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  • 1995-1999  (850)
  • 1960-1964  (10)
  • 1920-1924
  • Industrial Chemistry and Chemical Engineering  (746)
  • Alkenes
  • Phosphorus
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Mycorrhiza 9 (1999), S. 97-101 
    ISSN: 1432-1890
    Keywords: Key words Glomus mosseae ; Lipid ; Phosphorus ; Protein ; Seed ; Triticum durum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Root colonization by arbuscular mycorrhizal fungi (AMF) may affect protein and lipid composition of plants by altering P nutrition or by eliciting other metabolic responses in the host plant. This study was conducted to determine the effects of an AMF and soil P on seed protein and lipid contents and yield of two genotypes of durum wheat (Triticum durum L.). Plants were grown in a greenhouse using soil: sand mixes with different levels of P, and with or without the AMF Glomus mosseae [(Nicol. and Gerd.) Gerd. and Trappe]. Percentage AMF root colonization decreased as P added to soil increased. The wheat genotype CR057 had higher AMF root colonization but lower seed P and protein concentrations than CR006. Without added soil P, protein concentration was significantly lower and lipid concentration and seed dry weight higher in arbuscular mycorrhizal (AM) than in nonAM plants. Seed lipid and protein contents were highly correlated with P content of plants. In nonAM plants, seed lipid and protein contents were low with no added soil P and did not differ with added soil P. Seed protein/lipid (Pro/L) concentration ratios of AM plants were higher than those of nonAM plants only when no P was added to the soil. The data indicate different patterns of seed P accumulation and different relationships between seed P and protein and lipid in AM and nonAM plants. Thus, both the presence and degree of AMF root colonization affected seed lipid metabolism in these durum wheat genotypes.
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  • 2
    ISSN: 1432-1890
    Keywords: Key words Arbuscular mycorrhizae ; Lythrumsalicaria ; Phosphorus ; Wetland ; Emergent aquatic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The relationship between nutrient availability and mycorrhizal status has been well studied for terrestrial plant species, but has been examined rarely in aquatic and emergent aquatic species. The purpose of this study was to determine the effect of phosphorus availability on the arbuscular mycorrhizal (AM) status of an emergent aquatic, Lythrum salicaria L. L. salicaria was grown in hydroponic sand culture at five phosphorus concentrations (0, 100, 1000, 10 000, and 47 500 μg PO4/l nutrient solution) for 49 days with or without mycorrhizal inoculum obtained from wetland soil. Inoculated plants at the lowest three phosphorus concentrations were colonized by AM, whereas there was no colonization of plants grown at the highest two phosphorus concentrations. Colonization by AM fungi occurred in conjunction with symptoms of phosphorus deficiency in L. salicaria under experimental conditions: plants at the lowest three phosphorus concentrations had lower biomass and higher root: shoot weight ratios than plants at the highest two concentrations. However, total biomass and internal phosphorus concentration did not differ between inoculated and control plants. Further studies are needed under conditions more closely mimicking natural dynamics.
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  • 3
    ISSN: 1432-1890
    Keywords: Key words Competition ; Ectomycorrhiza ; External hyphae ; Phosphorus ; Pisolithus arhizus ; Uptake kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Our objective was to evaluate the ability of an ectomycorrhizal fungus to alter the competitive interaction of pine seedlings growing with grass, and to determine whether the interaction was modified by soil-phosphorus (P) concentration. Slash pine (Pinus elliottii), inoculated with the ectomycorrhizal fungus Pisolithus arhizus or fortuitously colonized by Thelephora terrestris, and a native grass (Panicum chamaelonche) were grown in a greenhouse at three P levels (0.32, 3.22, 32.26 μM H3PO4). Pine inoculated with P. arhizus took up more P when competing with the nonmycorrhizal grass than when competing with another pine (irrespective of pine mycorrhizal status). Phosphorus uptake kinetics (Cmin, the minimum concentration at which P can be absorbed from a solution; Imax, the maximum uptake rate) for pine and grass were also determined under hydroponic conditions. Pine had a higher Imax than grass but grass had a lower Cmin, suggesting that pine is more competitive at higher nutrient concentrations while grass is more competitive at lower nutrient concentrations. The controlled conditions used in these experiments allowed us to evaluate specific parameters (P uptake and absorbing surface area) affecting plant competition.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 28 (1999), S. 204-211 
    ISSN: 1432-0789
    Keywords: Key words Alley cropping ; Calcium ; Magnesium ; Nitrogen ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  Balances between nutrients applied or mineralized and nutrients removed in maize grain and stover were calculated in a hedgerow intercropping experiment in which Leucaena leucocephala and L. pallida prunings and cattle manure were applied. Hedgerow intercropping (also called alley cropping) is an agroforestry system in which trees are grown in dense hedges between alleys where short-cycle crops are grown. The hedges are pruned periodically during the cropping period and the prunings are added to the soil as green manure. In control treatments, nutrient depletion per season was in the order of 7–19 kg N ha–1, 4–12 kg P ha–1, 10–26 kg K ha–1, 0–2 kg Ca ha–1 and 3–6 kg Mg ha–1. N fertilizer reversed the depletion of N, but it accelerated the depletion of the other nutrients. Manure and at least two applications of leucaena prunings resulted in net positive balances of N, K, and Ca between amounts applied or mineralized and amounts removed by maize. The amounts of P and Mg applied with, or mineralized from, prunings or manure were insufficient to offset the negative balances of these nutrients.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 28 (1999), S. 182-195 
    ISSN: 1432-0789
    Keywords: Key words Alley cropping ; Calcium ; Magnesium ; Nitrogen ; Phosphorus ; Intercropping
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  A litter bag technique was used to study the decomposition and release of N, P, K, Ca, and Mg from Leucaena leucocephala and L. pallida prunings and cattle manure in a hedgerow intercropping trial conducted in the Ethiopian highlands. Hedgerow intercropping (also called alley cropping or alley farming) is an agroforestry system in which trees are grown in dense hedges between alleys where short-cycle crops are grown. The hedges are pruned periodically during the cropping period and the prunings are added to the soil as green manure. Manure was the most resistant to decomposition, losing only 15% of its dry matter (DM) in 15 weeks, compared to 41–57% lost by leucaena prunings. Large quantities of K (up to 104 kg ha–1) were mineralized from prunings and manure, but Ca and Mg were mostly immobilized. More N and P were released from prunings than from manure, which resulted in net immobilization of these nutrients in the initial stages of decomposition and net mineralization in later stages. Between the leucaenas more N was mineralized and less Ca and Mg were immobilized when L. leucocephala prunings were applied than when L. pallida prunings were applied. Fertilizer N increased DM decomposition and N mineralization. Mineralization of the nutrients was constrained by lignin and polyphenol contents. It is concluded that leucaena mulch and cattle manure may be significant sources of N and K for crop growth, but external sources of P, Ca and Mg may be required, particularly in acid soils which have low contents of these nutrients. However, this fertility effect has to be evaluated against the competition effect of trees to predict crop response.
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  • 6
    ISSN: 1432-0789
    Keywords: Key words Alley cropping ; Calcium ; Magnesium ; Nitrogen ; Phosphorus ; Leaf pruning
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  The effects of Leucaena leucocephala and L. pallida prunings and cattle manure on maize nutrient uptake and yield were investigated in a hedgerow intercropping trial in the Ethiopian highlands. Hedgerow intercropping (also called alley cropping) is an agroforestry system in which trees are grown in dense hedges between alleys where short-cycle crops are grown. The hedges are pruned periodically during the cropping period and the prunings are added to the soil as green manure. For each leucaena species, the experiment had 16 treatments resulting from a factorial combination of four levels of leucaena leaf prunings (no prunings applied; first prunings applied; first and second prunings applied; first, second and third prunings applied), two levels of air-dried cattle manure (0 and 3 t dry matter ha–1) and two levels of N fertilizer (0 and 40 kg N ha–1 as urea). Uptake of N, P and K increased significantly with application of the three nutrient sources, but uptake of Ca and Mg either did not respond or decreased with application of prunings and manure. All the three factors increased maize grain and stover yields significantly, usually with no significant interactions between the factors. At least two applications of prunings were required to significantly increase nutrient uptake and maize yield. Maize in the row closest to the hedge did not respond to these nutrient inputs. It is concluded that hedgerow intercropping, with or without manure application, can increase crop yields moderately (to 2–3 t ha–1 maize grain yields) in the highlands, but P, Ca and Mg may have to be supplied from external sources if they are deficient in the soil. Additional N is still required for higher yields (〉4 t ha–1 maize grain yields). However, quantification of the competition effects of the trees is also required to confirm these results.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 30 (1999), S. 7-13 
    ISSN: 1432-0789
    Keywords: Key words Earthworm ; Surface casts ; Rainfall events ; Soil erosion ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  We investigated whether, under a temperate climate and in a maize crop, earthworm casts could contribute to soil erosion and further favour the exportation of phosphorus by runoff waters. Recording of casts was made in compacted (wheel-tracks) and non-compacted inter-rows, for a 2-month period in spring. To assess the rainfall impact on cast evolution, half of the observation sites were protected against rain splash by a nylon mesh placed above the soil surface. The water runoff was collected and analysed for sediment contents and phosphorus concentration. The mean annual production of surface casts was calculated to be 34 kg (dry weight) year–1 kg–1 earthworm (fresh weight). Synchronization between cast erosion and rainfall events was shown under natural conditions (unprotected sites). The erosion rate was 4 times greater over rainy periods than dry ones, reaching 80% of cast numbers. It appeared that not the runoff effect but the splash effect, due to the kinetics of the drops, disrupted casts. Newly formed casts disappeared first, with the erosion rate decreasing twofold for casts more than 10 days old. Cast erosion and runoff, as well as worm casting activity, were greater under compacted sites than under non-compacted sites, indicating an influence of earthworms on soil erosion from compacted soils. The total phosphorus content was similar in casts and uningested soil (0.80 mg phosphorus g–1). Potential phosphorus losses from cast erosion was calculated to reach 25–49 mg phosphorus m–2 per rainfall event depending on soil compaction. The amounts of particulate phosphorus recovered in water runoff after each rainfall event varied from 1 mg to 11 mg phosphorus. These results are compared and discussed.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Oecologia 119 (1999), S. 247-255 
