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  • 17
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    Morphological characteristics of the oxidation of niobium II: The role of stresses on high-temperature morphologies (1994)
    Springer
    Oxidation of metals 41 (1994), S. 235-250 
    Details
    ISSN: 1573-4889
    Keywords: niobium ; oxidation ; morphology ; kinetics ; stresses
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of niobium at high temperature (900°C) leads to reaction products with “exotic” morphologies. Morphological and kinetics analysis have been undertaken with Nb platelets. A growth mechanism of the oxide at the edges of the platelet is proposed.
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    URL: http://dx.doi.org/10.1007/BF01080782
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  • 18
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    The effect of purity on high-temperature oxidation of zirconium (1994)
    Springer
    Oxidation of metals 42 (1994), S. 223-237 
    Details
    ISSN: 1573-4889
    Keywords: kinetics ; scale ; oxidation ; zirconium ; purity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation kinetics of zirconium of different purities were studied over the temperature range of 600–1300°C (α- and β-phases). The structure of the oxidized specimens was examined. TGA, XRD, EPMA, SEM, metallographic analysis, and microhardness measurements were carried out. Impurity elements were found to increase the oxidation rate of technical zirconium. The mechanism of the effect of impurity elements on zirconium oxidation was shown to differ for the α- and β-phases. Activation energies were calculated for the parabolic and linear stages of oxidation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01052024
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  • 19
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    The effect of purity on the high-temperature oxidation of hafnium (1994)
    Springer
    Oxidation of metals 42 (1994), S. 249-263 
    Details
    ISSN: 1573-4889
    Keywords: kinetics ; scale ; oxidation ; hafnium ; purity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation kinetics of hafnium of different purities were studied in the temperature range of 800–1200°C. This paper concerns the structure studies of the oxidized samples. TGA, XRD, SEM methods, and microhardness measurements were used. Hafnium oxidation follows the parabolic rate law, changing with time to the linear one. Oxidation-reaction products are HfO2(moncl) and α-solid solution of oxygen in hafnium. Anomalous oxidation behavior of hafnium having a high impurity content was found in the range 800–950°C. Activation energies for the parabolic and linear oxidation stages were calculated.
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    URL: http://dx.doi.org/10.1007/BF01052026
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  • 20
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    Enzymology of ADP-ribose polymer synthesis (1994)
    Springer
    Molecular and cellular biochemistry 138 (1994), S. 33-37 
    Details
    ISSN: 1573-4919
    Keywords: poly(ADP-ribose) polymerase ; structure ; chemistry ; kinetics ; automodification ; mechanism(s)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract In this minireview, we summarize recent advances on the enzymology of ADP-ribose polymer synthesis. First, a short discussion of the primary structure and cloning of poly(ADP-ribose) polymerase (PARP) [EC 2.4.2.30], the enzyme that catalyzes, the synthesis of poly(ADP-ribose), is presented. A catalytic distinction between the multiple enzymatic activities of PARP is established. The direction of ADP-ribose chain growth as well as the molecular mechanism of the automodification reaction catalyzed by PARP are described. Current approaches to dissect ADP-ribose polymer synthesis into individual reactions of initiation, elongation and branching, as well as a partial mechanistic characterization of the ADP-ribose elongation reaction at he chemical level are also presented. Finally, recent developments in the catalytic characterization of PARP by site-directed mutagensis are also briefly summarized.
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    URL: http://dx.doi.org/10.1007/BF00928440
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    A two-component, non-aqueous route to silica gel (1994)
    Springer
    Journal of sol gel science and technology 2 (1994), S. 35-41 
    Details
    ISSN: 1573-4846
    Keywords: carboxylic acids ; mechanism ; kinetics ; ultrafine porosity ; CO2 adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new means for generating silica gel has been developed. Simple two component systems comprising tetraalkoxysilanes and strong carboxylic acids such as formic acid can react rapidly to give transparent monolithic gels. The acid serves as solvent, water source, and catalyst for both hydrolysis and condensation. Water need not be present as an initial reactant; it is generated in situ during the reaction. The gelation reaction is at least two orders of magnitude faster than those conducted in conventional acid-catalyzed aqueous systems at comparable pH*. Kinetic evidence indicates a lowering of the activation energy of condensation reactions, believed to be associated with reaction of silyl carboxylates and silanol groups. Physical properties of the dry gels such as bulk density more closely resemble conventional acid-catalyzed gels than those associated with other rapidly gelling systems. Dry gels often exhibit porosity so fine that nitrogen (at 77°K) is not absorbed at significant rates. Independent evidence of porosity arises from comparison of skeletal and bulk densities, sample immersion in water and adsorption isotherms of CO2.
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    URL: http://dx.doi.org/10.1007/BF00486210
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    Substitution of the amino acid at position 102 with polar and aromatic residues influences substrate specificity of lactate dehydrogenase (1994)
    Springer
    The protein journal 13 (1994), S. 129-133 
    Details
    ISSN: 1573-4943
    Keywords: Lactate dehydrogenase ; kinetics ; mutagenesis ; specificity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The Gin residue at amino acid position 102 ofBacillus stearothermophilus lactate dehydrogenase was replaced with Ser, Thr, Tyr, or Phe to investigate the effect on substrate recognition. The Q102S and Q102T mutant enzymes were found to have a broader range of substrate specificity (measured byk cat/K m) than the wild-type enzyme. However, it is evident that either Ser or Thr at position 102 are of a size able to accommodate a wide variety of substrates in the active site and substrate specificity appears to rely largely on size discrimination in these mutants. The Q102F and Q102Y mutant enzymes have low catalytic efficiency and do not show this relaxed substrate specificity. However, their activities are restored by the presence of an aromatic substrate. All of the enzymes have a very low catalytic efficiency with branched chain aliphatic substrates.
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    DEDO: A specific, fluorescent inhibitor for spectroscopic investigations of Na,K-ATPase (1994)
    Springer
    Journal of fluorescence 4 (1994), S. 287-290 
    Details
    ISSN: 1573-4994
    Keywords: Na,K-ATPase ; fluorescent inhibitor ; kinetics ; energy transfer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract The interaction between the fluorescent ouabain derivative DEDO and purified renal Na,K-ATPase (isolated from different animal species) is investigated. Equilibrium binding studies provide a pK value of about 7.5 and a stoichoimetric coefficient of 1. Nonmodified ouabain exhibits the same affinity to the rabbit enzyme; the enzyme originating from the other sources binds DEDO 10 times less strongly than ouabain. Kinetic studies indicate that this is the consequence of a 10 times higher dissociation rate constant of the complexes formed with DEDO. The fluorescence emission intensity of DEDO is enhanced, being dependent on the enzyme source. The single decay time of DEDO is 3 ns in the absence and 21 ns in the presence of the rabbit enzyme and 14 ns in the presence of the pig renal enzyme. This result suggests that the fluorophore of DEDO is bound to a very hydrophobic environment of the enzyme. Further characterization of the static fluorescence spectra provides evidence for energy transfer between Trp residues of the enzyme and DEDO. Distance estimations suggest that one or two Trp residues are likely to be located in the proximity of the fluorophore.
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    URL: http://dx.doi.org/10.1007/BF01881441
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    Stopped-flow fluorescence studies of the interaction of a mutant form of cytochrome b5 with lipid vesicles (1994)
    Springer
    Journal of fluorescence 4 (1994), S. 227-233 
    Details
    ISSN: 1573-4994
    Keywords: Cytochrome b5 ; site-directed mutagenesis ; kinetics ; fluorescence ; membrane-binding
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Cytochrome b5 binds spontaneously to lipid vescles and also self-associates in aqueous solution. Two mutant proteins have been generated, one has a self-association constant which is less than that of the native protein, while the other has a larger self-association constant. All three proteins have Trp in the membrane-binding domain but as aqueous solutions of these proteins contain differing amounts of monomeric protein, the kinetics of fluorescence enhancement, when the proteins are mixed with lipid vesicles, are complex. Similar complex kinetics are seen when the Trp are quenched by the addition of bromolipid vesicles. The mutant which has Trp 108 and 112 both replaced by Leu does not self-associate and shows monoexponential stopped-flow fluorescence kinetics. Identical rate constants are seen with this mutant for fluorescence enhancement by POPC and fluorescence quenching by three bromolipids with bromines at the 6,7-, 9,10-, and 11,12-positions of thesn-2 acyl chain. This rate constant is only 1% of the calculated collisional rate constant and it is suggested that the reduced rate is caused by a reduction in the number of productive collisions rather than by a slow rate of penetration of the membrane-binding domain into the bilayer.
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    URL: http://dx.doi.org/10.1007/BF01878455
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    Kinetics and mechanisms of halide ion catalysis of CO substitution reactions in Os3(CO)12 and Ru3(CO)12 metal carbonyl clusters (1994)
    Springer
    Russian chemical bulletin 43 (1994), S. 1451-1456 
    Details
    ISSN: 1573-9171
    Keywords: metal carbonyl clusters ; osmium, ruthenium, alkynes ; kinetics ; catalytic effect of halide ions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The results of kinetic studies on ligand substitution in [M3(CO)11X]− complexes (M = Ru, Os; X = Cl, Br, I) are summarized. The [Os3(CO)11X]− complexes react with PPh3 under mild conditions to initially yield monosubstituted products [Os3(CO)10(PPh3)X]−. The rate of CO substitution obeys a first-order equation with respect to the concentration of the complex and does not depend on the ligand concentration. The rates of the reactions decrease in the order Cl 〉 Br 〉 I withΔH≠ values increasing from 15 to 18 kcal mol−1 and ΔS ≠ values varying from −19 to −13 cal mol−1 K−1. The enhanced reactivities of these complexes as well as the low activation energies and negative activation entropies are discussed in terms of the effects of μ-X bridge formation on the transition state of the reaction. Reactions of PPN[Ru3(CO)11−x (Cl)] (PPN is the bis(triphenylphosphine)iminium cation;x=0, 1) and PPN[Ru3(CO)9(μ3-I)] with alkynes are also reported. The reactivities of alkynes follow the order BuC≡CH ≥ PhC≡CH ≥ EtC≡CEt ≥ PhC≡CPh. The higher rates of the reactions of monosubstituted acetylenes compared with those of their disubstituted analogs are explained by agostic interaction between the metal atom and the C-H bond in the reaction transition state and by steric effects. The results obtained attest that the reaction with alkynes occursvia intermediates containing halide bridges and that μ3-halide complexes are more reactive than μ2-halide complexes.
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    Oxidation of organic amide ions by dioxygen (1994)
    Springer
    Russian chemical bulletin 43 (1994), S. 1646-1650 
    Details
    ISSN: 1573-9171
    Keywords: aromatic amines ; amide ions ; oxidation ; dioxygen ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Amide ions generated from secondary aromatic amines with pK a 〉 21 are readily oxidized by dioxygen in the system KOH+18-crown-6+DMSO at room temperature. It was found that the rate limiting stage of the reaction is the interaction of dioxygen with amide ions. The rate of the reaction is determined by two main factors, varying in opposite directions: the degree of ionization of the amine and the reactivity of the amide ions towards dioxygen.
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    Correlation between solvent-reorganization dynamics and the kinetics of metallotropy in polar media (1994)
    Springer
    Russian chemical bulletin 43 (1994), S. 368-371 
    Details
    ISSN: 1573-9171
    Keywords: kinetics ; solvent dynamics ; radical
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of metallotropy of the 3,6-di-tert-butyl-2-(triphenylstannyl)oxyphenoxyl radical has been studied by ESR. The correlation between chemical exchange time τex, solvent polarity, and longitudinal relaxation time of the solvent corresponds to the model of a process controlled by molecular dynamics. A linear relation between τex and correlation time τc for reorientation movements of the radical is found: τex = α · τc. The coefficient α depends on the dielectric properties of the solvent.
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    URL: http://dx.doi.org/10.1007/BF01169707
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    The role of suspended matter in the distribution of dissolved inorganic phosphate, iron and aluminium in the Ems estuary (1994)
    Springer
    Aquatic ecology 28 (1994), S. 383-395 
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    ISSN: 1573-5125
    Keywords: Ems estuary ; phosphorus ; iron ; fluorescence ; aluminium ; adsorption ; suspended matter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract In winter 1992/1993, a persistent local maximum in fluorescence, dissolved iron, dissolved aluminium and dissolved inorganic phosphate was found, upstream of the turbidity maximum in the freshwater zone of the Ems estuary (The Netherlands — Federal Republic Germany; western Europe). Upstream of this local maximum values ranged from 6 to 9 rel. units fluorescence, 0.9 to 2.4 μmol dm−3 iron, 0.5 to 0.7 μmol dm−3 aluminium and 0.6 to 2.3 μmol dm−3 dissolved inorganic phosphate. Within the maximum peak values of 24 rel. units fluorescence, 5.8 μmol dm−3 iron, 1.4 μmol dm−3 aluminium and 8.3 μmol dm−3 dissolved inorganic phosphate were observed. Downstream, fluorescence (indicator of dissolved organic carbon) showed conservative mixing with sea water, whereas dissolved iron, aluminium and dissolved inorganic phosphate did not. Dissolved aluminium and iron were quickly removed from solution to reach values of ∼100 nmol dm−3 aluminium and ∼0.3 μmol·dm−3 Fe at salinities of approximately 7 PSU. Further seaward iron concentrations gradually decreased to levels below 0.04 μmol dm−3. Dissolved aluminium first decreased to ∼20 nmol dm−3 at 29 PSU and increased again to concentrations of 30–44 nmol dm−3 at higher salinities. Dissolved inorganic phosphate, however, first decreased to upstream concentrations before reaching a secondary peak in the mid-estuarine reaches. At salinities 〉25 PSU dissolved inorganic phosphate mixed conservatively with sea water. It is hypothesized that adsorption-desorption equilibria are responsible for the local maximum values of fluorescence (DOC), iron, aluminium and dissolved inorganic phosphate. The similarity between the observed curves suggests a common underlying process, possibly related to the adjustment of new equilibria between suspended matter of marine and riverine origin.