    ISSN: 1432-1939
    Keywords: Key words Nitrogen ; Phosphorus ; Nutrient spiraling ; Uptake rate and length ; Stream nutrient cycling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Nitrate and phosphate solutions were released into two reaches of two central Idaho streams to determine within- and between-stream variability in uptake lengths, uptake rates, and mass transfer coefficients. Physical and biotic stream characteristics and periphyton nitrate-uptake rates in recirculating chambers were measured to determine their influence on nutrient dynamics. Phosphate uptake length did not differ among the four reaches. There were no within-stream differences in nitrate uptake lengths but they did differ between the two streams. Long nitrate uptake lengths likely were due to instream concentrations above saturation but also may have been influenced by differences in active surface area and algal abundance. Nitrate and phosphate uptake lengths were longer, and uptake rates higher, than most other published values. However, mass transfer coefficients were comparable to measurements in other streams. Mass transfer coefficients may be a better parameter for temporal and spatial comparisons of instream nutrient dynamics, and for determining the underlying causes of variability in uptake length.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Coral reefs 18 (1999), S. 263-271 
    ISSN: 1432-0975
    Keywords: Key words Syringodium isoetifolium ; Cyanobacteria ; Stable isotopes ; Nitrogen ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract  The natural carbon and nitrogen stable isotope ratios (δ13C, δ15N) of various autotrophs and heterotrophs were measured in a Syringodium isoetifolium-dominated seagrass bed at Dravuni Island, Fiji to define carbon and nitrogen sources for heterotrophic organisms in a system where few animals graze directly on seagrass leaves. The organic carbon, nitrogen, and phosphorus content of organisms was also determined. The δ13C and δ15N data suggest that herbivorous heterotrophs in this seagrass bed depend significantly on epiphytic cyanobacteria rather than seagrass leaves and its detritus. This can be attributed to relative differences in nitrogen content of those organic materials. The cyanobacteria nitrogen content (3.6–4.8% of DW) is nearly half that of heterotrophs (7.0–8.6% N of DW) while that of S. isoetifolium origin (0.6–1.1% N of DW) is less than one third of the cyanobacteria nitrogen content. Phosphorus content was similar among cyanobacteria (0.8–1.1 mg g-1) and S. isoetifolium (0.4–1.4 mg g-1). These results suggest that cyanobacteria are important food sources for heterotrophs at the study site, and that inorganic nitrogen released through breakdown of cyanobacteria by heterotrophs may support the continued production of S. isoetifolium.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 410 (1999), S. 123-130 
    ISSN: 1573-5117
    Keywords: Nitrogen ; Phosphorus ; rivers ; modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract In many European rivers, including the major streams of the Rhine and Elbe basins, the nutrient load (N and P) still exceeds target levels. In this paper, a model is presented that describes the river nutrient load as a function of nutrient sources, runoff and lithology in the upstream basin. The model was tested with independent data on nutrient sources (input) and nutrient river load (output) for 130 specific combinations of sub-basins and 5 year periods. A wide range of river systems within the Rhine and Elbe basins were included and the analysis covers a period of 25 years from 1970 to 1995. Most of the observed spatial and temporal variation in the average annual river nutrient load was successfully described by the model. It is therefore concluded that the model can be used to predict the effect of changes in nutrient sources (e.g. reduction of livestock numbers, further improvement of waste water treatment plants etc.) on the average annual nutrient loads of the rivers Rhine, Elbe and their main tributaries.
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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 91-96 
    ISSN: 1434-193X
    Keywords: Alkenes ; Electrophilic additions ; β-Sultones ; sec-Alkyl chlorosulfate ; 2-Chloro-1-alkanesulfonic acid ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -An exploratory study has been made on the reaction of a number of non-branched alkenes in [D]chloroform as an aprotic solvent, using chlorosulfuric acid as reagent both in the presence and the absence of [D8]1,4-dioxane as complexing agent. Reaction of cyclopentene (1a) with 1.1 mol-equiv. of chlorosulfuric acid in [D]chloroform in the presence of 2.2 mol-equiv. of [D8]1,4-dioxane at 0 °C yielded quantitatively 1,2-cyclopentanesultone (2a). Under similar reaction conditions, the linear alkenes 1b-g afforded the corresponding β-sultones 2b-g. The ClSO3H-dioxane complex acted as a sulfonating reagent with the alkenes to yield the corresponding β-sultones in a syn cycloaddition of SO3 to the Carbon-Carbon double bond. In the absence of [D8]1,4-dioxane the reaction of the linear alkenes 1a-1k in [D]chloroform with chlorosulfuric acid at -40 °C led to the formation of the sec-alkyl chlorosulfates 5a-i, which were formed after initial protonation of the alkene by the strongly acidic ClSO3H. Cyclopentyl chlorosulfate (5a) in [D]chloroform at 0 °C was quantitatively converted into 1,2-cyclopentanesultone (2a). The sec-alkyl chlorosulfates 5b-i at 0 °C gave rise to a mixture of the internal trans- and cis-β-sultones 2b-m. Reaction of 1-octene (1g) with both acetyl sulfate (6a) and trifluoroacetyl sulfate (6b) as reagent in [D]chloroform at -20 °C directly afforded the products 1,2-octanesultone (2g), and the (E) and (Z) isomer of 2-octene-1-sulfonic acid (4g).
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1659-1664 
    ISSN: 1434-1948
    Keywords: Phosphorus ; Iminophosphorane ; Staudinger reaction ; Heterocycles ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Staudinger-model reaction H3P (1) + HN3 (2) → H3P=NH (5) + N2 (6) has been investigated at the CCSD(T)/6-31G**//MP2(Full)/6-31G* level. Primary products formed in this reaction are the phosphazides H3P=N-N=NH (3) which exist as trans and cis isomers. In contrast to some previous assumptions, cis -3is 8.2 kcal mol-1 more stable than trans -3 but decomposes rather easily into the expected products H3P=NH and N2. This decomposition can be effectively hampered by intramolecular donor-acceptor interactions as shown by calculations on model compounds as well as by experiments. Thus the reaction of a methylene-σ3,λ3-phosphanyl-σ5,λ5-phosphorane with PhN3 led to a new four-membered heterocycle containing a thermally remarkable stable cis-phosphazide moiety.
    Additional Material: 4 Ill.
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  • 13
    ISSN: 1434-1948
    Keywords: Palladium ; Bidentate nitrogen ligands ; Carbohydrates ; Alkenes ; Enantioselectivity ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral N,N-chelates of formula 6-Me-pyridine-2-CH=N-R (1) and R-N=CH-CH=N-R (2) (R = 6-deoxy-α-D-glucoside or 6-deoxy-α-D-mannoside residue) and their palladium(0) complexes [Pd(N,N-chelate)(olefin)] (I) were prepared. Symmetrical type 2 ligands induced higher enantioselectivity in the coordination of prochiral olefins. The ability of a type 1 chelate to promote a stereoselective process was also assessed, i.e. dimethylfumarate inserted into the Pd-Me bond formed upon methylation of a type I complex with 50% ee. Finally, a water-soluble Pd0 complex was also prepared by deprotecting the alcoholic functions on the sugar residue, and its molecular structure determined through X-ray diffractometry.
    Additional Material: 2 Ill.
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  • 14
    ISSN: 1434-1948
    Keywords: Aluminium ; Amides ; Calcium ; Metallacycles ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of calcium bis[bis(trimethylsilyl)amide] with two equivalents of tris(trimethylsilylmethyl)alane yields (Me3SiCH2)2Al-N(SiMe3)2 (1) and the dimer [(Me3Si)2N-Ca(μ-CH2SiMe3)2Al(CH2SiMe3)2]2 (2). The five-coordinate bridging carbon atoms show Ca-C bond lengths of 264 and 268 pm. A similar reaction with calcium bis[bis(trimethylsilyl)phosphanide] gives the dimer [(Me3SiCH2)2Al-P(SiMe3)2]2 (3) with crystallographic C2 symmetry. A calcium-containing species is not isolable, however, in the presence of DME - ether cleavage reactions and the formation of the centrosymmetric dimer [(Me3SiCH2)2Al-OCH2CH2OMe]2 (4) are observed. The central moiety is an Al2O2 cycle with fivefold coordinated aluminium centers.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2215-2220 
    ISSN: 1434-1948
    Keywords: Magnesium ; Metalation ; Phosphorus ; Polyhedra ; X-ray structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The magnesiation of triisopropylsilylphosphane with dibutylmagnesium in toluene yields the octanuclear complex [Mg8(PSiiPr3)6{P(H)SiiPr3}4] (1) which consists of MgPSiiPr3 units forming a hexagonal Mg6P6 prism, with two opposite Mg2P2 moieties capped by additional Mg[P(H)SiiPr3]2 groups. If a small amount of THF is present during the metalation reaction [(THF)4Mg6(PSiiPr3)6] (2) also containing a hexagonal Mg6P6 prism can be isolated. The magnesiation of H2P-SiiPr3 in tetrahydrofuran leads to the formation of the tetrameric complex [(THF)MgPSiiPr3]4(3) with a slightly distorted Mg4P4 cubane-like structure.The structures depend strongly on the steric strain caused by the trialkylsilyl substituents and the neutral coligands at the magnesium center. The highest steric strain, which is induced by coordination to every magnesium atom, leads to the smallest MgnPn polyhedron - the central Mg4P4 heterocubane moiety. In compounds 1 and 2 the hexagonal Mg6P6 prism is formed, however, with reduced steric strain as observed for 2 where the Mg-P bond lengths become more similar.
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  • 16
    ISSN: 1434-1948
    Keywords: Phosphorus ; Ferrocenes ; Phosphorylated iminophosphoranes ; Dendrimers ; Cations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several R3P=N-P(X)R′2 and Fe[C5H4Ph2P=N-P(X)R′2]2 derivatives (X = S, O) are readily obtained from Staudinger reactions between phosphanes and N3-P(X)R′2. The P=N-P=X groups are easily alkylated on the × atom with methyl or isopropyl triflates. The alkylation induces a lengthening of the P-X bond, as shown by X-ray diffraction studies. This corresponds to a weakening of the P-X bond which can be cleaved with P(NMe2)3 to yield [P=N-P:] linkages. The presence of tricoordinated phosphorus atoms opens the way to a versatile reactivity, including the reaction with alkyl iodides and functionalized azides. These molecules are good models for screening which types of reagents and reactions could be used with macromolecules possessing also P=N-P=X linkages, such as dendrimers.
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  • 17
    ISSN: 1434-1948
    Keywords: Arsenic ; Barium ; Calcium ; Metalations ; NMR spectroscopy ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metalation of triisopropylsilylphosphane with bis(tetrahydrofuran-O)calcium bis[bis(trimethylsilyl)amide] in tetrahydropyran (thp) in a molar ratio of 3:2 yields (Me3Si)2NCa[μ-P(H)SiiPr3]3Ca(thp)3 (1) containing a trigonal-bipyramidal Ca2P3 core, the metal atoms occupying apical positions. Reaction of two equivalents of triisopropylsilylphosphane or -arsane with bis(tetrahydrofuran-O)barium bis[bis(trimethylsilyl)amide] in tetrahydrofuran gives the corresponding bis(phosphanide) 2 and bis(arsanide) 3, compounds of the type (thf)3Ba[μ-E(H)SiiPr3]Ba(thf)2E(H)SiiPr3 with E = P, As. The equimolar reaction of (tri-tert-butylsilyl)phosphane with (thf)2Ba[N(SiMe3)2]2 in toluene yields heteroleptic dimeric (thf)2Ba[N(SiMe3)2][P(H)SitBu3] (4). Addition of a further equivalent of H2PSitBu3 leads to the formation of homoleptic (thf)nBa[P(H)SitBu3]2 (5). Dissolution of the latter in aromatic hydrocarbons leads to the elimination of H2PSitBu3, yielding dimeric (thf)Ba3(PSitBu3)2[P(H)SitBu3]2 (6). The inner core of 6 consists of the tetramer (BaPSitBu3)4 based on a Ba4P4 heterocubane unit, two opposite faces being capped with (thf)Ba[P(H)SitBu3]2 molecules.
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  • 18
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2233-2241 
    ISSN: 1434-1948
    Keywords: Phosphorus ; Heterocycles ; Phosphinines ; Gold ; Cycloadditions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coordination behaviour of 2,6-disilyl-substituted phosphinines towards gold(I) has been examined. The reaction of the bis(trimethylsilyl)phosphinine 1 with [AuCl(SMe2)] gives the corresponding AuCl derivative 2. X-ray crystal structure analysis reveals that the aromaticity of the phosphinine ring is slightly reduced as a result of the poor π-back bonding ability of the AuCl fragment. The same phenomenon is observed in the cationic complex [Au(1)2][GaCl4] (3) which was readily prepared by reaction of two equivalents of 1 with [AuCl(SMe2)] followed by treatment with GaCl3 at low temperature. Reaction of 2,6-bis(phenylethynyldimethylsilyl)phosphinine (4) with the same precursor leads similarly to the complex [AuCl(4)] (5). Interestingly, this complex dimerizes upon crystallization to give the bis(phosphabarrelene) complex 6, also structurally characterized. The formation of 6 results from a [4 + 2] cycloaddition between one alkynyl group of each phosphinine with the other phosphinine subunit. The formation of the cationic complex [Au(4)][GaCl4] (8) occurs under classical conditions but it disproportionates to give the cationic complex [Au(4)2][GaCl4] (9) and colloidal gold deposition. The formation of 9 has been ascertained by treating 8 with one equivalent of ligand 4. Additionally, 9 can also be obtained in a straightforward fashion by treating two equivalents of 4 with [AuCl(SMe2)] followed by treatment with GaCl3 at low temperature. The structure of 9 has been elucidated. Despite a particular arrangement of the alkyne groups which encapsulate the gold coordination sphere, no gold-alkyne interactions are visible.
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  • 19
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2295-2299 
    ISSN: 1434-1948
    Keywords: Lewis acids ; Bismuth ; Aluminum ; Phosphorus ; Tin ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dilithium salts of N-methyl-N′,N′′-bis(diisopropyl)- and -(trimethylsilyl)-diethylenetriamine 1a,b react with SnCl2 affording the corresponding stannylenes 2a,b in 60 and 80% yield, respectively. Compound 1b also reacts with BiCl3 to give the bismuth chloride 5 (90% yield). Derivatives 2b and 5 have a symmetrical bicyclic structure and are monomeric both in solution and in the solid state. When 2b is treated with BiCl3 or PCl3, an oxidation reaction leads to the hypercoordinated tin(IV) dichloride 3 (58% yield), or a transmetallation gives rise to the oniophosphane 4 (95% yield), respectively. Transmetalation reactions also occurred when 5 was treated with AlCl3, GaCl3 or SnCl2 affording the corresponding aluminum chloride 6 (81% yield), gallium chloride 7 (38% yield) or tin dichloride 3 (38% yield). The observed reactivity for 2 and 5 is compared to that reported for Veith's stannylene or bismuth chloride.
    Additional Material: 4 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 887-898 
    ISSN: 1434-1948
    Keywords: Tin ; Phosphorus ; Intramolecular coordination ; O ligands ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New intramolecularly coordinated organotin compounds containing the monoanionic O,C,O-coordinating ligand {4-tert-Bu-2,6-[P(O)(OEt)2]2C6H2}- have been synthesized by substitution reactions starting from organotin halides. In view of the enhanced reactivity of the intramolecularly coordinated compounds {4-tert-Bu-2,6-[P(O)(OEt)2]2C6H2}SnR2R′ (2, R = Ph, R′ = CH2SiMe3; 3, R = R′ = Ph; 6, R = R′ = Cl), cationic tin species are suggested to occur as intermediates in the formation of the heterocyclic compounds [1(Sn),3(P)-Ph2SnOP(O)(OEt)-5-tert-Bu-7-P(O)(OEt)2]C6H2 (8), [1(Sn), 3(P)-Ph(Me3SiCH2)SnOP(O)(OEt)-5-tert-Bu-7-P(O)(OEt)2]C6H2 (15), and {[1(Sn),3(P)-Cl2SnOP(O)(OEt)-5-tert-Bu-7-P(O)(OEt)]C6H2}2 (16). The latter compounds are formed by intramolecular cyclizations of pentacoordinate cationic tin species under elimination of ethyl halide. Furthermore, the synthesis of [1(Sn),3(P)-Ph2SnOP(O)(OH)-5-tert-Bu-7-P(O)(OH)2]C6H2 (13) is described. Reaction of 8 with an excess of Me3SiBr leads to the unexpected formation of {2-[P(O)(OEt)(OSiMe3)]-4-tert-Bu-6-[P(O)(OEt)2]C6H2}SnPhBr2 (9) as a result of an O-Sn bond cleavage initiated by Me3SiBr and subsequent reaction of the intermediate with further Me3SiBr under Sn-C bond cleavage. The high donor capacity and the rigidity of the new ligand {4-tert-Bu-2,6-[P(O)(OEt)2]2C6H2}- are demonstrated by X-ray diffraction analyses of the tetraorganotin compound 2 and the monoorganotin trichloride 6. Furthermore, the molecular structures of the 2,3,1-oxaphosphastannoles 8 and 16 are discussed.
    Additional Material: 5 Ill.
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  • 21
    ISSN: 1434-1948
    Keywords: Phosphorus ; Rhenium ; 31P-NMR spectroscopy ; Tripodal polyphosphanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of white phosphorus with [(triphos)Re(CO)2(OTf)] (1) in dichloromethane affords the new tetraphosphorus complex [(triphos)Re(CO)2(η1-P4)](OTf) (2) [triphos = MeC(CH2PPh2)3; OTf = OSO2CF3]. Compound 2 reacts with a second equivalent of 1 to give the binuclear complex [{(triphos)Re(CO)2}2(μ,η1,η1-P4)](OTf)2 (3) in which a tetrahedro-P4 ligand behaves as tethering unit between two [(triphos)Re(CO)2]+ moieties. Complexes 2 and 3 represent the first soluble metal complexes of the tetraphosphorus molecule where the P4 ligand has not undergone any major modification.
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  • 22
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 945-949 
    ISSN: 1434-1948
    Keywords: Phosphorus ; Pn ; C5H3(SiMe3)2 ligands ; Cobalt ; Coordination chemistry ; Crystallography ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal or photochemical reaction of [Cp′′Co(CO)2] (1) [Cp′′ = C5H3(SiMe3)2-1,3] with white phosphorus (P4) gives [{Cp′′Co}2(P5-P5){CoCp′′}2] (2) and [{Cp′′Co}3P4(μ-CO)] (3) as well as [{Cp′′Co}2(μ-η2:η2-P2)2] (4). Cobalt complexes 2, 3, and 4 have been characterized by an X-ray crystal-structure determination.
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  • 23
    ISSN: 1434-193X
    Keywords: Fluorine ; vic-Difluorination ; Fluoroalkenes ; Xenon difluoride ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vic-Difluorination proceeds by the reaction of fluoroalkenes with xenon difluoride to afford the corresponding fluorinated compounds. From the reaction with polyfluoroalkenes, the products are obtained in high to excellent yields. In this reaction, the fluorine atom substituent of alkene stabilizes the cation intermediate and suppresses side-reactions such as rearrangement.
    Additional Material: 2 Tab.
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  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 2249-2255 
    ISSN: 1434-193X
    Keywords: Alkenes ; Eliminations ; Halogens ; Laser chemistry ; Photolysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dehydrochlorination of 1,2-dichloropropane (DCP) was conducted by thermal elimination and CO2 laser-induced dielectric breakdown, which was induced by focusing the 10.6 μm lines of a CO2 TEA laser. Thermal dehydrochlorination proceeded by a four-centered mechanism at 〉 425 °C and by a surface-catalyzed radical process at 〈 400 °C. The product distribution of the breakdown-induced reaction at 〈 400 °C resembled that of high temperature thermal elimination and the corresponding temperature was estimated to be 〉 2000 °C.
    Additional Material: 4 Ill.
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  • 25
    ISSN: 1434-193X
    Keywords: Alkenes ; Methylthiomethyl sulfone ; Carbenoids ; Hetero-substituted carbanions ; Vinyl sulfides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The reaction of methylthiomethyl p-tolyl sulfone with alkyl sulfones when lithiated gives regioselectively vinyl sulfides in high yields in the presence of Ni(acac)2 or Fe(acac)3.