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    URL: http://dx.doi.org/10.1007/BF02334208
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    Determination of orthophosphate in highly saline waters (1994)
    Springer
    International journal of salt lake research 3 (1994), S. 159-173 
    Details
    ISSN: 1573-8590
    Keywords: phosphorus ; orthophosphate ; phosphomolybdenum blue ; salt effect ; hypersaline ; saline ; lakes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geography
    Notes: Abstract Standard methods for the determination of phosphorus as phosphate ion are now well established for fresh and marine waters. In highly saline waters, however, salt effects due to ionic strength, or to particular ions present, may result in method interferences. Three methods of analysis of phosphate based on the formation of phosphomolybdenum blue complexes have been evaluated here for hypersaline waters. Stannous chloride reduction in aqueous media exhibits a substantial salt effect and its use is not recommended. Stannous chloride reduction following extraction into non aqueous solvents shows a significant salt effect (up to 30 per cent) in solutions of salinity 〉100 g L−1. Dilution of hypersaline waters to below this salinity may overcome the salt effect but the method suffers from other disadvantages involving resource constraints and health and safety considerations. Ascorbic acid reduction, catalysed by antimony (III) ions, appears to offer the most promise for hypersaline waters. Turbidity in samples having high salinity (〉 100 g L−1) and high phosphorus concentrations (〉 500 μg P L−1) changes the spectral characteristics of solutions but linear calibration curves still result for concentrations in the range 400 to 1,000 μg P L−1. The occurrence of turbidity is also affected by the ionic composition of hypersaline waters since solutions made from sea salt give different results to those made from sodium chloride. Dilution of samples, to give salinities less than 100 g L−1 prior to reduction is recommended to avoid turbidity. The salt effect in these lower salinity waters is less than 3 per cent up to 100 g L−1.
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    The Determination of Interfacial Transfer Constants Using Side-by-Side Diffusion Cells (1994)
    Springer
    Pharmaceutical research 11 (1994), S. 1325-1329 
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    ISSN: 1573-904X
    Keywords: interfacial transfer ; partition coefficients ; side-by-side diffusion cells ; kinetics ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A side-by-side diffusion cell setup has been used to determine the pH 7.4 buffer-octanol interfacial transfer constants for twelve compounds. The compounds are a diverse selection of pharmaceuticals, amino acids, and small organics which covers a log distribution coefficient (K) range of −3 to 2. A model based on the resistance summation approach, which deals explicitly with the various barriers involves in the transport process, was used to derive transfer constants from the transport data for each compound. The model gave constants that were well behaved in a published model describing the correlation of the forward and reverse transfer constants to equilibrium K values (r2 = 0.999). These studies demonstrate the utility of side-by-side diffusion cells for the determination of interfacial transfer constants. This type of setup offers the advantages of controlled interfacial area, measurable hydrodynamic effects, and a commercially available apparatus.
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    Entrapping Efficiency and Drug Release Profile of an Oil-in-Water (o/w) Emulsion Formulation Using a Polydimethylsiloxane-Coated Glass Bead Assay (1994)
    Springer
    Pharmaceutical research 11 (1994), S. 503-507 
    Details
    ISSN: 1573-904X
    Keywords: drug delivery ; emulsion ; entrapping efficiency ; polydimethylsiloxane ; glass beads ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Evaluation of entrapping efficiency is difficult for an o/w emulsion formulation containing a lipophilic oily drug, isocarbacyclin methyl ester (TEI-9090), by commonly employed techniques (dialysis, ultrafiltration, or gel filtration), because of its adsorption to the system materials. Employing this characteristic of TEI-9090, we developed an adsorption technique with polydimethylsiloxane-coated glass beads (PDMS-GB). The assay is based on the quantitative adsorption of unentrapped TEI-9090 to the PDMS-GB. The entrapping efficiency of a 10% soybean oil emulsion containing [3H]TEI-9090 (1 µg/mL) assayed by this method approached 100%. The PDMS-GB assay was performed for the emulsion diluted 100 times with physiological saline at different time intervals after dilution over a period of 24 hr. A plot of [3H]TEI-9090 in the emulsion particles versus time showed rapid release within 1 hr, followed by very slow release, reaching equilibrium. Applying first-order kinetics, the data were found to fit to a biexponential equation over the first hour of release. The terminal release resembled the first-order release of the drug from the phospholipid-rich infranatant, which was separated from the creamy layer by ultracentrifugation of the emulsion and contained 35% [3H]TEI-9090. These results suggest that the drug is released from two components in the emulsion.
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    Acid-Catalyzed Peptide Bond Hydrolysis of Recombinant Human Interleukin 11 (1994)
    Springer
    Pharmaceutical research 11 (1994), S. 72-76 
    Details
    ISSN: 1573-904X
    Keywords: interleukin 11 (IL-11) ; recombinant human IL-11 ; degradation ; kinetics ; products ; aspartate–proline cleavage
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Recombinant human interleukin 11 (rhIL-11) is a multispectrum cytokine that plays an important role in megakaryocytopoiesis and platelet production. Probing rhIL-11 chemical reactivity in aqueous solution is an important initial step in developing a dosage form for rhIL-11 clinical trials. This report documents rhIL-11 degradation kinetics at 50°C in solutions adjusted to pH 3.0 to 9.5. Stressed samples were analyzed by reverse-phase HPLC and degradation product peaks were isolated for structural characterization. The results show maximal stability in the region pH 6.5 to 7.0. Degradation product identification shows that the major reaction pathway in acidic solution involves peptide cleavage at aspartate133–proline134. In alkaline solution, protein disappearance proceeds via nonspecific loss to container surfaces. Degradation products at alkaline pH have not been identified.
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    Epimerization and Hydrolysis of Dalvastatin, a New Hydroxymethylglutaryl Coenzyme A (HMG-CoA) Reductase Inhibitor (1994)
    Springer
    Pharmaceutical research 11 (1994), S. 165-170 
    Details
    ISSN: 1573-904X
    Keywords: dalvastatin ; hydroxymethylglutaryl coenzyme A (HMG-CoA) reductase inhibitor ; epimerization ; hydrolysis ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In aqueous solutions, dalvastatin (1) undergoes epimerization as well as hydrolysis. The transformation of the drug was studied as a function of pH at 25°C in aqueous solutions containing 20% acetonitrile. At all pH values, first-order plots for the conversion are biphasic, indicating rapid equilibration of 1 with its epimer (2) and slower hydrolysis of 1 to the corresponding β-hydroxy acid (3). Apparent first-order rate constants for the biexponential equation are given as a function of pH. The alkyl–oxygen cleavage of the lactone ring results in the epimerization of 1 to 2, whereas the acyl–oxygen cleavage results in the hydrolysis of 1 to 3. The epimerization is an SN1 reaction reaching an equilibrium of [l] eq/[2] eq = 1.27. The epimerization rate is increased with an increase in the water content of the solvent. The hydrolysis of 1 to 3 is acid and base catalyzed. The hydrolysis is reversible in acidic media and irreversible in neutral and basic media. At pH values greater than 9, the hydrolysis reaction proceeds more rapidly than the epimerization.
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    Entrapping Efficiency of an Oil-in-Water Emulsion Containing Isocarbacyclin Methyl Ester (TEI-9090) in Dog and Human Sera (1994)
    Springer
    Pharmaceutical research 11 (1994), S. 1677-1679 
    Details
    ISSN: 1573-904X
    Keywords: o/w emulsion ; serum ; entrapping efficiency ; kinetics ; SDS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1023/A:1018938627408
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    Is Stability Prediction Possible for Protein Drugs? Denaturation Kinetics of β- Galactosidase in Solution (1994)
    Springer
    Pharmaceutical research 11 (1994), S. 1721-1725 
    Details
    ISSN: 1573-904X
    Keywords: protein drug ; denaturation ; aggregation ; kinetics ; Eyring equation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Denaturation and aggregation kinetics of Aspergillus oryzae β-galactosidase in solution were studied in order to determine whether the stability of protein drugs can be predicted. Denaturation of β-galactosidase, monitored by measuring enzyme activity, conformed to first-order kinetics, whereas aggregation of the denatured form, monitored by high performance size exclusion chromatography, showed a reaction order higher than 1. Denaturation of β-galactosidase was irreversible and exhibited a biphasic kinetic pattern which could be explained by assuming that two isoenzymes denatured irreversibly at different rates. Linear Arrhenius plots were obtained for the estimated rate constants, and ΔH
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    Block copolymerization initiated by Mn(III)-poly(ethylene glycol) redox system — general features and kinetics (1994)
    Springer
    Colloid & polymer science 272 (1994), S. 777-783 
    Details
    ISSN: 1435-1536
    Keywords: Mn(III)-poly(ethylene glycol) ; acrylonitrile ; block copolymerization ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The kinetics and mechanism of thermal polymerization of acrylonitrile initiated by Mn(III) pyrophosphate — poly(ethylene glycol) (PEG, molecular weight 6000) redox system in aqueous sulfuric acid medium was studied in the temperature range 30–60°C. The overall rates of polymerization and the disappearance of Mn3+ were determined. The polymerization was initiated by the organic free radical produced from the Mn3+-PEG reaction and the termination was by the metal ions. The rate of polymerization of acrylonitrile was found to be directly proportional to the square of the monomer concentration and first power of PEG concentration, and inversely proportional to the concentration of Mn3+. The rate of manganic ion disappearance was found to be directly proportional to manganic ion concentration and PEG concentration, and independent of the monomer concentration. Based on these observations, a plausible reaction scheme was suggested and suitable kinetic expressions were evaluated.
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    Growth and elemental content of several sagebrush-steppe species in unburned and post-wildfire soil and plant effects on soil attributes (1994)
    Springer
    Plant and soil 164 (1994), S. 35-41 
    Details
    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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    Subterranean clover decline in permanent pastures in north-eastern Victoria (1994)
    Springer
    Plant and soil 164 (1994), S. 231-241 
    Details
    ISSN: 1573-5036
    Keywords: phosphorus ; root disease ; soil acidity ; subterranean clover ; yield decline
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Experimental sites were established at two locations in north-eastern Victoria to define factors limiting the establishment and growth of Trifolium subterranean L. (subterranean clover). Liming the soil, seed inoculation and fungicide application were used in renovating subterranean clover pasture on two acidic soils (Longwood: brown/grey sandy loam DY 3.14 and Seymour: grey brown light clay DY 3.22, Northcote classification) with mean annual rainfall of 650 mm and 600 mm respectively. Soil acidity, low available soil phosphorus and plant disease were identified as factors limiting clover yield on these soils. Significant yield responses to lime (35–140%) were obtained with subterranean clover at both sites, with corresponding decreases in Al in the 0–10 cm soil horizon. Liming the soil, when combined with seed inoculation, increased the number and effectiveness of root nodules at both sites. Soil P available for plant growth was low at both sites (6.1 and 8.4 μg g−1) resulting in sub-optimal P concentrations in the clover herbage (45 mmol kg−1 at Longwood). Levels of root disease were low but Aphanomyces euteiches and Phytophthora clandestina (causal agents of lateral and tap root rot) were detected frequently on roots. Application of fungicide resulted in higher dry matter yields (p=0.05) at both sites. An assessment of the relative contributions of these limiting factors and the benefits to be obtained from better management would provide a clearer picture of the profitability and sustainability of this farming system.
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    Phosphorus depletion in the rhizosphere as influenced by soil moisture (1994)
    Springer
    Plant and soil 159 (1994), S. 213-218 
    Details
    ISSN: 1573-5036
    Keywords: concentration gradient ; diffusion ; phosphorus ; rhizosphere ; soil moisture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract To study the influence of soil moisture on phosphorus (P) depletion in the rhizosphere, maize (Zea mays cv. Trak) was pre-grown in vermiculite filled-PVC tubes for 9 days and then the plants with the tubes were transplanted into soil columns maintained at two soil moisture levels (θ) of 0.14 and 0.20 cm3 cm−3 for 10 days. The soil columns were separated at 1 cm depth by a nylon screen of 53 μm inner mesh size, into 1 cm soil layer above and 3 cm soil column below screen. A root mat developed over the screen, but root hairs only could penetrate it. Regardless of the soil moisture level in the columns, and adequate and equal water and nutrients supply was maintained via wicks from an external nutrient solution to the plant roots in vermiculite. After 10 days, the soil columns were separated from the root mats, quickly frozen in liquid nitrogen and sliced into thin layers (0.2mm) using a refrigerated microtome to give soil samples at defined distances from the root mats for analyses. Lower soil moisture (θ=0.14) resulted in narrower and steeper depletion profile of 0.5 M NaHCO3 extractable P (NaHCO3-Pi) as compared to higher soil moisture (θ=0.20). Depletion of P in soil solution in the immediate vicinity of root mats did not differ much but the extension of the depletion zones was 0.10 cm at θ=0.14 and 0.20 cm at θ=0.20. The depletion up to 0.05cm with θ=0.14 and up to 0.07 cm with θ=0.20 was uniform, and may be attributed to the depletion in the root hair zone. Beyond the root hair zones, the theory of diffusion and mass flow was able to explain the observed differences in shape and extent of the P depletion profiles at the two soil moisture levels.
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    Effect of elevated CO2 on mycorrhizal colonization of loblolly pine (Pinus taeda L.) seedlings (1994)
    Springer
    Plant and soil 165 (1994), S. 81-88 
    Details
    ISSN: 1573-5036
    Keywords: carbohydrates ; ectomycorrhizae ; elevated CO2 ; phosphorus ; Pinus taeda L. ; Pisolithus tinctorius (Pers.) Coker & Couch
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Interactive effects of elevated atmospheric CO2 and phosphorus supply on mycorrhizal colonization rates were investigated using loblolly pine (Pinus taeda L.) seedlings from Florida and coastal North Carolina. Seedlings from both populations were grown in greenhouses maintained at either 35.5 Pa or 71.0 Pa CO2. In both CO2 treatments, seedlings were grown in a full factorial experiment with or without mycorrhizal inoculum and with an adequate or a limiting supply of phosphorus. Seedlings were harvested 60, 90 and 120 days after emergence and at each harvest root subsamples were examined to determine the percent of fine roots that were mycorrhizal. Additionally, root carbohydrate and nutrient levels were measured at each harvest. Root starch, sugar and total non-structural carbohydrate (TNC) concentrations were increased by growth in elevated CO2 and decreased by mycorrhizal colonization. Phosphorus stress decreased root starch concentrations, increased root sugar concentrations and did not significantly affect TNC concentrations. However, despite significant effects on root carbohydrate levels, there were generally no significant treatment effects on mycorrhizal colonization. Additionally, at all harvests, root starch and sugar concentrations were not correlated with percent of fine roots that were mycorrhizal. These results suggest that although elevated CO2 may significantly increase root carbohydrate levels, the increases may not affect the percent of fine roots that are mycorrhizal.
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    Enhanced root system C-sink activity, water relations and aspects of nutrient acquisition in mycotrophic Bouteloua gracilis subjected to CO2 enrichment (1994)
    Springer
    Plant and soil 165 (1994), S. 139-146 
    Details
    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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    Growth response and phosphorus uptake of rye with long and short root hairs: Interactions with mycorrhizal infection (1994)
    Springer
    Plant and soil 167 (1994), S. 247-254 
    Details
    ISSN: 1573-5036
    Keywords: efficiency ; Glomus intraradices ; phosphorus ; root hair ; rye ; Secale cereale L. ; VA mycorrhiza
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Plant growth and phosphorus (P) uptake of two selections of rye (Secale cereale L.) differing in length of root hairs, in response to mycorrhizal infection were investigated. Rye plants with short root hairs (SRH) had a greater length of root infected by Glomus intraradices (up to 32 m pot−1) than those with long root hairs (LRH) (up to 10 m pot−1). Application of P decreased the percentage of root length infected in both selections. In low-P soil, mycorrhizal infection increased shoot and root P concentration, especially in LRH plants. Generally, LRH had higher shoot dry weight than SRH plants. P uptake was increased both by LRH and by mycorrhizal infection. Differences in specific P uptake and P utilization efficiency between SRH and LRH plants were observed in non-mycorrhizal plants. With low P supply, P utilization efficiency (dry matter yield per unit of P taken up) of LRH plants increased with time. However, mycorrhizal infection reduced P utilization efficiency, particularly of SRH plants. SRH plants, which were agronomically less efficient (i.e. low dry matter yield at low P supply) were more responsive to either mycorrhizal infection or P addition than the LRH plants. No interaction was observed between mycorrhizal infection and root hair length.
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    Nutrient uptake in eastern deciduous tree seedlings (1994)
    Springer
    Plant and soil 160 (1994), S. 193-199 
    Details
    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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    Carbon cost of root systems: an architectural approach (1994)
    Springer
    Plant and soil 165 (1994), S. 161-169 
    Details
    ISSN: 1573-5036
    Keywords: carbon cost ; phosphorus ; Phaseolus vulgaris ; root architecture ; root growth ; root simulation model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Root architecture is an important component of nutrient uptake and may be sensitive to carbon allocational changes brought about by rising CO2. We describe a deformable geometric model of root growth, SimRoot, for the dynamic morphological and physiological simulation of root architectures. Using SimRoot, and measurements of root biomass deposition, respiration and exudation, carbon/phosphorus budgets were developed for three contrasting root architectures. Carbon allocation patterns and phosphorus acquisition efficiencies were estimated for Phaseolus vulgaris seedlings with either a dichotomous, herringbone, or empirically determined bean root architecture. Carbon allocation to biomass, respiration, and exudation varied significantly among architectures. Root systems also varied in the relationship between C expenditure and P acquisition, providing evidence for the importance of architecture in nutrient acquisition efficiency.
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    Effects of growth period, plant age and changes in solution aluminium concentrations on aluminium toxicity in wheat (1994)
    Springer
    Plant and soil 166 (1994), S. 21-30 
    Details
    ISSN: 1573-5036
    Keywords: aluminium ; growth period ; phosphorus ; plant age ; root length ; root width ; solution culture ; techniques ; Triticum aestivum ; variation ; wheat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The effects of growth period (time between transplanting and harvesting), plant age at which aluminium (Al) was added to solution, changes in Al concentration, and solution culture techniques (monitoring and adjusting solution Al concentrations thrice weekly or weekly replacement of the solutions) were investigated using a low ionic strength (2.7×10−3 M) solution culture technique. The wheat (Triticum aestivum L.) cultivars Waalt (Al-tolerant) and Warigal (Al-sensitive), or the near isogenic lines bred from these cultivars (RR for the Al-tolerant line and SS for the Al-sensitive line) were grown. In all experiments and treatments, Al additions were required to maintain the nominal concentration. The decline in solution Al concentrations was partially attributed to formation of an Al-hydroxy-phosphate precipitate with an Al:P molar ratio of 2.8 to 4.0. Increasing the growth period from 14 to 28 days increased Al sensitivity in Warigal but not in Waalt. When plants were exposed to Al for the same time, increasing the age of the plants that Al was added to solution decreased sensitivity to Al. Differential Al tolerance between the two lines was evident when solutions were monitored thrice weekly or replaced weekly. However, the Al concentration required to reduce relative yield by a given amount when the solutions were replaced weekly was about twice that when the solutions were monitored. With a constant growth period of 28 days, increasing solution Al concentrations for 3 or more days resulted in decreased yields at harvest. The exact effect depended on the cultivar, plant part (tops or roots), when solution Al concentrations were increased and the duration of the increase. For example, increasing Al concentrations from 5 μM to 20 μM for 10 days reduced yield in the RR line by approximately 50% in the tops and 30% in the roots beyond the effect of 5 M but had no effect in the SS line due to yields already being low at 5 μM. Adding 10 μM Al to solution for 6 days at the beginning of the experiment reduced yield by 25% in the RR line and 50% in the SS line. In contrast, adding 10 μM Al for 6 days in the middle of the growth cycle had no effect on the RR line but reduced yield by approximately 25% in the SS line. These results show that growth period, the age of the plants at which Al is added and the technique used (monitored or weekly replacement) all need to be considered when comparing results from different experiments. These results also show that the Al concentrations in solution need to be regularly monitored in long term experiments.
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    Colonisation of wheat by VA-mycorrhizal fungi was found to be higher on a farm managed in an organic manner than on a conventional neighbour (1994)
    Springer
    Plant and soil 160 (1994), S. 33-40 
    Details
    ISSN: 1573-5036
    Keywords: organic agriculture ; phosphorus ; rock phosphate ; VA-mycorrhizas ; wheat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Levels of colonisation by vesicular-arbuscular (VA)-mycorrhizal fungi were compared between adjacent farms, one operated in a conventional manner and the other run according to organic farming principles. Wheat grown on the organic farm was found to have VA-mycorrhizal colonisation levels consistently 2 to 3 times higher than wheat on the conventional farm. Glasshouse and field trials indicated that the lower colonisation levels on the conventional farm were due to continual use of fertiliser containing soluble phosphorus (P). The fertiliser appeared to have an immediate negative effect on the rate of colonisation, and also appeared to have a long term negative effect through maintaining higher levels of soluble P in the soil, and by decreasing inoculum levels. Use of the relatively insoluble reactive rock phosphate fertiliser on the organic farm did not decrease levels of VA-mycorrhizas. Colonisation levels did not vary between wheat varieties, and herbicides and seed dressings were also not found to be having any significant effect on levels of colonisation.
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    URL: http://dx.doi.org/10.1007/BF00150343
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    Nutrient balances and phytoplankton dynamics in two agriculturally loaded shallow lakes (1994)
    Springer
    Hydrobiologia 275-276 (1994), S. 359-369 
    Details
    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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    URL: http://dx.doi.org/10.1007/BF00026726
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    A diatom-phosphorus transfer function for shallow, eutrophic ponds in southeast England (1994)
    Springer
    Hydrobiologia 275-276 (1994), S. 391-410 
    Details
    ISSN: 1573-5117
    Keywords: diatoms ; phosphorus ; palaeolimnology ; transfer function ; United Kingdom ; shallow
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Shallow ponds in southeast England are often eutrophic with high phosphorus concentrations. The aim of this study was to develop a diatom-phosphorus ‘transfer function’ to enable past phosphorus levels in such waters to be inferred from the sediment record. A water chemistry survey of 123 randomly chosen, shallow, artificial ponds in southeast England was carried out. Principal components analysis (PCA) revealed that phosphorus was an important environmental variable. A subset of 31 sites was selected along a total phosphorus (TP) gradient (winter TP range 7–1123 µg 1-1), in order to explore the relationship between the surface-sediment diatom assemblages and the contemporary water chemistry using canonical correspondence analysis (CCA). Annual mean TP was the most significant variable in explaining the variance in the diatom species data. Weighted averaging (WA) regression and calibration techniques were used to generate a transfer function, enabling annual mean TP (range 25–646 µg 1-1) to be inferred from the diatom species TP optima of 102 common taxa in the dataset (r 2 = 0.79; RMSE = 0.161; RMSE(boot) = 0.279; n = 30). The model was applied to fossil diatom assemblages in a sediment core from Marsworth Reservoir, Hertfordshire, a Site of Special Scientific Interest (SSSI), with currently high TP levels of 476 µg 1-1, to reconstruct past epilimnetic annual mean TP concentrations. The study shows that artificial, shallow waters can be suitable for palaeolimnological research and that it is possible to reliably infer lake water TP using the WA technique, across a large range of phosphorus concentrations. This method has the potential to provide limnologists, conservationists and water quality managers with an estimate of pre-enrichment phosphorus concentrations and an indication of the onset and development of eutrophication at a site. This information is essential for lake management strategies and restoration programmes.
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    Nutrient metabolism (C, N, P, and Si) in the trophogenic zone of a meromictic lake (1994)
    Springer
    Hydrobiologia 277 (1994), S. 17-39 
    Details
    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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    URL: http://dx.doi.org/10.1007/BF00023983
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    The importance of avian-contributed nitrogen (N) and phosphorus (P) to Lake Grand-Lieu, France (1994)
    Springer
    Hydrobiologia 279-280 (1994), S. 133-147 
    Details
    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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    Different responses to changes in phosphorus, P, among lakes. A study of slopes in chl-a = f(P) graphs (1994)
    Springer
    Hydrobiologia 286 (1994), S. 27-36 
    Details
    ISSN: 1573-5117
    Keywords: Lake ; eutrophication ; phytoplankton ; phosphorus ; non-linear interpolation ; chlorophyll-a
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The least squares estimator of a linear regression coefficient βL will give an overall expression for the change in Δ with Δx. In fresh water ecology, however, subgroups, % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamiuaSGaci% 4Aaaaa!37BE!\[P\operatorname{k}\], of a parent population may have slopes which differ from the overall slope, βκ ≠ βL. By constructing frequency histograms for the set of angles: Arctang % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaci4uaSGaam% yAaiaadQgaaaa!38AE!\[\operatorname{S} ij\],% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaci4uaSGaam% yAaiaadQgaaaa!38AE!\[\operatorname{S} ij\]= para sa y and x% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaiikaiaadM% faliaadMgakiabgkHiTiaadMfaliaadQgakiaacMcacaGGVaGaaiik% aiaadIhaliaadMgakiabgkHiTiaadIhaliaadQgakiaacMcaaaa!42F0!\[(Yi - Yj)/(xi - xj)\], i 〈 j, % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamiEaSGaam% yAaOGaeyiyIKRaamiEaSGaamOAaaaa!3BAB!\[xi \ne xj\], peaks in the distribution may be identified and related to ecological phenomenon. To identify peaks we fit Gaussian distributions to the frequency histograms. For a set consisting of 142 observations of chlorophyll-a and total phosphorus (nutrient) concentrations (TP) from 16 lakes we found four Gaussian peaks corresponding to four subgroups, % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamiuaSGaci% 4Aaaaa!37BE!\[P\operatorname{k}\]k = 1,4. One group identified a response of chl-a to changes in TP which correspond approximately to the average slope found by least square regression (the slope was 0.49). The second group consisted of steeper response than the average (1.28). A third group showed that there is an enhanced proportion of cases where chl-a does not respond to TP (zero slope, all the three deep lakes 〉 10 m, included in the date set contributed to this group). The size of the last group, spanning a wide range of slopes, suggested that about 30% of the inter annual changes in chl-a is unrelated to TP. The results are compared to result obtained by simple least squares regression and to the Theil non-parametric slope estimator.