    Additional Material: 2 Ill.
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  • 26
    ISSN: 1434-193X
    Keywords: Hydrogen transfer ; Zirconium ; Alkenes ; Isobutylzirconocene chloride ; Lewis acid catalysis ; Lewis acid catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The hydrozirconation reaction of monosubstituted alkenes with iBuZrCp2Cl can be significantly accelerated by catalytic amounts of various Lewis acidic metal compounds, most notably AlCl3, Me3SiI, and Pd complexes, such as Li2PdCl4 and Cl2Pd(PPh3)2.Supporting information for this article is available on the WWW under -http://www.wileY-Vch.de/contents/jc_2046/1999/99042_s.pdf or from the author.
    Additional Material: 1 Tab.
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  • 27
    ISSN: 1434-193X
    Keywords: Alkenes ; Chirality ; Longicorn beetle ; Pheromones ; Psacotheahilaris ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Both the enantiomers of (Z)-21-methyl-8-pentatriacontene (1), the major component of the female-produced contact sex pheromone of the yellow-spotted longicorn beetle (Psacotheahilaris), were synthesized by starting from the enantiomers of citronellol (2)
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  • 28
    ISSN: 1434-193X
    Keywords: Alkenes ; Epoxidation ; Manganese ; Porphyrins ; Catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of MnIII porphyrins progressively halogenated in the β-pyrrolic positions was employed to catalyse the epoxidation of cis-stilbene by iodosylbenzene, and to study the role of the electronic effects on the stereoselectivity of this process. A gradual improvement in the stereoselectivity on increasing the number of β-halogen atoms was observed. The role of steric effects upon the epoxidation was also investigated by placing ortho-substituents in the meso-phenyl rings, and it was found that steric effects are more important than electronic effects toward the stereoselectivity of this process. These results can be rationalised by proposing a competition between a nonstereoselective electrophilic pathway of addition and a stereospecific pathway of oxygen insertion, the former being disfavoured by electron-withdrawing substituents. Alternatively, the formation of an open intermediate between the MnV oxene and the substrate could be suggested, where the stereoselectivity ought to be determined by the competition between closure of the epoxide ring and rotation around the C-C bond. In this case, the enhanced stereoselectivity given by our polyhalogenated porphyrins might be attributed to an acceleration of the epoxide ring closure caused by the electron-withdrawing effect of the halogen substituents.
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  • 29
    ISSN: 1432-1890
    Keywords: Key words Arbuscular mycorrhiza ; Iron ; Peanut ; Phosphorus ; Sorghum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The influence of an arbuscular mycorrhizal (AM) fungus on phosphorus (P) and iron (Fe) uptake of peanut (Arachis hypogea L.) and sorghum (Sorghum bicolor L.) plants was studied in a pot experiment under controlled environmental conditions. The plants were grown for 10 weeks in pots containing sterilised calcareous soil with two levels of Fe supply. The soil was inoculated with rhizosphere microorganisms only or with rhizosphere microorganisms together with an AM fungus (Glomus mosseae [Nicol. & Gerd.] Gerdemann & Trappe). An additional small soil compartment accessible to hyphae but not roots was added to each pot after 6 weeks of plant growth. Radiolabelled P and Fe were supplied to the hyphae compartment 2 weeks after addition of this compartment. After a further 2 weeks, plants were harvested and shoots were analysed for radiolabelled elements. In both plant species, P uptake from the labelled soil increased significantly more in shoots of mycorrhizal plants than non-mycorrhizal plants, thus confirming the well-known activity of the fungus in P uptake. Mycorrhizal inoculation had no significant influence on the concentration of labelled Fe in shoots of peanut plants. In contrast, 59Fe increased in shoots of mycorrhizal sorghum plants. The uptake of Fe from labelled soil by sorghum was particularly high under conditions producing a low Fe nutritional status of the plants. These results are preliminary evidence that hyphae of an arbuscular mycorrhizal fungus can mobilise and/or take up Fe from soil and translocate it to the plant.
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  • 30
    ISSN: 1432-1890
    Keywords: Key words Allium cepa ; Appressorium ; Arbuscular mycorrhiza ; Root colonisation ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The effect of root exudates from P-deficient onion on root colonisation by an arbuscular mycorrhizal fungus was examined. Onions (Allium cepa L.) were grown in solution culture at phosphorus concentrations of 0 (P0) and 2 (P2) mg P l–1. Root exudates were collected and fractionated with Amberlite XAD-4 resin to give EtOH and water soluble fractions. Onions inoculated with the arbuscular mycorrhizal fungus Gigaspora margarita Becker & Hall were grown with or without (control) root exudates and exudate fractions in a growth chamber. After 24 days, arbuscular mycorrhiza levels and appressoria formation had increased in plants treated with P0-root exudate or the P0-EtOH fraction when compared to corresponding P2 treatments or control plants. P0 and P2 water-soluble fractions did not significantly affect either aspect of fungal development. These results suggest that hydrophobic compounds found in root exudates from P-deficient onion increase appressorium formation and, therefore, enhance mycorrhiza development.
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  • 31
    ISSN: 1432-1890
    Keywords: Key words Acaulospora ; Hyacinthoides non-scripta ; Bluebell ; Disturbance ; Glomus ; Fine endophytes ; Phosphorus ; Scutellospora
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Early-season colonisation of new roots of Hyacinthoides non-scripta (L.) Chouard ex Rothm. was investigated to determine how arbuscular mycorrhizal symbiosis is re-established after the annual root system is shed. During the rootless phase in summer, colonies of bulbs were removed and replanted after the soil around and below the bulb had been mixed (major disturbance) so as to disrupt the external mycelium of arbuscular mycorrhizal (AM) fungi. As a minor disturbance treatment, top soil was removed, bulbs were turned or not in their growth position with as little other disturbance as possible, and the top soil replaced. Control plants were left undisturbed. Half of the plants were harvested 3–4 weeks after the onset of root emergence. Populations of all AM fungi in roots were greatly reduced by major disturbance, whilst those in other treatments and controls were unaffected. At the second harvest, in spring, when shoots had emerged, root colonisation by fine endophytes and Scutellospora morphotypes developed in all treatments, whereas that of Acaulospora morphotypes remained low after major disturbance. Disturbance treatments delayed the appearance, at the second harvest, of mycorrhizas with degenerate arbuscules. Leaf phosphorus concentration was unaffected by soil disturbance, possibly due to partial recovery of AM fungal populations or buffering by resources stored in the bulb.
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  • 32
    ISSN: 1432-1890
    Keywords: Key words Winter wheat ; Mycorrhiza ; Phosphorus ; Dryland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  A field experiment was conducted to determine the seasonal patterns of arbuscular mycorrhiza (AM) in a dryland winter wheat (Triticum aestivum L.) system and to determine wheat growth and P uptake responses to inoculation with mycorrhizal fungus. Broadcast-incorporated treatments included (1) no inoculation with mycorrhizal fungus, with and without P fertilizer, and (2) mycorrhizal fungal inoculation at a rate of 5000 spores of Glomus intraradices (Schenck and Smith), per 30 cm in each row, with and without fertilizer P. Winter wheat was seeded within a day after treatments were imposed, and roots were sampled at five growth stages to quantify AM. Shoot samples were also taken for determination of dry matter, grain yield and yield components, and N and P uptake. No AM infection was evident during the fall months following seeding, which was characterized by low soil temperature, while during the spring, the AM increased gradually. Increases in wheat grain yields by enhanced AM were of similar magnitude to the response obtained from P fertilization. However, responses differed at intermediate growth stages. At the tillering stage, P uptake was mainly increased by P fertilization but not by fungal inoculation. At harvest, enhanced AM increased P uptake regardless of whether or not fertilizer P was added. The AM symbiosis increased with rising soil temperatures in the spring, in time to enhance late-season P accumulation and grain production.
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  • 33
    ISSN: 1432-1890
    Keywords: Key words Peas ; Aphanomyces euteiches ; Phosphorus ; PAGE ; Isozymes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The effects of inorganic phosphate levels and the presence of arbuscular mycorrhiza on disease severity of Aphanomyces euteiches in pea roots were studied. Disease severity on roots and epicotyl as well as the oospore number within infected root tissue were correlated with the phosphorus (P) level in the growth medium. The arbuscular mycorrhizal fungus Glomus intraradices increased P uptake and the P concentration in the plant but reduced disease development in peas. Polyacrylamide gel electrophoresis followed by densitometry of glucose-6-phosphate dehydrogenase specific to A.euteiches was used to measure the activity of the pathogen in roots. The enzyme activity increased with disease severity and disease incidence, except in plants supplemented with P at the highest level, where a peak in activity was seen 12 days after inoculation with the pathogen, followed by a decrease in activity. The epicotyl of mycorrhizal plants showed a reduction in disease severity although this part of the plants was not mycorrhizal. Thus, an induced systemic factor may be responsible for increased resistance in mycorrhizal plants.
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  • 34
    ISSN: 1432-0789
    Keywords: Key words Rhizobia ; Cowpea ; Antibiotic resistance ; Phosphorus ; Aluminium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  A large collection of cowpea rhizobia strains was obtained from soil samples collected from either a semi-arid or a tropical rain forest area located at about the same latitude in the north-eastern region of Brazil and evaluated for their intrinsic antibiotic resistance to eight commercial antibiotics. The aim of this study was to correlate antibiotic resistance of native rhizobia strains to edaphic-climatic factors as a way to establish suitable inoculants for specific areas. A large diversity regarding intrinsic antibiotic resistance was found, and 17 clusters were identified as varying from sensitive to gradually resistant up to 500 μg·ml–1 of the antibiotics tested. Clustering analysis did not show any pattern related to the geographic region where isolates have been obtained. On the other hand, an increase in the antibiotic-resistant rhizobia population was associated with an increase in soil P and Al contents. lsolates which were sensitive to spectinomycin, ampicillin, streptomycin, chloramphenicol and tetracycline were present at higher rates in soils devoid of Al. Rhizobia bacteria producing mucus type I (fluid and capable of spreading over the solid media) were found preferentially in soil with Al concentrations up to 36 mg·kg–1, diminishing quickly at higher levels.