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    Chlorophyll-phosphorus relationship in acidified lakes of the High Tatra Mountains (Slovakia) (1994)
    Springer
    Hydrobiologia 274 (1994), S. 171-177 
    Details
    ISSN: 1573-5117
    Keywords: chlorophyll ; phosphorus ; mountain lakes ; acidification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Concentrations of total phosphorus (TP) and chlorophyll a (CHLA) were measured in 28 lakes in the High Tatra Mountains (Slovakia) from 1983 to 1990. The relationship between log CHLA and log TP in the Tatra lakes is similar to relationships developed for lakes in other regions, but variation is higher. A part of this variation is caused by acidification of the lakes. In the lakes with pH between 4.9 and 6.3 the CHLA concentrations are often extremely low while TP concentrations decreased, but not as drastically.
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    URL: http://dx.doi.org/10.1007/BF00014640
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    Nutrient cycling in shallow, oligotrophic Lake Kvie, Denmark (1994)
    Springer
    Hydrobiologia 275-276 (1994), S. 267-276 
    Details
    ISSN: 1573-5117
    Keywords: phosphorus ; redox potential ; sediment ; rhizosphere ; macrophyte ; lake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The importance of isoetids for the exchange of phosphorus between sediment and water was studied in the shallow Lake Kvie, Denmark. Vegetated sediments from the littoral zone (55% of lake area) were compared to unvegetated sediments from the littoral and profundal zone. Porewater concentration of soluble reactive phosphate (SRP) was in general low, however, different distributions were found in the three sediments. The vegetated littoral sediment showed highest conc. of SRP just below the surface and decreasing conc. with sediment depth. The SRP release was low on all stations ( 〈 40 µmol m-2 d-1). The observed release of SRP on the vegetated station was much lower than the calculated diffusional flux probably due to assimilation of P by isoetids and binding of SRP to oxidized Fe. The high redox potential in the rhizosphere was probably caused by oxygen excretion from roots. The annual P release from vegetated sediments were only 5% of the P requirements of the macrophytes. The efficient plant assimilation of SRP from the porewater resulted in a small SRP pool with a very fast turnover of P of 500–900 times per year. Both the effects of isoetids on the P cycle in littoral sediments and on the P budget of the entire lake indicate that this plant group is important for keeping lakes in an oligotrophic state.
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    Can Chara control phosphorus cycling in Lake Łuknajno (Poland)? (1994)
    Springer
    Hydrobiologia 275-276 (1994), S. 277-283 
    Details
    ISSN: 1573-5117
    Keywords: phosphorus ; eutrophication ; Chara aspera ; phytoplankton
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Waters of Lake Łuknajno (623 ha, 3 m max. depth postglacial basin in Masurian Lakeland) are of meso-eutrophic type in spite of an intensive land impact and substantial phosphorus loading. The reason of this peculiarity is an abundance of 4 species of charophytes (Chara aculeolata, C. aspera, C. contraria and C. tomentosa) which dominate the submerged vegetation of the lake and yielded 417 g m-2 dry biomass in summer 1991. The plants have high potential for phosphorus uptake and accumulation as was checked in laboratory experiments. Due to this potential Chara can outcompete planktonic algae in mixed cultures at different mineral P supplies.
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    URL: http://dx.doi.org/10.1007/BF00026718
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    Phosphorus fluctuation in water and deposition into sediment within an emergent macrophyte stand (1994)
    Springer
    Hydrobiologia 275-276 (1994), S. 285-292 
    Details
    ISSN: 1573-5117
    Keywords: phosphorus ; sediment ; lake littoral ; Equisetum fluviatile
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Seasonal fluctuation of phosphorus in water, and total phosphorus and different inorganic P fractions (extracted by NH4Cl, NH4F, NaOH and H2SO4) and organic P fraction (residual P) in surface sediment, were measured in the littoral of oligotrophic Lake Pääjärvi (southern Finland). After the emergence of Equisetum fluviatile L. shoots in mid June, water exchange between the littoral and pelagial area diminished and phosphorus concentrations in water and in surface sediment increased in the inner and mid littoral zones. Phosphorus pool in flocculent, ‘easily resuspensible’ sediment composed on average 62% of inorganic phosphorus and 38% of organic phosphorus. 63% of the inorganic phosphorus, on the average, was extracted from ‘apatite-P fraction’ 29% from ‘iron-P fraction’ 7% from ‘aluminum-P fraction’ and less than 1% from ‘loosely-bound P fraction’. During the growing season, net accumulation of sediment and phosphorus was measured only in the inner littoral zone whereas the outer littoral zones acted rather as a source of phosphorus for the pelagic area. The results of this study indicated that nutrient dynamics in littoral environment was through changes in flow environment greatly governed by the macrophytes.
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    Recent palaeolimnology of three shallow Danish lakes (1994)
    Springer
    Hydrobiologia 275-276 (1994), S. 411-422 
    Details
    ISSN: 1573-5117
    Keywords: diatoms ; phosphorus ; weighted averaging ; lake sediments ; carbonates ; radionuclides ; mixing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Recent eutrophication histories of three shallow lakes (mean depths 〈3 m) were studied using palaeolimnological methods. Freeze-cores were dated using 210Pb, 137Cs, 134Cs and 241Am. Resultant chronologies were problematical at two sites (Væng Sø and Vesterborg Sø) due to sediment-water interface mixing, indicated by uniform 137Cs profiles over the surface 20–30 cm. Sediments at Langesø and Vesterborg Sø have a high carbonate content, which together with the high mixing rate have resulted in diatom dissolution below 30 cm at Vesterborg Sø. Diatom stratigraphy indicates relatively small biological changes at both Væng Sø and Langesø both lakes have been eutrophic for at least the last 150–200 years. Væng Sø is dominated by planktonic diatoms together with high percentages of benthic Fragilaria spp., and Langesø by planktonic diatoms, especially Cyclostephanos dubius and Stephanodiscus parvus. Epilimnetic phosphorus concentrations were inferred using weighted averaging; at Væng Sø the diatom-inferred TP (DI-TP) concentrations were close to observed values in the early 1980s, but failed to record the post-biomanipulation decrease to 55 μg l-1 after 1988, presumably due to the smoothing of the sediment record by resuspension and mixing. At Langesø two increases in DI-TP suggest a two-phase enrichment of the lake, initial eutrophication ∼ 1880, and hypertrophy after 1950. The recent DI-TP values are lower than the annual observed values, and reasons for this are discussed. Despite problems associated with sediment mixing, the sediment records of these shallow systems can still be used for monitoring and for environmental reconstructions.
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    High resolution measurements of sediment resuspension above an accumulation bottom in a stratified lake (1994)
    Springer
    Hydrobiologia 284 (1994), S. 43-57 
    Details
    ISSN: 1573-5117
    Keywords: sediment ; resuspension ; lakes ; optical measurements ; transmissometer ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A detailed record of suspended particulate matter (SPM) concentrations in the benthic boundary layer (BBL) 1.5 m above an accumulation bottom and 13.5 m below the surface was obtained from frequent (30 min interval) beam attenuation measurements made with a Sea Tech transmissometer in the main basin of Lake Erken, a moderately deep (mean depth 9 m, maximum depth 21 m) dimictic lake in central Sweden. Concentrations of SPM (g m−3) were not as strongly correlated to the beam attenuation coefficient (c, [m−1]), as were concentrations of the inorganic SPM fraction. Apparently, this was caused by large optically inactive organic particles which significantly affected the measurements of SPM, but had little effect on the attenuation of light. When the water column was thermally stratified, SPM concentrations in the BBL showed a seasonal increase which was related to an increase in the thermocline depth. As the epilimnion deepened, there was also a marked increase in the occurrence of rapid and large changes in SPM concentration. After the loss of stratification, the amount of SPM and the temporal variability in its concentration was reduced. Since surface waves could not influence sediment resuspension at the depth of measurement, these data show the importance of internal waves in promoting sediment resuspension in areas of sediment accumulation. The relatively short period in each summer, when the thermocline reaches a sufficient depth to allow for resuspension over accumulation bottoms, can have important consequences for both the redistribution of lake sediments and the internal loading of phosphorus.
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    Bioavailability of phosphorus in agriculturally loaded rivers in southern Finland (1994)
    Springer
    Hydrobiologia 287 (1994), S. 179-194 
    Details
    ISSN: 1573-5117
    Keywords: agriculture ; phosphorus ; bioavailability ; bioassays ; isotherms ; eutrophication
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The potential bioavailability of phosphorus in agriculturally loaded rivers of southern Finland was determined by an algal bioassay and the release of the potentially bioavailable particulate P was estimated by sorption studies. According to the bioassay 0 to 13.2 per cent (mean 5.1%) of the particulate P in river water samples was potentially bioavailable. Dissolved reactive P (DRP) in river waters appeared to be totally bioavailable whereas the dissolved unreactive P appeared not to be utilized by algae. In addition to river waters two lake sediment samples were also assayed. In these samples 0 and 2.6% of the P was bioavailable. The potential bioavailability of particulate P in agriculturally loaded rivers obtained in this study was lower than that reported in studies from other countries. The difference was assumed to arise partly from methodological factors and partly from the nature of the Finnish soils. The EPC (equilibrium phosphate concentration) values indicated that during the period when most of the agricultural loading enters the lakes in Finland, potentially bioavailable P is not released from the particles because of the relatively high DRP concentration in the receiving waters. However, during the algal production period the DRP concentration in lakes decreases below the EPC and potentially bioavailable particulate P is desorbed. The increase in pH during this period may further enhance the desorption of P.
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    Scion-rootstock relationships with respect to height growth and foliar concentrations of nitrogen and phosphorus in reciprocal grafts of Pinus caribaea var. hondurensis (1994)
    Springer
    New forests 8 (1994), S. 71-79 
    Details
    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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    URL: http://dx.doi.org/10.1007/BF00034132
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    Assessment of nutrient availability and limitation using macroalgae (1994)
    Springer
    Journal of aquatic ecosystem stress and recovery 3 (1994), S. 27-34 
    Details
    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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    Variable rates of phosphate uptake by shallow marine carbonate sediments: Mechanisms and ecological significance (1994)
    Springer
    Biogeochemistry 25 (1994), S. 127-146 
    Details
    ISSN: 1573-515X
    Keywords: carbonate sediments ; phosphate adsorption ; phosphorus ; phosphorus limitation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We determined phosphate uptake by calcareous sediments at two locations within a shallow lagoon in Bermuda that varied in trophic status, with one site being mesotrophic and the other being more eutrophic. Phosphate adsorption over a six hour period was significantly faster in sediments from the mesotrophic site. Uptake at both sites was significantly less than that reported for a similar experiment on calcareous sediments in an oligotrophic lagoon in the Bahamas. The difference in phosphorus adsorption between our sites did not appear to be related to sediment characteristics often cited as important, such as differences in surface area (as inferred from grain size distributions), total organic matter content, or iron content. However, the sediment total phosphorus contents were inversely related to phosphorus uptake at our sites in Bermuda, and at the previously studied Bahamas site. We hypothesize that phosphate uptake in these calcareous sediments is a multi-step process, as previously described for fluvial sediments or pure calcium carbonate solids, with rapid initial surface chemisorption followed by a slower incorporation into the carbonate solid-phase matrix. Accordingly, sediments already richer in solid phase phosphorus take up additional phosphate more slowly since the slower incorporation of surface-adsorbed phosphate into the carbonate matrix limits the rate of renewal of surface-reactive adsorption sites. Although carbonate sediments are a sink for phosphate, and thereby reduce the availability of phosphorus for benthic macrophytes and phytoplankton in the shallow overlying water, phosphate uptake by these sediments appears to decrease along a gradient from oligotrophic to eutrophic sites. If our result is general, it implies a positive feedback in phosphorus availability, with a proportionately greater percentage of phosphorus loading being biologically available longer as phosphorus loading increases. This pattern is supported by the significantly higher tissue phosphorus content of the seagrass,Thalassia testudinum, collected from the eutrophic inner bay site. Over time, this effect may tend to cause a shift from phosphorus to nitrogen limitation in some calcareous marine environments.
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    Are cell redox or lactate dehydrogenase kinetics responsible for the absence of gluconeogenesis from lactate in sea raven, hepatocytes? (1994)
    Springer
    Fish physiology and biochemistry 13 (1994), S. 59-67 
    Details
    ISSN: 1573-5168
    Keywords: fish ; sea raven ; gluconeogensis ; hepatocytes ; redox ; LDH ; isozymes ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Previous studies have reported very low rates of gluconeogenesis from lactate in sea raven (Hemitripterus americanus) hepatocytes compared to other teleosts studied. This study examines whether hepatic cell redox or lactate dehydrogenase (LDH) characteristics may explain this observation. Sea raven hepatic optimal LDH activities (pyruvate reductase direction) were more than 40 times less compared with rainbow trout liver values (40 vs 1914 μmol·min−1·g−1 protein). The Km(lactate) was 9.24 and 0.86 mM for sea raven and trout hepatic LDH, but the Km(pyruvate) was similar between the two species (0.11 and 0.21 mM, respectively). These results suggested that sea raven liver LDH did not favour lactate use and was more indicative of the mammalian M-isozyme. Gel electrophoresis showed a predominant intermediate isozyme, with a small amount of the M-type LDH. Phosphoenolpyruvate carboxykinase (PEPCK) was localized to the mitochondrial compartment, while there was no apparent mitochondrial glutamate-oxaloacetate transaminase (GOT) activity. No in vitro lactate flux to glucose was found in untreated, 10 mM ethanol-treated, or 3 mM NH4Cl-treated sea raven hepatocytes, although CO2 production from lactate was decreased by ethanol and increased by NH4Cl. These results provide evidence that cell redox does not limit gluconeogenesis from lactate, while low activities and the kinetic characteristics of LDH may partially explain the low lactate gluconeogenesis reported in sea raven hepatocytes.
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    Morphological responses of the rainbow trout (Oncorhynchus mykiss) gill to hyperoxia, base (NaHCO3) and acid (HCl) infusions (1994)
    Springer
    Fish physiology and biochemistry 12 (1994), S. 465-477 
    Details
    ISSN: 1573-5168
    Keywords: fish ; chloride cell ; morphology ; kinetics ; Km ; Jmax ; acid-base
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Marked morphological responses occur in the gills of freshwater rainbow trout in response to experimental acid-base disturbance and these responses play an important role in acid-base correction. Compensated respiratory acidosis induced by 70h exposure to environmental hyperoxia (elevated water PO2) caused a 33% decrease in branchial chloride cell fractional surface area (CCFA). Metabolic alkalosis induced by normoxic recovery (6h) from hyperoxia (72h) caused a 50% increase in CCFA, whereas metabolic alkalosis induced by infusion (19h) of NaHCO3 caused a 70% rise. However, the largest increase (135%) in CCFA was seen in response to infusion (19h) of HCl. NaCl infusion had no effect. A particular goal was to assess the relative importance of changes in CCFA vs. changes in internal substrate (HCO3 −) availability in regulating the activity of the branchial Cl−/HCO3 − exchange system. For each of the experimental treatments, the accompanying blood acid-base status and branchial transport kinetics (Km, Jmax) for Cl− uptake had been determined in earlier studies. In the present study, a positive linear relationship was established between CCFA and JCl− max in individual control fish in the absence of an acid-base disturbance. By reference to this relationship, observed changes in JCl− max during metabolic acid-base disturbances were clearly due to changes in both CCFA and internal substrate levels (plasma [HCO3 −]) with the two factors having approximately equal influence.
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    Transport of calcium by mitochondria (1994)
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    Journal of bioenergetics and biomembranes 26 (1994), S. 471-485 
    Details
    ISSN: 1573-6881
    Keywords: Mitochondria ; transport ; calcium ; metabolic mediator ; kinetics ; calcium pulses
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Physics
    Notes: Abstract The identification of intramitochondrial free calcium ([Ca2+ m) as a primary metabolic mediator [see Hansford (this volume) and Gunter, T. E., Gunter, K. K., Sheu, S.-S., and Gavin, C. E. (1994)Am. J. Physiol. 267, C313–C339, for reviews] has emphasized the importance of understanding the characteristics of those mechanisms that control [Ca2+]m. In this review, we attempt to update the descriptions of the mechanisms that mediate the transport of Ca2+ across the mitochondrial inner membrane, emphasizing the energetics of each mechanism. New concepts within this field are reviewed and some older concepts are discussed more completely than in earlier reviews. The mathematical forms of the membrane potential dependence and concentration dependence of the uniporter are interpolated in such a way as to display the convenience of consideringV max to be an explicit function of the membrane potential. Recent evidence for a transient rapid conductance state of the uniporter is discussed. New evidence concerning the energetics and stoichiometries of both Na+-dependent and Na+-independent efflux mechanisms is reviewed. Explicit mathematical expressions are used to describe the energetics of the system and the kinetics of transport via each Ca2+ transport mechanism.
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    The effects of flow rate and distance travelled on the mobility of phosphate in soils (1994)
    Springer
    Transport in porous media 16 (1994), S. 237-251 
    Details
    ISSN: 1573-1634
    Keywords: phosphate ; soil ; adsorption ; leaching ; kinetics ; computer simulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Technology
    Notes: Abstract Effects of flow rate and distance travelled on average mobilities of phosphate in a soil are estimated from breakthrough curves of phosphate at the outlets of small columns of soil, following step increases in the concentration at the inlets. Experimental results are compared with results from a computer simulation model of leached columns of soil. Average mobilities of phosphate in columns of soil, following a step increase in the input concentration, decrease with decreasing rate of flow and with increasing distance travelled and appear to be linearly correlated on a logarithmic scale with both flow rate and distance travelled. An empirical equation, describing these relationships, is fitted to data from leaching experiments at flow rates between 30 and 600 cm/day in ≈ 10 cm long columns of soil. Coefficients are obtained by curve fitting breakthrough curves, calculated with a numerical computer simulation model, to experimental breakthrough curves. The fitted equation enables extrapolation to flow rates and travel distances that are more relevant to a field situation.
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    URL: http://dx.doi.org/10.1007/BF00617149
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    The isothermal crystallization of engineering polymers — POM and PEEK (1994)
    Springer
    Colloid & polymer science 272 (1994), S. 1-16 
    Details
    ISSN: 1435-1536
    Keywords: Polymer crystallization ; kinetics ; modeling ; POM ; PEEK
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The isothermal crystallization of two engineering polymers — POM and PEEK — was studied, both theoretically and experimentally. The experiments were performed by means of differential scanning calorimetry (DSC) and polarized light optical microscopy (OM). Building on previously developed theoretical formalisms (Avrami/Evans, Hillier and Tobin), a new procedure is presented, based on Tobin's model coupled with a modification of Hillier's calculation technique, to accurately describe the kinetics and mechanism of the crystallization of polymers from quiescent melts. First, it is shown that Tobin's model alone, without modification, is more accurate than Avrami/Evans model to describe single-mechanism processes, for a wide range of materials and for longer crystallization times, despite having exactly the same nature and number of parameters (the kinetic, nucleation and growth rate-related, parameterK and the dimensionalityn). Then, Hillier's formalism is modified and combined with Tobin's model, to accurately predict the kinetics of dual mechanism crystallization processes; a clear contrast is drawn with Hillier's Avrami-based, original procedure which uses the same number and nature of parameters, but cannot adequately predict the experimental behavior. The parameter values predicted by the model(s) and procedure presented in this work are all given, are then physically interpreted and, in the case of POM, related to independent morphological observations by polarized light optical microscopy. They are also consistent with electron microscopy observations made by other authors on the detailed morphology of the spherulitic crystallization of polymers.
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    URL: http://dx.doi.org/10.1007/BF00653305
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    Mycorrhizal dependency of micropropagated argan tree (Argania spinosa): II. Mineral nutrition (1994)
    Springer
    Agroforestry systems 27 (1994), S. 67-77 
    Details
    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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    URL: http://dx.doi.org/10.1007/BF00704835
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    Influence of small river conditions on the abundance of Tubificidae (1994)
    Springer
    Hydrobiologia 278 (1994), S. 129-131 
    Details
    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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    URL: http://dx.doi.org/10.1007/BF00142320
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    Assessment of eutrophication in Loch Lomond by desk analysis (1994)
    Springer
    Hydrobiologia 290 (1994), S. 51-52 
    Details
    ISSN: 1573-5117
    Keywords: Loch Lomond ; Scotland ; eutrophication ; phosphorus ; loss coefficients ; chlorophyll
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Phosphorus and chlorophyll a levels were predicted for Loch Lomond from desk-derived P loss coefficients and flushing rates related according to existing eutrophication models. These were in close keeping with measured values.
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    URL: http://dx.doi.org/10.1007/BF00008952
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    Nutrient uptake in mycorrhizal symbiosis (1994)
    Springer
    Plant and soil 159 (1994), S. 89-102 
    Details
    ISSN: 1573-5036
    Keywords: copper ; ectomycorrhizas ; hyphal uptake ; phosphorus ; vesicular-arbuscular mycorrhizas ; zinc
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The role of mycorrhizal fungi in acquisition of mineral nutrients by host plants is examined for three groups of mycorrhizas. These are; the ectomycorrhizas (ECM), the ericoid mycorrhizas (EM), and the vesicular-arbuscular mycorrhizas (VAM). Mycorrhizal infection may affect the mineral nutrition of the host plant directly by enhancing plant growth through nutrient acquisition by the fungus, or indirectly by modifying transpiration rates and the composition of rhizosphere microflora. A capacity for the external hyphae to take up and deliver nutrients to the plant has been demonstrated for the following nutrients and mycorrhizas; P (VAM, EM, ECM), NH4 + (VAM, EM, ECM), NO3 - (ECM), K (VAM, ECM), Ca (VAM, EM), SO4 2- (VAM), Cu (VAM), Zn (VAM) and Fe (EM). In experimental chambers, the external hyphae of VAM can deliver up to 80% of plant P, 25% of plant N, 10% of plant K, 25% of plant Zn and 60% of plant Cu. Knowledge of the role of mycorrhiza in the uptake of nutrients other than P and N is limited because definitive studies are few, especially for the ECM. Although further quantification is required, it is feasible that the external hyphae may provide a significant delivery system for N, K, Cu and Zn in addition to P in many soils. Proposals that ECM and VAM fungi contribute substantially to the Mg, B and Fe nutrition of the host plant have not been substantiated. ECM and EM fungi produce ectoenzymes which provide host plants with the potential to access organic N and P forms that are normally unavailable to VAM fungi or to non mycorrhizal roots. The relative contribution of these nutrient sources requires quantification in the field. Further basic research, including the quantification of nutrient uptake and transport by fungal hyphae in soil and regulation at the fungal-plant interface, is essential to support the selection and utilization of mycorrhizal fungi on a commercial scale.
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    URL: http://dx.doi.org/10.1007/BF00000098
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    Desorption and plant-availability of phosphate sorbed by some important minerals (1994)
    Springer
    Plant and soil 162 (1994), S. 89-97 
    Details
    ISSN: 1573-5036
    Keywords: desorption ; phosphorus ; rice ; variable-charge mineral
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Experiments were conducted to study the desorption characteristics and plant-availability of phosphate sorbed by some important variable-charge minerals including kaolinite, goethite and amorphous Al oxide. Phosphate desorption from the complexes of goethite-P, kaolinite-P and Al oxide-P by equilibration with 0.02M KCl, resin or some commonly used chemical extractants was slow compared to desorption from a permanent-charge mineral (montmorillonite). However, rice plants were not observed under P deficiency in a pot trial with a phosphate-mineral complex as the only P source for both the permanent-charge mineral and the variable-charge minerals at either 50% or 100% sorption saturation with the exception of goethite-P at 50% saturation. In the exceptional goethite-P treatment, plant P concentration (1.0 g kg−1) was on the threshold of P deficiency. From 15% to 31% of the applied P was recovered by the plants within a growing period of three months, depending on sorption saturation and mineral type. Both the dry matter yield and P uptake decreased with decreasing sorption saturation for all the tested complexes except for Al oxide-P100 (100% saturation). In the case of Al oxide-P100, Al toxicity may have occurred, for poor root growth and high Al concentration in the plants were observed. The effect of sorption saturation on the yield and P uptake of plant was obvious for kaolinite and goethite but not very significant for montmorillonite. Based on the recovery of applied P, the plant-availability decreased in the following order: kaolinite-P100 〉 goethite-P100 〉 Al oxide-P50 〉 montmorillonite-P100 〉 montmorillonite-P50 〉 kaolinite-P50 〉 goethite-P50. Fractionation of the sorbed P before and after plant uptake showed that most of the P uptake originated from the resin-exchangeable P fraction in montmorillonite-P complex, but came mainly from NaOH-extractable fractions in goethite-P complex, whereas all the resin-P, NaHCO3-P and NaOH-P fractions in kaolinite- and amorphous Al oxide-P complex made a contribution to P uptake.