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  • 35
    ISSN: 1432-1939
    Keywords: Key words Mangrove species zonation ; Sulfate reduction ; Pyrite formation ; Phosphorus ; Decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract We examined soil porewater concentrations of sulfate, alkalinity, phosphorus, nitrogen, and dissolved organic carbon and solid phase concentrations of pyrite in relation to mangrove species distributions along a 3.1-km-long transect that traversed a 47.1-km2 mangrove forest in the Dominican Republic. Iron, phosphorus, and sulfur dynamics are closely coupled to the activity of sulfate-reducing bacteria, the primary decomposers in anoxic soils of mangrove ecosystems. Patterns in the chemistry data suggested that sulfate reduction rates and storage of reduced sulfur were greater in the inland basin forest dominated by Laguncularia racemosa than the Rhizophora mangle dominated forest of the lower tidal region. The distribution of Laguncularia was significantly correlated with concentrations of total phosphorus (r= 0.99) and dissolved organic carbon (r= 0.86), alkalinity (r= 0.60), and the extent of sulfate depletion (r= 0.77) in the soil porewater and soil pyrite concentrations (r= 0.72) across the tidal gradient. Leaf tissue chemistry of Laguncularia was characterized by lower C:N and C:P ratios that could fuel the higher rates of decomposition in the Laguncularia-dominated forest. We suggest that a plant-soil-microbial feedback contributes to the spatial patterning of vegetation and soil variables across the intertidal zone of many mangrove forest communities.
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  • 36
    ISSN: 1432-1939
    Keywords: Key words Dinitrogen fixation ; Plant functional types ; legumes ; Nutrient limitation ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Plant nutrient responses to 4 years of CO2 enrichment were investigated in situ in calcareous grassland. Beginning in year 2, plant aboveground C:N ratios were increased by 9% to 22% at elevated CO2 (P 〈 0.01), depending on year. Total amounts of N removed in biomass harvests during the first 4 years were not affected by elevated CO2 (19.9 ± 1.3 and 21.1 ± 1.3 g N m−2 at ambient and elevated CO2), indicating that the observed plant biomass increases were solely attained by dilution of nutrients. Total aboveground P and tissue N:P ratios also were not altered by CO2 enrichment (12.5 ± 2 g N g−1 P in both treatments). In contrast to non-legumes (〉98% of community aboveground biomass), legume C/N was not reduced at elevated CO2 and legume N:P was slightly increased. We attribute the less reduced N concentration in legumes at elevated CO2 to the fact that virtually all legume N originated from symbiotic N2 fixation (%Ndfa ≈ 90%), and thus legume growth was not limited by soil N. While total plant N was not affected by elevated CO2, microbial N pools increased by +18% under CO2 enrichment (P = 0.04) and plant available soil N decreased. Hence, there was a net increase in the overall biotic N pool, largely due increases in the microbial N pool. In order to assess the effects of legumes for ecosystem CO2 responses and to estimate the degree to which plant growth was P-limited, two greenhouse experiments were conducted, using firstly undisturbed grassland monoliths from the field site, and secondly designed `microcosm' communities on natural soil. Half the microcosms were planted with legumes and half were planted without. Both monoliths and microcosms were exposed to elevated CO2 and P fertilization in a factored design. After two seasons, plant N pools in both unfertilized monoliths and microcosm communities were unaffected by CO2 enrichment, similar to what was found in the field. However, when P was added total plant N pools increased at elevated CO2. This community-level effect originated almost solely from legume stimulation. The results suggest a complex interaction between atmospheric CO2 concentrations, N and P supply. Overall ecosystem productivity is N-limited, whereas CO2 effects on legume growth and their N2 fixation are limited by P.
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  • 37
    ISSN: 1432-072X
    Keywords: Key words Anaerobic alkane oxidation ; Sulfate-reducing bacteria ; Cyclodextrin ; Alkenes ; Fatty acids ; Alkane activation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Natural relationships, improvement of anaerobic growth on hydrocarbons, and properties that may provide clues to an understanding of oxygen-independent alkane metabolism were studied with two mesophilic sulfate-reducing bacteria, strains Hxd3 and Pnd3. Strain Hxd3 had been formerly isolated from an oil tank; strain Pnd3 was isolated from marine sediment. Strains Hxd3 and Pnd3 grew under strictly anoxic conditions on n-alkanes in the range of C12–C20 and C14–C17, respectively, reducing sulfate to sulfide. Both strains shared 90% 16 S rRNA sequence similarity and clustered with classified species of completely oxidizing, sulfate-reducing bacteria within the δ-subclass of Proteobacteria. Anaerobic growth on alkanes was stimulated by α-cyclodextrin, which served as a non-degradable carrier for the hydrophobic substrate. Cells of strain Hxd3 grown on hydrocarbons and α-cyclodextrin were used to study the composition of cellular fatty acids and in vivo activities. When strain Hxd3 was grown on hexadecane (C16H34), cellular fatty acids with C-odd chains were dominant. Vice versa, cultures grown on heptadecane (C17H36) contained mainly fatty acids with C-even chains. In contrast, during growth on 1-alkenes or fatty acids, a C-even substrate yielded C-even fatty acids, and a C-odd substrate yielded C-odd fatty acids. These results suggest that anaerobic degradation of alkanes by strain Hxd3 does not occur via a desaturation to the corresponding 1-alkenes, a hypothetical reaction formerly discussed in the literature. Rather an alteration of the carbon chain by a C-odd carbon unit is likely to occur during activation; one hypothetical reaction is a terminal addition of a C1 unit. In contrast, fatty acid analyses of strain Pnd3 after growth on alkanes did not indicate an alteration of the carbon chain by a C-odd carbon unit, suggesting that the initial reaction differed from that in strain Hxd3. When hexadecane-grown cells of strain Hxd3 were resuspended in medium with 1-hexadecene, an adaptation period of 2 days was observed. Also this result is not in favor of an anaerobic alkane degradation via the corresponding 1-alkene.
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  • 38
    Electronic Resource
    Electronic Resource
    Springer
    Journal of computer-aided materials design 5 (1998), S. 81-88 
    ISSN: 1573-4900
    Keywords: Aggregation ; Arsenic ; Diffusion ; Lattice Monte Carlo ; Phosphorus ; Silicon ; Vacancy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In this work, we show that lattice Monte Carlo simulations can be used to span the time and distance scales between underlying atomistic processes and macroscopic diffusion behavior. We use ab- initio calculations of binding energies versus configuration to calculate hopping rates of vacancies for use in lattice Monte Carlo (LMC) simulations of diffusion and aggregation in silicon. The LMC simulations consider the biased nature of vacancy hop frequencies in the neighborhood of dopants, with interactions up to sixth-nearest- neighbor distances included. We use these simulations to investigate the expected macroscopic diffusion behavior, as well as the process by which dopant/defect aggregation occurs. Specific phenomena investigated include collective behavior leading to greatly enhanced diffusivity at high doping levels, the time dependence of effective diffusivity due to the formation of dopant/vacancy clusters, and dopant fluxes in the presence of a vacancy gradient.
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  • 39
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and applied genetics 97 (1998), S. 777-783 
    ISSN: 1432-2242
    Keywords: Key words Rice ; QTL ; Phosphorus ; Use efficiency ; Deficiency tolerance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Phosphorus (P) deficiency of soils is a major yield-limiting factor in rice production. Increasing the P-deficiency tolerance of rice cultivars may represent a more cost-effective solution than relying on fertilizer application. The objective of this study was to identify putative QTLs for P-deficiency tolerance in rice, using 98 backcross inbred lines derived from a japonica×indica cross and genotyped at 245 RFLP marker loci. Lines were grown on P-deficient soil and P uptake, internal P-use efficiency, dry weight, and tiller number were determined. Three QTLs were identified for dry weight and four QTLs for P uptake, together explaining 45.4% and 54.5% of the variation for the respective traits. Peaks for both traits were in good agreement which was to be expected considering the tight correlation of r=0.96 between dry weight and P uptake. For both traits the QTL linked to marker C443 on chromosome 12 had a major effect. Two of the three QTLs detected for internal P-use efficiency, including the major one on chromosome 12, coincided with QTLs for P uptake; however, whereas indica alleles increased P uptake they reduced P-use efficiency. We concluded that this was not due to the tight linkage of two genes in repulsion but rather due to an indirect effect of P uptake on P-use efficiency. Most lines with high use efficiency were characterized by very low P uptake and dry weight and apparently experienced extreme P-deficiency stress. Their higher P-use efficiency was thus the result of highly sub-optimal tissue-P concentrations and did not represent a positive adaptation to low P availability. The number of tillers produced under P deficiency is viewed as an indirect indicator of P-deficiency tolerance in rice. In addition to the major QTL on chromosome 12 already identified for all other traits, two QTLs on chromosome 4 and 12 were identified for tiller number. Their position, however, coincided with QTLs for tiller number reported elsewhere under P-sufficient conditions and therefore appear to be not related to P-deficiency tolerance. In this study P-deficiency tolerance was mainly caused by differences in P uptake and not in P-use efficiency. Using a trait indirectly related to P-deficiency tolerance such as tiller number, we detected a major QTL but none of the minor QTLs detected for P uptake or dry weight.
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  • 40
    ISSN: 1432-0878
    Keywords: Key words Calvaria ; Mineralization ; Calcium ; Phosphorus ; Apatite ; Atomic-force microscopy ; Transmission electron microscopy ; Rat (Sprague Dawley)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  The application of transmission electron microscopy (TEM) and atomic-force microscopy (AFM) aid the acquisition of detailed structural information on the process of hard tissue formation. The sutural mineralization of rat calvaria is taken as a model for a collagen-related mineralization system. After cryofixation or chemical fixation an anhydrous tissue preparation technique with no staining procedures is used. The atomic-force microscope and the transmission electron microscope are used for structural analysis of the mineralizing region of the sutural tissue. With the application of AFM the collagen macroperiod is shown to be well represented in the unmineralized sutural tissue. At the mineralization front the collagen fibrils are found to be thickened and to change to a characteristic stacked platelet structure. Using TEM the macroperiod is faintly visible before mineral crystallites have formed and is more prominent after the apatite crystallization has started in the fibrils. In this step a needle-like structure of the newly formed apatitic crystals is visible.
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  • 41
    ISSN: 1573-143X
    Keywords: Cage culture ; Dietary lipid ; Dietary water ; Feeding frequency ; Moist diets ; Nitrogen ; Phosphorus ; Rainbow trout (Oncorhynchus mykiss)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The nutrient losses into the water from rainbow trout (Oncorhynchus mykiss) cage culture using locally caught low-fat Baltic herring, herring-based moist diets and fishmeal-based dry diets were estimated. Feeding with herring led to nitrogen and phosphorus losses into the water twice as high as those feeding with dry pellets (78–162 versus 37–39 g N and 15–39 versus 7–18 g P per kg growth). This was supported by direct measurements of ammonia and phosphate excretion. Increasing feeding frequencies resulted in increased nutrient losses irrespective of diet. Increasing dietary lipid level had a more pronounced effect in reducing the expected nutrient losses in dry pellets than herring. The reduction within the herring was approximately 18% on average for nitrogen and 25% for phosphorus losses. Dietary water content did not affect the nutrient losses. © Rapid Science Ltd. 1998
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  • 42
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Alkenes ; Epoxides ; Retention index
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Retention indices or five 1-alkenes, seven branched alkenes and five cycloalkenes and the corresponding epoxides were determined at two temperatures on a fused-silica capillary column coated with cyanopropyl methyl siloxane to interpret their chromatographic behaviour. The standard deviation was 0.2 index units.
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  • 43
    ISSN: 1434-1948
    Keywords: Palladium ; Platinum ; Bidentate nitrogen ligands ; p-Quinone ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Compounds of the type M(N∩N-κN)(nq)2 and M2(μ2-N∩N)(μ2-pbq)2, in which nq = 1,4-naphthoquinone, pbq = 1,4-benzoquinone, and N∩N is a monodentate or bridging ligand of the α-diimine type, were obtained from reactions of Pd(dba)2 in toluene with the 3,3′-annelated-2,2′-bipyridines: 4,5-diazafluoren-9-one (dafo) and 4,5-diazafluorene (dafe) in the presence of the appropriate p-quinone. In the corresponding reactions with 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 2,2′-bipyrimidine (bpym), N,N′-dicyclohexyl-1,4-diaza-1,3-butadiene (chex-dab), bis[N-(o,o′-diisopropyl)phenylimino]acenaphthene (o,o′-iPr2-bian) and 5,6-dihydro-1,10-phenanthroline (dh-phen) only complexes of the type M(N∩N-κ2N)(Q) were formed (Q = nq, pbq). The structures of the complexes have been established by NMR in solution and by X-ray diffraction in the solid state; crystal structures of Pd(bpy-κ2N)(η2-pbq) (1) Pd(dafo-κN)(η2-nq)2 (14) and Pd2(μ2-dafo)(μ2,η2:η2-pbq)2 (16) have been determined. Of the ligands, dafo and dafe are the only ones apt to form complexes containing a monodentate or bridging N∩N ligand. This behaviour is ascribed to the geometrical constraints of dafo and dafe; the annelation by one carbon atom at the 3,3′-positions in these ligands causes an increase in bite angle from approximately 77° to 82°.
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  • 44
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 407-414 
    ISSN: 1434-1948
    Keywords: Ruthenium ; Phosphorus ; Triphos complexes ; Fluxionality ; Arm-off dissociation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structural fluxionality is apparent in the 1H- and 31P-NMR spectra of compounds of the type [Ru(L)(MeCN)(triphos)](CF3SO3), 2-5, at 25°C, where L represents a diorganyldithiocarbamate or a heterocyclic κ2N,S coordinating thioamide. In contrast, complexes [Ru(Et2NCS2)(Y)(triphos)]n+ (6, n = 1, Y = CO; 7, n = 0, Y = CN-; 8, n = 0, Y = H-) are stereochemically rigid in solution at this temperature, indicating that MeCN dissociation must occur for the crowded octahedral coordination spheres of 2-5. Reaction of [Ru(MeCN)3(triphos)](CF3SO3)2, 1, with Na(Et2NCS2) at a 1:2 molar ratio yields [Ru(Et2NCS2-κ2S)(Et2NCS2-κS)(triphos)], 9, which slowly converts to [Ru(Et2NCS2-κ2S)2(triphosO-κ2P)], 10, on recrystallization from ethanol/acetone under air [triphosO is O=P(Ph)2CH2C(CH3)(CH2PPh2)2]. A similar κ3P→κ2P arm-off dissociation leads to the formation of [Ru(mpy-κ2N,S)2(triphosO-κ2P)] (13) and [Ru(mmim-κ2N,S)2(triphosO-κ2P)] (14) (Hmpy = 2-mercaptopyridine, Hmmim = 2-mercapto-1-methylimidazole). Crystal structures are reported for [Ru(mbt-κ2N,S)(MeCN)(triphos-κ3P)](CF3SO3) (4) (Hmbt = 2-mercaptobenzothiazole), [Ru(mpym-κ2N,S)(mpym-κS)(triphos-κ3P)] (11) (Hmpym = 2-mercaptopyrimidine) and 14, the latter of which is present as the OC-6-13 isomer.
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  • 45
    ISSN: 1434-1948
    Keywords: Silicon ; Phosphorus ; Oligophosphides and -phosphanes ; NMR spectra ; X-ray structure analysis ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The violet THF adduct (tBu3Si)2P3Na(THF)4 (1a) of the triphosphide (tBu3Si)2P3Na (1) is prepared, (i) by protolysis of the tetraphosphide (tBu3Si)2P4Na2 (2) with an equimolar amount of CF3CO2H in THF (transformation of 2 into 1), (ii) by the reaction of tBu3SiNa and the oligophosphane (tBu3SiP3)n in THF (building-down of Pn), and (iii) by the action of tBu3SiNa on PCl3 in THF (building-up of Pn). According to X-ray structural analysis, the SiPPPSi skeleton of the anionic part [tBu3SiPPPSitBu3]- of 1a is W-shaped with two P-P 11/2 bonds; in addition, 1a contains a planar deltoid P3Na backbone with the 4 THF molecules coordinated to Na. The protolysis of 1a leads to cyclotriphosphane (tBu3Si)2P3H (11), and the oxidation of 1a leads to 1,1′-bicyclotriphosphane (tBu3Si)2P3-P3(SitBu3)2 (12) as the main product and bicyclo[3.1.0]hexaphosphane (tBu3Si)4P6 (13) as an isomer of 12. The structures of 11, 12, and 13 as well as the structure of 1a have been unambiguously determined by 31P-NMR studies. Ab initio structure and energy calculations show that the acyclic P3H2- with allylic conjugation and P-P 11/2 bonds is thermodynamically more stable than the cyclic isomer whereas, in contrast, the neutral compound P3H3 prefers the cyclic form. The exceptional downfield shift of the NMR signal of the central phosphorus in 1a is in agreement with DFT NMR calculations for a model compound [H3SiPPPSiH3]Na with P-P 11/2 bonds.
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  • 46
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 1759-1762 
    ISSN: 1434-193X
    Keywords: Alkenes ; Cycloadditions ; Cage compounds ; Ab initio calculations ; Double-bond pyramidalization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The twofold bridged sesquinorbornenes 2 and 6 were prepared using sequential [4 + 2] cycloadditions of benzoquinone with 1,5-dihydropentalenes 1 and 5. These syntheses were improved using dilution conditions or a more reactive substituted benzoquinone. Results from semiempirical and ab initio DFT calculations indicated remarkably high pyramidalization angles (φ = 46-47°) for the central C-C double-bond atoms. The chemical reactivity with triplet and singlet oxygen, dimethyldioxirane and N-methyl-1,2,4-triazoline-3,5-dione supports these structural assignments.
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  • 47
    ISSN: 1434-193X
    Keywords: Alkenes ; Ketones ; O-O activation ; Palladium ; Zeolites ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Simple ammonia complexes {cis-[PdCl2(NH3)2], [Pd(NH3)4]Cl2 or [Pd(NO2)2(NH3)2]} with copper(II) chloride and LiCl or PdII (or Pd0) inserted into zeolite (faujasite Y or mordenite Z)/CuII-LiI-Cl- precursors in anhydrous ethanol catalyse the oxidation of terminal olefins to methyl ketones by dioxygen. One oxygen atom is incorporated into the olefinic substrate, while the other is involved in a cooxidation process of the solvent leading to the formation of water. With 1-octene and ethanol, octan-2-one can be obtained selectively (up to 99 %), acetaldehyde and diethyl acetal being the main cooxidation products. Chorohydridopalladium species are key intermediates in the isomerization of 1-alkenes; it appears that the introduction of NH3, NO2- or zeolite ligands reduces the extent of isomerization and subsequently the formation of isomeric ketones (octan-3-one and octan-4-one). Although homogeneous catalysis cannot be ruled out, the improved selectivities and variations of selectivity and conversion with different zeolites suggest that a “ship-in-a-bottle” catalysis may be important.
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  • 48
    ISSN: 1434-1948
    Keywords: Phosphorus ; Phosphonic anhydrides ; Oligophosphonic acids ; Peptide synthesis ; Solid-state structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By reaction of RP(O)Cl2 with RP(O)(OSiMe3)2, phosphonic anhydrides (RPO2)3 (R = tBu, 2-methylphenyl, 2,4,6-trimethylphenyl) 1a-c are conveniently obtained. In contrast to 1b and 1c, compound 1a is remarkably stable against protolysis. Intermediates of hydrolysis of 1a, namely tris(tert-butyl)triphosphonic acid (2) and bis(tert-butyl)diphosphonic acid (3), can also be isolated in good yield. The structures of 1-3 were determined mainly by NMR spectroscopy (1 H, 13C, 31P). Assuming an energetic preference for the chair conformations in solution, and considering the steric requirements of the bulky substituents R, configurations Ia (point group Cs, two R in equatorial positions) for 1a and b, and IIa (point group C3v, all R equatorial) for 1c are suggested. - Reaction of 1a with N-benzyloxycarbonylglycine (4) in methanol affords strong evidence that in the first step of peptide synthesis with (RPO2)3, a mixed anhydride of triphosphonic acid and the N-protected amino acid is formed. - The crystal structure of 1a (monoclinic, space group P21/n) widely corresponds to the suggested configuration Ia, but reveals an envelope conformation for the six-membered ring with a P3O2 plane in the crystal. In the crystal structure of the octahydrate of the disodium salt of 2 (monoclinic, space group P21/c), it can be seen that the polar end groups of the anions [tBu3P3O7]2- together with the water molecules and the Na+ cations, form hydrogen-bonded double-layers, strictly separated from each other by the non-polar tert-butyl groups of the anions.