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    URL: http://dx.doi.org/10.1007/BF01416093
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    Selection for improved adaptation of white clover to low phosphorus and acid soils (1994)
    Springer
    Euphytica 77 (1994), S. 243-250 
    Details
    ISSN: 1573-5060
    Keywords: Acid soils ; phosphorus ; selection ; Trifolium repens ; white clover
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary A total of 490 white clover genotypes were grown in competition withAgrostis tenuis and repeatedly defoliated, in a glasshouse trial. The percentage change in shoot yield from the first to the last harvest (harvest 6) was negatively correlated with the soil-P level from which ecotypes were collected. High- and low-yielding genotypes were selected from this study and compared in a field trial on a low-P soil (12 mg Olsen P/kg soil), in a grazed mixed species sward. Over the first year there was no significant difference in spread into the sward, and over three years no significant difference in persistence. Selection in glasshouses for yield is unlikely to improve edaphic stress tolerance in the field. In a field study in New Zealand, comparison of six ecotype populations showed that after one year the highest-spreading population had been collected from a low-P soil while the lowest spreading population came from a high-P soil, although the correlation between spread and soi-P from which ecotypes were collected was not significant (r=−0.67 p〉0.05). However, in another field trial in England it was shown that populations collected from low-P soils not only outyielded those, collected from high-P soils but that they also responded less to added P. It was concluded that populations collected from low-P soils will be a useful source of germplasm to identify genotypes adapted to low-P soils. Successful identification of such genotypes is most likely to be made in the field rather than in controlled more artificial environments.
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    URL: http://dx.doi.org/10.1007/BF02262637
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    The kinetics of reactions around the cytochrome bf complex studied in an isolated system (1994)
    Springer
    Photosynthesis research 40 (1994), S. 199-206 
    Details
    ISSN: 1573-5079
    Keywords: cytochrome bf complex ; electron transfers ; kinetics ; quinol oxidation ; Q-cycle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The kinetics of oxidation and reduction of P700, plastocyanin, cytochrome f and cytochrome b-563 were studied in a reconstituted system consisting of Photosystem I particles, cytochrome bf complex and plastocyanin, all derived from pea leaf chloroplasts. Decyl plastoquinol was the reductant of the bf complex. Turnovers of the system were initiated by laser flashes. The reaction between oxidised P700 and plastocyanin was non-homogeneous in that a second-order rate coefficient of c. 5×10−7 M−1 s−1 applied to 80% of the P700+ and c. 0.7×107 M−1 s−1 to the remainder. In the presence of bf complex, but without quinol, the electron transfer between cytochrome f and oxidised plastocyanin could be described by a second-order rate coefficient of c. 4×107 M−1 s−1 (forward), and c. 1.6×107 M−1 s−1 (reverse). The equilibrium coefficient was thus 2.5. Unexpectedly, there was little reduction of cytochrome f + or plastocyanin+ by electrons from the Rieske centre. With added quinol, reduction of cytochrome b-563 occurred. Concomitantly, electrons appeared in the oxidised species. It was inferred that either the Rieske centre was not involved in the high-potential chain of electron transfer events, or that, only in the presence of quinol, electrons were quickly passed from the Rieske centre to cytochrome f +. Additionally, the presence of quinol altered the equilibrium coefficient for the cyt f/PC interaction from 2.5 to c. 5. The reaction between quinol and the bf complex was describable by a second-order rate coefficient of about 3×106 M−1 s−1. The pattern of the redox reactions around the bf complex could be simulated in detail with a Q-cycle model as previously found for chloroplasts.
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    URL: http://dx.doi.org/10.1007/BF00019337
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    Degradation of the Antiarthritic Prodrug, 3-Carboxy-5-methyl-N-[4-(trifluoromethoxy)phenyl]-4-isoxazolecarboxamide, in Aqueous Solution (1994)
    Springer
    Pharmaceutical research 11 (1994), S. 345-348 
    Details
    ISSN: 1573-904X
    Keywords: kinetics ; decarboxylation ; leflunomide ; deacetylation ; dissociation constant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1018940415770
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    Growth characteristics of Geotrichum ingens on propionic acid and acetic acid in batch and continuous culture (1994)
    Springer
    World journal of microbiology and biotechnology 10 (1994), S. 505-509 
    Details
    ISSN: 1573-0972
    Keywords: Acetic acid ; chemostat ; Geotrichum ingens ; growth ; inhibition ; kinetics ; monocarboxylic acids ; propionic acid ; yeast
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Growth of Geotrichum ingens in batch cultures was completely inhibited by 47 g acetic acid/l or 33 g propionic acid/I. With mixtures of acetic and propionic acids, however, growth only ceased at 55 g/l. Acetic acid inhibited growth linearly, whereas propionic acid inhibited growth non-linearly. In continuous culture, two steady states at each dilution rate were observed at high dilution rates for acetic acid and propionic acid. The highest yield coefficient (0.69 g cells/g substrate) was achieved with propionic acid as substrate. On both substrates and their mixtures, the protein content of the biomass increased when the dilution rate was increased.
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    Thermal decomposition of 1-ethyl-5-iodotetrazole (1994)
    Springer
    Russian chemical bulletin 43 (1994), S. 1812-1815 
    Details
    ISSN: 1573-9171
    Keywords: kinetics ; mechanism ; thermolysis ; 1-ethyl-5-iodotetrazole ; mass spectrometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition of 1-ethyl-5-iodotetrazole in a melt and in solutions was studied using thermogravimetry, manometry, pyrolytic mass spectrometry, and IR spectroscopy. The kinetic and activation parameters of the process and the nature of the decomposition products were determined. The reaction mechanism is assumed to involve equilibrium tautomeric rearrangement of the tetrazole to azidoazomethine form followed by homolytic cleavage of the C-I bond.
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    Effect of the nature of the cation in 2,6-di-tert-pentylphenolates on the kinetics and mechanism of the reaction of 2,6-di-tert-pentylphenol with methyl acrylate (1994)
    Springer
    Russian chemical bulletin 43 (1994), S. 769-773 
    Details
    ISSN: 1573-9171
    Keywords: 2,6-di-tert-pentylphenol, methyl acrylate, Na and K cations ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The nature of the cation (K or Na) in 2,6-di-tert-pentylphenolates (ArOK or ArONa) affects the kinetics of the reaction of 2,6-di-tert-pentylphenol (ArOH) with methyl acrylate. This is associated with the ability of ArONa to replace the cation with a proton during interaction with methyl 3-(4-hydroxy-3,5-di-tert-pentylphenyl)propionate (HOArAlkOMe) to form a more efficient catalyst, sodium 4-(2-methoxycarbonylethyl)-2,6-di-tert-pentylphenolate (NaOArAlkOMe). Two different kinetic schemes, which describe the kinetics of the consumption of ArOH in the presence of ArOK and ArONa, are proposed. The elemental-stage rate constants are calculated by mathematical simulation of the reaction kinetics with consideration of the features of catalysis in the presence of ArOK and ArONa.
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    URL: http://dx.doi.org/10.1007/BF00717335
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    A method to determine the relative value of the barriers of carbon chain growth and termination in Fischer-Tropsch synthesis: elementary reaction kinetics for chain growth (1993)
    Springer
    Catalysis letters 19 (1993), S. 93-97 
    Details
    ISSN: 1572-879X
    Keywords: Fischer-Tropsch synthesis ; reaction activation barrier ; carbon chain growth and termination ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A method is established, by which the difference of the reaction activation barriers of carbon chain growth and termination in Fischer-Tropsch (FT) synthesis can be determined from experiments. A FT synthesis is carried out on Fe/Zn catalyst. We apply the method to analyze the experimental result and obtain the difference of reaction activation barriers of carbon chain growth and termination of α-olefins on the catalyst.
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    The polymerization of sickle hemoglobin in solutions and cells (1993)
    Springer
    Cellular and molecular life sciences 49 (1993), S. 110-117 
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    ISSN: 1420-9071
    Keywords: Polymerization ; sickle hemoglobin ; sickle cell disease ; kinetics ; thermodynamics ; polymer domains ; nucleation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The polymerization of sickle hemoglobin occurs by the same mechanisms in solutions and in cells, and involves the formation of 14 stranded fibers from hemoglobin molecules which have assumed a deoxy quaternary structure. The fibers form via two types of highly concentration-dependent nucleation processes: homogeneous nucleation in solutions with hemoglobin activity above a critical activity, and heterogeneous nucleation in similarly supersaturated solutions which also contain hemoglobin polymers. The latter pathway is dominant, and creates polymer arrays called domains. The individual polymers bend, but also cross-link, and the resulting mass behaves as a solid. The concentration of polymerized hemoglobin increases exponentially unless clamped by rate limiting effects such as oxygen delivery.
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    URL: http://dx.doi.org/10.1007/BF01989414
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    Effect of mineral nutrients on the kinetics of methane utilization by methanotrophs (1993)
    Springer
    Biodegradation 4 (1993), S. 163-170 
    Details
    ISSN: 1572-9729
    Keywords: factorial analysis ; kinetics ; methane ; methanotrophs ; nutrients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The effect of different mineral nutrients on the kinetics of methane biodegradation by a mixed culture of methanotrophic bacteria was studied. The substrate factors examined were ammonia, iron, copper, manganese, phosphate, and sulphide. The presence of iron in the growth medium had a strong effect on the yield coefficient. Yield coefficients up to 0.49 mg protein per mg methane were observed when iron was added at concentrations of 0.10–5.0 mg/l. Iron addition also increased the maximum methane utilization rate. The same effect was observed after addition of ammonium to a medium where nitrate was the only nitrogen source. The observed Monod constant for methane utilization increased with increasing concentration of ammonia. This shows that ammonia is a weak competitive inhibitor as observed by other researchers. Relatively high levels of both ammonia (70 mg/l) and copper (300 µg/l) inhibited the methane degradation, probably due to the toxic effect of copper-amine complexes.
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    Hydrology of the Peel-Harvey estuary catchment (1993)
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    Nutrient cycling in agroecosystems 36 (1993), S. 127-133 
    Details
    ISSN: 1573-0867
    Keywords: hydrology ; water balance ; phosphorus ; Streamflow ; Peel-Harvey
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract This paper discusses the land types, hydrologic characteristics and processes, and the major modification of these, in relation to mechanisms and magnitude of phosphorus losses to drains and riverine systems which discharge to the Peel-Harvey estuary. About 75% of the coastal plain part of the catchment is cleared of native vegetation and used for dryland, dairy and beef grazing. There are small areas devoted to irrigated pasture and commercial horticulture. Seventy-five percent of the soils of the catchment are sandy surfaced with a poor capacity to retain phosphorus. Though the area is flat, catchment water yields are high because of a large winter rainfall excess and low soil storage capacity. Drainage schemes have been constructed in much of the catchment to remove excess water quickly. This was required initially to allow agricultural expansion and is now important for protecting a growing infrastructure which serves the most populous region of Western Australia.
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    Fertilization of millet cv. Souna III in Senegal: dry matter production and nutrient uptake (1993)
    Springer
    Nutrient cycling in agroecosystems 35 (1993), S. 217-226 
    Details
    ISSN: 1573-0867
    Keywords: calcium ; dry matter distribution ; fertilizer ; harvest index ; magnesium ; manure ; millet ; nitrogen ; nutrient uptake ; phosphorus ; potassium ; Senegal
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract In a fertilizer and manure experiment, millet was grown under four treatments (no fertilizer or manure, farmyard manure, chemical fertilizer, and both). Grain yield and total aboveground biomass production of the unfertilized plot were relatively high. The observed differences in total dry matter production must be attributed to differences in nutrient availability, as amount of rainfall and its distribution were favourable. Results show only small differences in distribution of dry matter among the various plant organs between the best and the non-fertilized treatments. Nutrient supply from natural sources, defined as crop content of N, P, and K at maturity without fertilizer application, amounted to 104, 16 and 103 kg ha−1, respectively, which are very high values. Total uptake of calcium and magnesium is related to that of potassium, as the combined content of these three elements is linearly related to total aboveground biomass production. Minimum removal of nitrogen and phosphorus per ton grain dry matter amounts to 29 and 4kg, respectively, and 9 kg potassium per ton total aboveground dry matter. A possible double function of phosphorus as element of structural biomass and for maintenance of electro-neutrality is discussed.