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  • 49
    ISSN: 1434-1948
    Keywords: Bis(silyl)phosphanes ; Magnesium ; NMR spectroscopy ; Oligomers ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metathesis reaction of (dme)LiPH2 and chlorodiisopropylsilane yields HP(SiHiPr2)2 (1) and P(SiHiPr2)3 (2). The metalation of 1 by n/sec-dibutylmagnesium in heptane leads to the formation of dimeric magnesium bis[bis(diisopropylsilyl)phosphanide] [(3)2]. A toluene solution of magnesium bis[bis(trimethylsilyl)phosphanide] (4) shows a dimer-trimer equilibrium in the 31P{1H}-NMR spectrum at -40°C with an increasing amount of the dimer with increasing temperature. A molecular mass determination by freezing-point depression in benzene yields a value of 516 g·mol-1, which lies between a monomeric and a dimeric molecule. Cooling of the toluene solution to -30°C leads to the precipitation of single crystals of monoclinic {(Me3Si)2P-Mg[μ-P(SiMe3)2]2}2Mg [(4)3].
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  • 50
    ISSN: 1434-1948
    Keywords: Hydrogenations ; Parahydrogen ; Platinum ; Alkynes ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of hydrogenation of alkynes catalyzed by the [(PR3)2PtHX]/SnX2 system (PR3 = PPh3, PMePh2; × = Cl, Br) has been studied by means of parahydrogen-induced polarization of 1H spectra (PHIP). Dihydride intermediates confirming the stepwise hydrogenation at room temperature were observed when the reaction was run in acetone. The obtained 1H-PHIP spectra, together with NMR data for related species, are consistent with the formulation of these intermediates as cis-[H2Pt(PR3)(SnX3)(σ-alkenyl)(acetone)], where the σ-alkenyl ligand originates from an insertion reaction of the alkyne (1-phenyl-1-propyne, 1-phenyl-1-butyne, diphenylacetylene, 3,3-dimethylbutyne). At elevated temperatures, the hydrogenation in acetone proceeds as a cis-synchronous transfer of the two hydrogen atoms of parahydrogen to the substrate molecule. A mechanism for this synchronous hydrogenation is suggested.
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  • 51
    ISSN: 1434-1948
    Keywords: Carbene complexes ; Tungsten ; Phosphorus ; 2H-Azaphosphirene complexes ; Cyclization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first syntheses of pentacarbonyl[2-(pentamethyl-2,4-cyclopentadien-1-yl)-2H-azaphosphirene]tungsten complexes are reported, using a one-pot reaction of dichloro(pentamethyl-2,4-cyclopentadien-1-yl)phosphane (Cp*PCl2) with triethylamine and {[amino(aryl)carbene]pentcarbonyltungsten(0)}. [Pentamethyl-2,4-cyclopentadien-1-yl]phosphanediyl-bridged dinuclear carbene complexes are formed as long-lived intermediates, which, by elimination and rearrangement reactions, led to the final products. If traces of water were present, then by-products were formed; in one case, a dinuclear carbene complex with a P(Cp*)-O-P(Cp*) bridging unit was isolated. Under ordinary reaction conditions 2H-azaphosphirene complexes are slowly transformed into {pentacarbonyl[chloro(pentamethyl-2,4-cyclopentadien-1-yl)phosphane]tungsten(0)}. NMR-spectroscopic and single-crystal X-ray structural data of some dinuclear carbene complexes and 2-(pentamethyl-2,4-cyclopentadien-1-yl)-2H-azaphosphirene complexes are presented.
    Additional Material: 6 Ill.
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  • 52
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 951-955 
    ISSN: 1434-1948
    Keywords: Ab initio calculations ; Phosphorus ; Strained molecules ; Substituent effects ; Pericyclic reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: According to quantum chemical calculations at an ab initio level parent 1,2-diphosphete is slightly more stable than its corresponding 1,4-diphosphabutadiene structural isomer. The quantum chemical calculations indicate that substituents at phosphorus and to a much less extent at carbon exert strong influences on the equilibrium geometries of 1,2-diphosphete structures: π donors at phosphorus strongly elongate the P-P bond while electronegative substituents at phosphorus increase the interflap angle of the four-membered ring systems, bringing an envelope conformation to the fore. The lengthening of the P-P bond gives rise to a Möbius-type delocalization within the ring moiety.
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  • 53
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2775-2784 
    ISSN: 1434-193X
    Keywords: Heterocycles ; Cycloadditions ; Diatomic carbon ; Sulfones ; Alkenes ; Polycycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Chloro-1,4-benzodithiin 1,1,4,4-tetraoxide 11 is a reactive dienophile that forms Diels-Alder adducts with a number of dienes. Adducts 17a-j undergo facile dehydrochlorination to give 2,3-substituted 1,4-benzodithiin tetraoxides 18a-j, which react further with another molecule of diene (the same or a different one) affording the “double” adducts 19-23. Upon reductive desulfonylation with sodium amalgam, the latter are transformed to tetrasubstituted polycyclic olefins 24-27. These olefins correspond to the cycloadducts that would theoretically have been formed by the cycloaddition of diatomic carbon with two molecules of diene, reacting in a Diels-Alder fashion.
    Additional Material: 4 Ill.
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  • 54
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2885-2896 
    ISSN: 1434-193X
    Keywords: Alkenes ; Alkynes ; Cycloadditions ; Nitrogen heterocycles ; Tetrazines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Full details on the reactivity of the title compound as 4π component in inverse-type Diels-Alder reactions, including kinetic data, are reported. Donor-substituted alkynes, alkenes, donor-substituted and unsubstituted cycloalkenes, ketene acetals and aminals, as well as several cyclic enol ethers were used as dienophiles in these investigations. A number of 4-mono- and 4,5-disubstituted pyridazines can easily be obtained by this method.
    Additional Material: 5 Ill.
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  • 55
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 409-417 
    ISSN: 0268-2605
    Keywords: antitumor activity ; cancer cell lines ; dibutyltins ; NCI ; organotins ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper reports the activity of four dibutyltin(IV)-N-arylidene-α-amino acid complexes against the National Cancer Institute (NCI) panel of 60 cell lines. The results indicated that three of the organotin complexes (C17H25NO3Sn, C18H27NO3Sn and C20H31NO3Sn) exhibit their highest cytotoxic effect on the NCI-522 (non-small cell lung cancer) cell line. The fourth complex, C21H27NO3Sn, exhibits its highest cytotoxic activity on the cell line RXF-631L (renal cancer). In general, a low to moderate cellular response was observed for all the organotin complexes, with at least one cell line in each subpanel of cells exhibiting a very low growth inhibition response to all the organotin complexes. The low-responding cell lines included HOP-62 (non-small lung cancer), DLD-1 (colon cancer), SF-539 (CNS cancer), SK-MEL-5 (melanoma), IGROV-1 (ovarian cancer) and RPMI-8226 (leukemia). The results also indicated that the compounds did not exhibit any significant subpanel activity and suggested that the compounds were not active in all the cell lines contained in any subpanel. The low to moderate activity of these compounds across the cell lines was attributed to the presence of nitrogen-bearing ligands which prevented the dissociation of the compound and the subsequent binding to DNA. © 1998 John Wiley & Sons, Ltd.
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  • 56
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 449-455 
    ISSN: 0268-2605
    Keywords: trimethylantimony ; biomethylation ; anaerobic bacteria ; inorganic antimony ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The volatile antimony compound trimethylantimony (TMA) was detected in headspace gases over anaerobic soil enrichment cultures spiked with potassium antimony tartrate. The presence of TMA was variable (12 positives from 104 cultures) and dependent upon both the inoculum source (environmental sample) and enrichment culture conditions. Positives for TMA formation were obtained with variable frequency for four of the six soils tested and for three types of enrichment culture, designed to encourage growth of nitrate-reducing, methane-producing or fermentative bacteria. The identity of the volatile antimony compound produced in each of the three types of enrichment culture was confirmed by gas chromatography-mass spectrometry and gas chromatography-atomic absorption spectroscopy. There was no evidence of any other volatile antimony compound in the headspace gases. These data suggest that the capability to generate TMA is widely distributed in the terrestrial environment and is attributable to different metabolic types of micro-organisms. © 1998 John Wiley & Sons, Ltd.
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  • 57
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 467-467 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 58
    ISSN: 0268-2605
    Keywords: fungicidal activity ; Ceratocystis ulmi ; triphenyltin(IV) ; tributyltin(IV) ; phenolic bridge ; carboxylate bridge ; polymers ; trigonal bipyramidal structures ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The methods of synthesis, elemental analysis, IR and NMR spectroscopic data and fungicidal activity against Ceratocystis ulmi are reported for a series of triorganotin esters of N-arylidene-ω-amino acids of general formula R3SnOCO(CH2)nN = CHAr (R = Ph, n-Bu; Ar = 2-HOC6H4, 2-HOC10H6; n = 1, 2, 3 and 5). The crystal structures for two of the compounds, tributyltin N-2-hydroxynaphthalidene glycinate (1) and tributyltin N-2-hydroxynaphthalidene-β-alaninate (2), have been determined. Although both of these compounds have a trans-R3SnO2 structure, in compound 1 the carboxylate group is monodentate and the fifth coordination position around the tin atom is taken up by a coordinated phenolic group, whereas in 2 the carboxylate group is bridging. These two examples thus correspond to the two different structures reported for trans-R3SnO2 complexes. Both compounds were found to be active against Ceratocystis ulmi, but there was no significant difference in their levels of biological activity against this particular fungus. Apart from compound 1, the other tributyltin compounds reported are believed to adopt the carboxylate bridging mode shown by compound (2).Crystal data: for 1, crystals monoclinic, space group P21/c, a = 12.9435(11) Å, b = 13.5769(10) Å, c = 15.7715(12) Å, β = 108.919(6)°, Z = 4, Rf = 0.046 and Rw = 0.058 for 1448 significant reflections; for 2, crystals monoclinic, space group C 2/c,a = 24.588(14) Å, b = 9.733(3) Å, c = 27.611(12) Å,β = 113.49(4)°, Z = 8, Rf = 0.053 and Rw = 0.069 for 3822 significant reflections. © 1998 John Wiley & Sons, Ltd.