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    Fertilizers and eutrophication in southwestern Australia: Setting the scene (1993)
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    Nutrient cycling in agroecosystems 36 (1993), S. 95-103 
    Details
    ISSN: 1573-0867
    Keywords: eutrophication ; phosphorus ; fertilizer ; Peel-Harvey estuary ; algal blooms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract An excess of plant nutrients has caused serious eutrophication in aquatic ecosystems of southwestern Australia manifested by excessive growth and accumulation of green and bluegreen algae. Phosphorus is generally the limiting nutrient for algal growth and phosphatic fertilizers applied to nutrient-deficient, leaching, sandy soils are the main source of P, supplemented by rural industry point sources. Nitrogen is the limiting nutrient in marine embayments with little drainage from the land. Measures to reduce the load of P delivered to drainage include basing fertilizer application rates on soil testing for P and the use of less soluble P fertilizers. Catchment management plans are being implemented with community involvement to reduce P loads and maintain agricultural production. This introductory paper reviews the history of eutrophication in southwestern Australia and of studies into its causes, principally in the large Peel-Harvey estuary. It briefly summarises other papers in this special issue concerned with different aspects of the problem: how to fertilize the land without causing eutrophication.
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    Phosphorus retention and release from sandy soils of the Peel-Harvey catchment (1993)
    Springer
    Nutrient cycling in agroecosystems 36 (1993), S. 115-122 
    Details
    ISSN: 1573-0867
    Keywords: phosphorus ; retention ; release ; sandy soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract In order to manage phosphorus (P) losses from soils to waterbodies, knowledge of the mechanisms through which P is retained or released from the soil is essential. Sandy soils of the Peel-Harvey catchment (Western Australia) were subjected to a range of environmental and management factors in the laboratory and field in order to gain an understanding of the mechanisms that affect the magnitude of P losses. Sandy soils accumulated P, despite having little sorption capacity, and this accumulation could be monitored by measuring an acid-extractable fraction. The potential, short-term P loss could be estimated by determination of water-soluble soil solution P prior to winter rains. An annual cycle of the change in arbitrarily defined soil-P pools is discussed in relation to environmental and management factors. Laboratory experiments indicated that P rundown and potential annual P loss in the absence of P fertilizers could be estimated using bicarbonate extractable P. Phosphorus losses were decreased by the application of fertilizers with a low content of water-soluble P. The low ability of sandy soils of the Peel-Harvey coastal catchment to retain P, when compared to other Western Australian soils, is because of low contents of clay minerals and iron and aluminium hydrous oxides.
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    What controls levels of dissolved phosphate and ammonium in surface waters? (1993)
    Springer
    Aquatic sciences 55 (1993), S. 132-142 
    Details
    ISSN: 1420-9055
    Keywords: nitrogen ; phosphorus ; uptake ; regeneration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Dissolved inorganic nutrient pools are small relative to particulate pools, and dissolved pools turnover rapidly. It has been observed that pools change little from day to day on the sampling scales usually employed. A simple model is presented where uptake and regeneration rates balance to cause a local steady state concentration for dissolved inorganic nutrients. Enrichment and dilution perturbation experiments with lake water support the idea of steady state nutrient concentrations. Although inorganic nutrient concentrations are often controlled by biota, the absolute concentrations present tell little about the activity of that biota.
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    Kinetics of redox cycling of iron coupled with fulvic acid (1993)
    Springer
    Aquatic sciences 55 (1993), S. 103-111 
    Details
    ISSN: 1420-9055
    Keywords: iron(III) (hydr)oxide ; fulvic acid ; iron redox cycling ; dissolution ; surface reactivity ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10−4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the 〉 FeIII-OH/Fe(II) “wheel” coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)3(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.
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    URL: http://dx.doi.org/10.1007/BF00877439
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    Bioavailability of controlled release carbamazepine estimated by mixed effect modelling (1993)
    Springer
    European journal of clinical pharmacology 44 (1993), S. 231-235 
    Details
    ISSN: 1432-1041
    Keywords: Carbamazepine ; kinetics ; population pharmacokinetics ; bioavailability ; controlled release ; non-linear model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The absorption properties of a conventional tablet of carbamazepine (T) and a controlled release form of carbamazepine (TCR) have been compared using a nonlinear mixed effect model (NONMEM). Plasma carbamazepine concentration data were obtained from an open, steady-state, crossover bioavailability study in which 494 measurements were obtained from 13 patients, with an equal number of samples per patient for each dosage form. The pharmacokinetic model used was a one-compartment open model with first-order absorption and elimination. The objective function was used as a measure of the goodness of fit of the model to the data. Body weight was an important determinant of carbamazepine clearance (CL) but not volume of distribution (V). Accounting for the interindividual variability in volume of distribution did not significantly influence the objective function. Including different rates of absorption (ka) for the two dosage forms resulted in a significant improvement in the objective function, as well as reducing the interindividual variability in the rate of absorption. Adding a parameter for relative bioavailability (f) of TCR improved the objective function statistically, but an unrealistic value for V was obtained, and the absorption and elimination rates appeared to be transposed in the classical “flip-flop” manner. Fixing V to the value obtained before introducing f did not change the objective function and permitted estimation of f without the confounding influence of excessive parameters. The final population parameter estimates (standard error of estimate) were: CL, 0.0522 (0.0019) l·h−1·kg−1; V, 63.7 (FIXED)l; kaT, 0.312 (0.064) h−1; kaTCR, 0.149 (0.016) h−1; f, 1.01 (0.0326); variance (additive) in CL, 0.291 (0.083) (l·h−1·kg−1)2; residual intrasubject error variance (additive), 0.572 (0.082) (mg·l−1)2. The 95% confidence interval of the extent of absorption (f) of 93.6%–107.4% was well within the generally accepted range of ±20%, while the rate of absorption of Tegretol CR was significantly slower than that of Tegretol, as expected for a controlled release product.
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    A new thermobalance for studies of the high-temperature sulphidation of metals and alloys (1993)
    Springer
    Journal of thermal analysis and calorimetry 39 (1993), S. 15-20 
    Details
    ISSN: 1572-8943
    Keywords: alloys ; high-temperature sulphidation ; kinetics ; new thermobalane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird ein neue Apparat zur Untersuchung der Hochtemperatur-Sulfidierung von Metallen in H2/H2S Atmosphare beschrieben. Der Unterschied zwischen diesem Apparat und dem fruher benutzten, besteht im Gasdosierungsystem. Wasserstoff reagiert teilweise mit Schwefel, was eine stabile Zusammensetzung des Gasgemisches beim niedrigen Schwefeldampfdruck sichert. Gewichtsmessungen von Metallen und Legierungen konnen in diesem System bei Temperaturen von 1073 bis 1473 K mit einer Genauigkeit von 10−6 g ausgefuhrt werden.
    Notes: Abstract A new thermogravimetric apparatus for studying the kinetics of metal sulphidation in a H2/H2S gas mixture is described. The main difference between this device and other equipment is the application of hydrogen to obtain a H2/H2S mixture at suitable sulphur partial pressures at a total mixture pressure of 1 atm. The use of the carrier gas allows the measurement of sulphidation kinetics under dynamic conditions and consequently over a much wider pressure range of sulphur vapour, down to 10−12 atm.
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    Thermal and temperature dependence of electrical conductivity studies on Zn, Cd and Hg hydrazone complexes (1993)
    Springer
    Journal of thermal analysis and calorimetry 39 (1993), S. 65-74 
    Details
    ISSN: 1572-8943
    Keywords: electrical conductivity ; hydrazone complexes ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Bei zwei verschiedenenpH-Werten wurden die Zn-, Cd- und Hg-Komplexe von Isatinisonicotinoylhydrazon hergestellt. Diese wurden thermisch untersucht (TG, DTG, DTA) und die Gleichstromleitfähigkeit von gepreßten Pulverproben als eine Funktion der Temperatur untersucht. Sowohl für die Liganden als auch für die Komplexe wurden die Aktivierungsenergien (ΔE) berechnet, wobei sich für die Liganden niedrigere Werte ergaben. Man fand, daß die Größe von ΔE durch die Art des Metalles und denpH-Wert bei der Herstellung beeinflußt wird.
    Notes: Abstract The complexes of Zn, Cd and Hg of isatin isonicotinoyl hydrazone were prepared at two differentpHs. Their thermal studies (TG, DTG and DTA) have been made and the DC electrical conductivity of compressed powder samples as a function of temperature was investigated. The activation energies (ΔE) were calculated for the ligand and the complexes which showed that the ligand has a lower value of ΔE than the complexes. The magnitude of ΔE was found to be affected by the nature of the metal and thepH of preparation.
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    Effect of alkali additives on the kinetics of WO3+CCl4 reaction (1993)
    Springer
    Journal of thermal analysis and calorimetry 39 (1993), S. 75-86 
    Details
    ISSN: 1572-8943
    Keywords: chlorination ; kinetics ; WO3+CCl4 reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels Thermogravimetrie wurde die Chlorierungskinetik von alkaliversetztem (K und Li) Wolframtrioxid untersucht, wobei CCl4 als Chlorierungsreagens fungierte. Die Reaktivität der modifizierten Proben wurden mit der von reinem WO3 verglichen. Für die reinen und für die alkaliversetzten Proben wurden ähnliche scheinbare Aktivierungsenergien gefunden. Der Zusatz von Kalium verursacht jedoch eine starke Abnahme der ursprünglichen Reaktionsgeschwindigkeit, während oberflächiges Lithium keinen Effekt zeigt. Während der Chlorierung wurde eine ständige Senkung der linearen Reaktionsgeschwindigkeit für beide Proben festgestellt, was mit Rückhalteeffekten von oberflächigen Nebenprodukten und Alkalizusätzen erklärt wird. Zur Beschreibung der isothermen TG-Kurven wurde ein entsprechendes kinetisches Modell angenommen, welches auf einer monoton steigenden Inhibition dieser Proben basiert. Die auf der Grundlage dieses Modelles berechnete Kurve stimmt recht gut mit den experimentellen Ergebnissen überein.
    Notes: Abstract The chlorination kinetics of alkali-added (K and Li) tungsten trioxide were studied by thermogravimetry, using gaseous CCl4 as chlorinating agent. The reactivity of the modified samples was compared to the results on the chlorination of pure WO3. Similar apparent activation energies were found for the pure and alkali-added samples. However, potassium additive resulted in a strong decrease of the initial reaction rate, while surface lithium has no influence on it. During the chlorination a continuous decrease of the linear reaction rate was observed for both samples, which was explained by retarding effects of surface by-products and alkali additives. For describing the isothermal TG curves an appropriate kinetic model, based on the monotonously increasing inhibition of these species was assumed. The curve calculated with this model fits well to the experimental results.
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    Comparative studies on the curing kinetics and thermal stability of tetrafunctional epoxy resins using various amines as curing agents (1993)
    Springer
    Journal of thermal analysis and calorimetry 39 (1993), S. 229-238 
    Details
    ISSN: 1572-8943
    Keywords: epoxy resins ; kinetics ; thermal stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die Vernetzungsreaktionen der Epoxidharze Tetraglycidyl-diamino-diphenyl-methan (TGDDM) und Tetraglycidyl-methylen-bis(o-toluidin) (TGMBT) unter Verwendung von Diaminodiphenylsulfon (DDS), Diaminodiphenylmethan (DDM) und Diethylentriamin (DETA) als Vernetzungsmittel wurden kinetisch mittels DSC untersucht. Die dynamischen Scans im Temperaturbereich 20°–300°C wurden analysiert, um unter Anwendung einiger empirischer Gleichungen die Aktivierungsenergie und die Reaktionsordnung des Vernetzungsprozesses zu ermitteln. Die Aktivierungsenergie der einzelnen Epoxy-Systeme liegt im Bereich 71.9–110.2 kJ·mol−1. An der ausgehärteten Harze wurde mittels TG in einer statischen Luftatmosphäre un deiner Aufheizgeschwindigkeit von 10 Grad/min die Kinetik des termischen Abbaues untersucht. Man fand, daß die thermiscehn Abbaureaktionen in einem Schritt ablaufen und ihre Aktivierungsenergie im Intervall 27.6–51.4 kJ·mol−1 liegt.
    Notes: Abstract The curing reactions of the epoxy resins tetraglycidyl diaminodiphenyl methane (TGDDM) and tetraglycidyl methylenebis (o-toluidine) (TGMBT) using diaminodiphenyl sulfone (DDS), diaminodiphenyl methane (DDM) and diethylenetriamine (DETA) as curing agents were studied kinetically by differential scanning calorimetry. The dynamic scans in the temperature range 20°–300°C were analyzed to estimate the activation energy and the order of reaction for the curing process using some empirical relations. The activation energy for the various epoxy systems is observed in the range 71.9–110.2 kJ·mol−1. The cured epoxy resins were studied for kinetics of thermal degradation by thermogravimetry in a static air atmosphere at a heating rate of 10 deg·min−1. The thermal degradation reactions were found to proceed in a single step having an activation energy in the range 27.6–51.4 kJ·mol−1.
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    Gamma-radiation effects on the reduction of hematite to iron in the graphite-iron(III) oxide system (1993)
    Springer
    Journal of thermal analysis and calorimetry 39 (1993), S. 87-95 
    Details
    ISSN: 1572-8943
    Keywords: gamma radiation effects ; graphite-hematite system ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels isothermer und dynamischer TG wurde im Graphit-Eisen(III)oxidsystem in Luft der Einfluß von60Co-Gammastrahlung und von verschiedenen Probenzusammensetzungen auf die Reduktion von Hämatit zu Eisen untersucht. Entsprechend verschiedener theoretischer Modelle heterogener Reaktionen wurde eine kinetische Analyse der isothermen Daten durchgeführt und die Ergebnisse zeigten, daß das dreidimensionale Phasengrenzenmodell die beste Übereinstimmung liefert. Die Analyse der dynamischen TG-Daten wurde mittels der Integralmethode von Ozawa, der Coats-Redfem-Methode und einer zusammengesetzten Methode auf der Grundlage der modifizierten Coats und Redfern Gleichung durchgeführt. Die Aktivierungsparameter wurden berechnet und die Ergebnisse der verschiedenen Methoden miteinander verglichen und diskutiert. Strahlung scheint keine Änderung des Reaktionsmodelles oder des Mechanismus hervorzurufen. Durch Bestrahlung gibt es aber ein Absinken der Aktivierungsenergie und des Frequenzfaktors sowie ein Absinken der Halbwertszeit der Reaktion, was bei höheren Temperaturen und höherer Dosis bemerkenswert groß ist.
    Notes: Abstract The effects of60Co-gamma radiation and of various sample composition on the reduction of hematite to iron in the graphite-iron(III) oxide system in air were studied using isothermal and dynamic TG techniques. Kinetic analysis of isothermal data were performed according to various theoretical models of heterogeneous reactions and the results showed that the three-dimensional phase boundary model gives the best fit of data. Analysis of dynamic TG data were made using Ozawa integral method, Coats-Redfern method and a composite method based on the modified Coats and redfern equation. The activation parameters were calculated and the results of the different methods were compared and discussed. Radiation apparently did not introduce a change in the reaction model or mechanism. However, there is a decrease in activation energy and frequency factor upon irradiation and a decrease in the half-life time of the reaction which is remarkable at the higher temperatures and higher doses.
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    Isothermal DSC investigation of the kinetics of thermooxidative decomposition of some edible oils (1993)
    Springer
    Journal of thermal analysis and calorimetry 39 (1993), S. 217-220 
    Details
    ISSN: 1572-8943
    Keywords: DSC ; edible oils ; isothermal method ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Unter Einsatz der isothermen Methode wurden kinetische Untersuchungen der thermooxidativen Zersetzung einiger Speiseöle durchgeführt. Zur Bestimmung des Umwandlungsgrades wurde ein DS-Kalorimeter von DuPont eingesetzt. Grundlage der Untersuchung bildeten Leinöl, Rizinusöl und Olivenöl.
    Notes: Abstract The thermooxidative decompositions of some edible oils were investigated. Isothermal measurements of convention were made with a Du Pont differential scanning calorimeter. Linseed oil, castor oil, olive oil and cod-liver oil were investigated.
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    Study on curing of novolac epoxy resin (1993)
    Springer
    Journal of thermal analysis and calorimetry 39 (1993), S. 351-358 
    Details
    ISSN: 1572-8943
    Keywords: epoxy resin ; kinetics ; polyamide hardener
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels DSC wurde die Optimierung des Einsatzverhältnisses von Epoxidnovolackharz Dobeckot E4 und Polyamidhärtungsmittel EH411 durchgeführt. Die Daten ergaben, daß ein Harz-Polyamid-Verhältnis von 100∶40 bzw. 100∶50 das Optimum zu sein scheint, bei dem die Aushärtung am größten ist. Mittels isothermer und dynamischer DSC-Methoden wurden die kinetischen Parameter für diese Ansätze ermittelt. Unter Anwendung der isothermen DSC-Methode im Temperaturbereich 70°–90°C wurde die Geschwindigkeitskonstante für den Aushärtungsprozeß dieser Ansätze ermittelt. Diese wurden mittels Extrapolation der erhaltenen Angaben für höhere Temperaturen auch für die Temperatur 201°C (Raumtemperatur) vorhergesagt. Vorhergesagte und experimentell ermittelte Werte stehen in guter Übereinstimmung zueinander.
    Notes: Abstract The optimization of proportions of novolac epoxy resin, Dobeckot E4 and polyamide hardener, EH411 has been established by DSC and the data indicates that resin-polyamide, 100∶40 and 100∶50, appear to be optimum where ‘extent of cure’ is maximum. The kinetic parameters for these formulations have been evaluated using isothermal and dynamic modes by employing DSC. The rate constants have been evaluated for curing process of these formulations using isothermal DSC mode in the temperature range of 70°–90°C. These have also been predicted at 20°±1°C (room temperature) by extrapolating the data obtained at elevated temperatures. A comparison of the predicted values with the experimental values shows that there is a good agreement between them.
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    Hemoglobins with multiple reactive sulphydryl groups: The reaction of pigeon hemoglobin with 5,5′-dithiobis (2-nitrobenzoic acid) (1993)
    Springer
    The protein journal 12 (1993), S. 639-646 
    Details
    ISSN: 1573-4943
    Keywords: Sulphydryl groups ; multiple ; hemoglobin ; kinetics ; ionizable groups
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Pigeon hemoglobin has eight reactive sulphydryl groups per (tetramer) molecule, as determined by Boyer titration with p-chloromercuribenzoate. However, only four of these are titra-table with 5,5′-dithiobis(2-nitrobenzoate) under the same experimental conditions. The time course of the reaction of pigeon hemoglobin with 5,5′-dithiobis(2-nitrobenzoate) is biphasic. In thepH range 6–9, the fast phase is between one and two orders of magnitude faster than the slow phase. For the fast phase,k app, the apparent second-order rate constant, increases monotonously withpH. Quantitative analysis reveals that the reactionof the sulphydryl group responsible for this phase is coupled to the ionization of two groups with pK a values of 6.15±0.1 and 8.5±0.1. These pK a values are assigned to HisHC3(146)β and to the CysF9(93)β sulphydryl group, respectively. For the slow phase thek app vs.pH profiles are bowl-shaped. Analysis reveals that the reaction of the sulphydryl group to which this phase may be attributed is coupled to the ionization of two groups with mean pK a values of 6.53±0.1 and 8.25±0.1. Examination of the structure of hemoglobin allows us to assign these values to HisG19(117)β and CysB5(23)β, respectively. The CysB5(23)β sulphydryl is in the region of the molecule where amino acid substitutions have been found to give rise to significant changes in the oxygen affinity of hemoglobin [Huanget al. (1990),Biochemistry 29, 7020–7023.
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    Hemoglobins with multiple reactive sulphydryl groups: The reaction of dog hemoglobin with 5,5′-dithiobis (2-nitrobenzoate) (1993)
    Springer
    The protein journal 12 (1993), S. 33-37 
    Details
    ISSN: 1573-4943
    Keywords: Hemoglobin ; sulphydryl group ; ionizable groups ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Dog hemoglobin has four sulphydryl groups per (tetramer) molecule located at the G18(111)a and F9(93)β positions. The two sulphydryls at the G18(111)a positions are unreactive toward nonmercurial sulphydryl reagents, but those at the F9(93)β positions are reactive toward these reagents. We have studied the kinetics of the reaction of dog hemoglobin with 5,5′-dithiobis (2-nitrobenzoic acid) as a function ofpH. At allpH values studied, the reaction is kinetically monophasic. Quantitative analysis of thepH dependence of the apparent second-order rate constant shows that two ionizable groups are linked to the reaction of the sulphydryl group. TheirpK a values are 5.57 and 9.0. These values are assigned to HisHC3(146)β and to the CysF9(93)β sulphydryl. We find that dog carbonmonoxyhemoglobin is significantly—almost an order of magnitude—less reactive than the aquomet, azidomet, and oxy derivatives. This result may be due to a greater tendency (at acidpH) for the salt bridge between HisHC3(146)β and AspFG1(94)β to form in the carbonmonoxy than in the other derivatives. Formation of this salt bridge is known to hinder access to the CysF9(93)β sulphydryl [Perutz, M. F. (1970),Nature 228, 734–739].
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    Initial steps of αand β-d-glucose binding to intact red cell membrane (1993)
    Springer
    The journal of membrane biology 132 (1993), S. 167-178 
    Details
    ISSN: 1432-1424
    Keywords: red cell ; glucose transport protein ; GLUT1 ; kinetics ; rapid reactions ; tryptophan
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary The kinetics of the initial phases of d-glucose binding to the glucose transport protein (GLUT1) of the human red cell can be followed by stopped-flow measurements of the time course of tryptophan (trp) fluorescence enhancement. A number of control experiments have shown that the trp fluorescence kinetics are the result of conformational changes in GLUT1. One shows that nontransportable l-glucose has no kinetic response, in contrast to d-glucose kinetics. Other controls show that d-glucose binding is inhibited by cytochalasin B and by extracellular d-maltose. A typical time course for a transportable sugar, such as d-glucose, consists of a zero-time displacement, too fast for us to measure, followed by three rapid reactions whose exponential time courses have rate constants of0.5–100 sec+−1 at 20°C. It is suggested that the zero-time displacement represents the initial bimolecular ligand/GLUT1 association. Exponential 1 appears to be located at, or near, the external membrane face where it is involved in discriminating among the sugars. Exponential 3 is apparently controlled by events at the cytosolic face. Trp kinetics distinguish the K d of the epimer, d-galactose, from the K dfor d-glucose, with results in agreement with determinations by other methods. Trp kinetics distinguish between the binding of the α- and β-d-glucose anomers. The exponential 1 activation energy of the β-anomer, 13.6 ± 1.4 kcal mol+−1, is less than that of α-d-glucose, 18.4 ± 0.8 kcal mol+−1, and the two Arrhenius lines cross at ≈23.5°C. The temperature dependence of the kinetic response following α-d-glucose binding illustrates the interplay among the exponentials and the increasing dominance of exponential 2 as the temperature increases from 22.3 to 36.6°C. The existence of these interrelations means that previously acceptable approximations in simplified reaction schemes for sugar transport will now have to be justified on a point-to-point basis.
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    Characterization of ion channels from Acetabularia plasma membrane in planar lipid bilayers (1993)
    Springer
    The journal of membrane biology 133 (1993), S. 145-160 
    Details
    ISSN: 1432-1424
    Keywords: Acetabularia ; K+ channels ; kinetics ; planar lipid bilayers ; voltage dependence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary Plasma membrane from Acetabularia acetabulum was prepared by aqueous-polymer two-phase partitioning and incorporated into planar 1-palmitoyl-2-oleoyl phosphatidylethanolamine bilayers by stirring in the presence of a (cis∶trans) 325∶100 mm KCl gradient. Under these conditions five distinct K+-selective channels were observed which had unitary chord-conductances (determined between 30 mV either side of the reversal potential) and frequencies of incorporation (in parentheses) of 1,600 pS (26%), 485 pS (21%), 259 pS (53%), 140 pS (37%) and 27 pS (37%). Two Cl−-selective channels were also observed, which had unitary chord-conductances of 8 and 48 pS and were present in 21 and 16% of bilayers, respectively. The voltage dependencies of channel open probability (P o ), open-state time constant (τ o) and closed-state time constant (τ c) were determined for the 259, 140 and 27 pS K+ channels. The P o of all three channels increased with increasingly positive membrane potentials. Thus, since these channels were oriented with their extracellular face adjacent to the cis chamber, which was grounded, all would exhibit outward rectification in vivo. Changes in P o were effected by modulation of τ c in all channels, which shortened as membrane potentials became more positive, and also of τ o in the 140 and 27pS channels, which increased as membrane potentials became more positive. Extracellular (cis) KCl concentration (and/or the KCl gradient across the bilayer) affected the P o of all three K+ channels, shifting the P o /membrane potential relationship in the direction of the change in the potassium reversal potential. In all channels this was achieved largely by changes in τ c .
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  • 99
    Electronic Resource
    Electronic Resource
    Study of the mechanism of the addition of benzyl bromide to trimethylvinylsilane in the presence of the Fe(CO)5—DMF system (1993)
    Springer
    Russian chemical bulletin 42 (1993), S. 1352-1356 
    Details
    ISSN: 1573-9171
    Keywords: benzyl bromide, trimethylvinylsilane, addition ; radicals ; metal-complex initiation ; kinetics ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The general kinetics of the addition of benzyl bromide to trimethylvinylsilane in the presence of the Fe(CO)5—DMF system has been studied. The reaction orders with respect to each reagent found in the study correspond to a radical chain mechanism of the process. The metal-complex system takes part only in the initiation stage and only at a strictly defined ratio of the components.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00699930
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  • 100
    Electronic Resource
    Electronic Resource
    The influence of the mercury and thallium atoms in organomercury and organothallium nitroxyl radicals on their reactivity (1993)
    Springer
    Russian chemical bulletin 42 (1993), S. 205-207 
    Details
    ISSN: 1573-9171
    Keywords: kinetics ; organomercury nitroxyls ; organothallium nitroxyls ; coordination bond ; hydrazobenzene ; reduction ; rate constant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An increase is found in the reactivity of organomercury and organothallium nitroxyl mono- and biradicals of the imidazoline type in comparison with the analogous compounds without organometallic fragments. This is explained by the formation of coordination bonds N→Hg, N→Tl, and N→O→Hg.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00700013
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    Paper (German National Licenses)
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