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  • 59
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 878-878 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract
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  • 60
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 801-807 
    ISSN: 0268-2605
    Keywords: metal-containing vinylic monomers ; vinylbenzoyl complexes ; cinnamoyl complexes ; tungsten-olefin monomers ; iron-olefin monomers ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of metal-containing vinylic monomers of the type LnM(COC6H4CH=CH2) and LnM (COCH=CHC6H5) [LnM = (η5-C5H5)Fe(CO)2, (η5-C5Me5)Fe(CO)2 and (η5-C5H5)W(CO)3] were prepared by the reaction of the appropriate metal anion with either 4-vinylbenzoyl chloride or cinnamoyl chloride. (η5-C5H5)(CO)2FeCOCH=CH2 was prepared by the reaction of Na[(η5-C5H5)Fe(CO)2] and acryloyl chloride, whereas the compound (η5-C5H5)(CO)2Fe(C6H4CH=CH2) was prepared via a transmetallation reaction using a palladium catalyst. All compounds were fully characterized using FTIR, 1H and 13C NMR spectroscopy and mass spectrometry. Copyright © 1998 John Wiley & Sons, Ltd.
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  • 61
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    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 879-879 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract
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  • 62
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    Applied Organometallic Chemistry 12 (1998), S. 793-799 
    ISSN: 0268-2605
    Keywords: anticancer ; antineoplastic ; ferrocene/ferricenium ; biological redox ; free radical ; polyaspartamide ; tumor ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ferrocene/ferricenium redox system plays a significant role in biological oxidation, reduction and free-radical reactions. Of particular interest are the findings of earlier investigations which showed certain water-soluble ferricenium salts to possess appreciable antiproliferative activity against various murine tumor lines and a xenografted human colorectal adenocarcinoma. Solubility in water, a prerequisite for efficacious transport and dissipation in central circulation, was then proposed as a principal requirement for the ferrocene complex system to exert antineoplastic activity irrespective of the oxidation state in which it is administered. In order to shed more light on this question, we decided to investigate the antiproliferative properties of polymer-ferrocene conjugates containing the metal complex in the non-oxidized (ferrocene) form while fulfilling the critical requirement of water solubility. To this end, five selected, water-soluble conjugates, synthesized by reversible coupling of 4-ferrocenylbutanoic acid to variously structured polyaspartamides featuring pendant primary amino groups as coupling sites, were tested in vitro against cultured HeLa cells at concentrations up to 50 µg Fe ml-1. Optimal antiproliferative activities, with IC50 in the range of 2-7 µg Fe ml-1, were determined for three compounds possessing tertiary-amine functions susceptible to protonation at physiological pH. Lower activities (IC50 = 45-60 µg Fe ml-1) were demonstrated for two poly(ethylene oxide)-containing conjugates. However, no reasonable structure-performance relationships can be derived at this stage from the small number of compounds tested. Copyright © 1998 John Wiley & Sons, Ltd.
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  • 63
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 64
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    Applied Organometallic Chemistry 12 (1998), S. 880-880 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract
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  • 65
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    Applied Organometallic Chemistry 12 (1998), S. 855-859 
    ISSN: 0268-2605
    Keywords: butyltin ; phenyltin ; gibberellates ; antitumour ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of di-n-butyl-, tri-n-butyl- and triphenyltin gibberellates are reported. Their antitumour activities in vitro against a panel of seven human tumour cell lines are given and compared with those of drugs used clinically. Copyright © 1998 John Wiley & Sons, Ltd.
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  • 66
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    Applied Organometallic Chemistry 12 (1998), S. 873-876 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 67
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    Applied Organometallic Chemistry 12 (1998), S. 531-539 
    ISSN: 0268-2605
    Keywords: methylmercury ; estuarine sediment ; certification ; (BCR) ; quality control ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Legislation on methylmercury within the European Union (EU), e.g. in food (national regulations) or water (EC Directives), requires that the determinations are of proven quality; thus implies that they should be carried out under strict quality control (QC). One method of achieving good quality control in chemical analysis is to verify the analytical performance of methods by analysing Certified Reference Materials (CRMs). While CRMs of biological matrices (e.g. fish, mussels) are already available, there was a lack of materials for the QC of sediment analysis. This paper describes the preparation of an estuarine sediment reference material, the homogeneity and stability studies and the analytical work performed for the certification of the contents of total mercury and methylmercury. The results of a group of expert laboratories are discussed and the methods used to certify the mass fractions of total mercury (132 ± 3 mg kg-1 on a dry mass basis) and methylmercury (75.5 ± 3.7 μg kg-1 as CH3Hg+ on a dry mass basis) are described. © 1998 John Wiley & Sons, Ltd.
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  • 68
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    Applied Organometallic Chemistry 12 (1998), S. 571-576 
    ISSN: 0268-2605
    Keywords: zerovalent metals ; bromoalkyltriphenylphosphonium bromides ; methylmercuric acetate ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aqueous solutions of bromoalkyltriphenylphosphonium bromides react with zerovalent metals, causing their dissolution. The reaction initially follows second-order kinetics, with the rate depending on both metal and bromide concentrations. Zerovalent metals similarly react with aqueous methylmercuric acetate and other dissolved organometals. © 1998 John Wiley & Sons, Ltd.
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  • 69
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    Applied Organometallic Chemistry 12 (1998), S. 643-650 
    ISSN: 0268-2605
    Keywords: tributyltin ; sediment ; degradation ; coastal British Columbia ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Butyltin concentrations in the sediments of two coastal areas of British Columbia, Canada, are reported. Two recent box cores from the deepest basin in the Strait of Georgia were sectioned and analyzed by GC-atomic emission spectrometry. No butyltin compounds were detected above 0.5 μgSn kg-1 (dry weight) in either core. These results are compared to those for a previous (1991) core from the same area. In that study, tributyltin (TBT) concentrations were in the range 1-2 μgSn kg-1 down the core and were higher than those of either of the degradation products, dibutyltin (DBT) and monobutyltin (MBT). Radioisotope dating (210Po-210Pb counting methods) was used to establish the rates of sedimentation of 0.25 and 2.6 cm y-1 at the two sites. Data suggest that a combination of rapid deposition of new, less-contaminated material and degradation of previously deposited butyltin compounds has resulted in the observed absence. Thirty-three surface sediments from the northern BC coastal harbor at Prince Rupert, collected in 1995, were analyzed for butyltin residues by GC-FPD. Concentrations of TBT, DBT and MBT were in the ranges from below the appropriate limit of detection (LOD) to 1262, to 109 and to 37 μgSn kg-1, respectively. TBT/DBT ratios ranged from 0.2 to 62 with most above unity, indicating that there is continuing fresh input of TBT. The sources are almost exclusively large ocean-going vessels that use the harbor for long-term anchorage. These findings are discussed with reference to the global TBT status. © 1998 John Wiley & Sons, Ltd.
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  • 70
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    Applied Organometallic Chemistry 12 (1998), S. 577-584 
    ISSN: 0268-2605
    Keywords: organotin ; extraction ; analysis ; GC-FPD ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of: (1) the modifier type (methanol and formic, acetic and propionic acids), (2) complexing agents (diethylammonium diethyldithiocarbamate, ammonium pyrrolidinedithiocarbamate) either with or without acidic modifiers, (3) the extraction temperature (50-80 °C) and pressure (30-50 MPa), (4) the extraction procedure (static-dynamic or dynamic), and (5) the volume of static modifier, on the extraction efficiency of native butyl- and phenyl-tin compounds from sediment, were evaluated comprehensively. The highest extraction efficiency for butyl- and phenyl-tin compounds was obtained at 30 MPa and 50 °C by using CO2 modified with acetic acid (200 μl in the cell). Supercritical fluid extraction (SFE) extracts were hexylated and determined by GC-FPD using a 610 nm bandpass filter without any clean-up step. In summary, the developed analytical procedure is robust (no restrictor clogging; free from FPD interferences), it is low-cost (no complexing agents needed), it has a high sample throughput (〈3 h), it is independent of the matrix for the determination of butyltin compounds in sediment, and it provides the highest precision among the SFE procedures reported for organotin determination. © 1998 John Wiley & Sons, Ltd.
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  • 71
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    Applied Organometallic Chemistry 12 (1998), S. 585-590 
    ISSN: 0268-2605
    Keywords: butyltin ; estuarine microcosm ; environmental fate ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A radiotracer experiment was conducted in a controlled experimental ecosystem (microcosm) to determine the persistence and behavior of tributyltin (TBT) under conditions simulating a temperate, shallow estuarine ecosystem. Radiolabeled TBT was introduced to the estuarine microcosm, which contained estuarine water, sediment and fish. TBT and its degradation products were monitored for 40 days. TBT rapidly distributed among the compartments of the microcosm. The TBT half-life in the water column was 2.55 days for the first 11 days and then slowed to 13.4 days. More than 60% of the TBT and its metabolites were found in the sediment, indicating that the sediment was an important sink for butyltins. Higher concentrations of butyltins, relative to the water column concentrations, were found in the surface microlayer. TBT could be bioconcentrated by the fish to levels more than 200 times the exposure concentration, and underwent rapid degradation in the fish body, so that high concentrations of its metabolites were found in the fish. The concentrations of TBT adsorbed on the suspended particles were three orders of magnitude greater than that in dissolved form. © 1998 John Wiley & Sons, Ltd.
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  • 72
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    Applied Organometallic Chemistry 12 (1998), S. 591-599 
    ISSN: 0268-2605
    Keywords: arsenic speciation ; LC-ICP-MS ; validation ; urine samples ; background levels ; The Netherlands ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method validation for the speciation of five arsenic species in urine samples by liquid chromatography hyphenated to inductively coupled plasma mass spectrometry is described. Arsenic species which are identified and quantified in urine samples are the anions of arsenic(III), arsenic(V), monomethylarsonic acid and dimethylarsinic acid, and the cationic arsenobetaine. Detection limits were obtained in the range 0.3-0.4 μg As l-1 while the repeatability was in the range 3-4% (RSD) for concentrations above five times the detection limit. Urine samples could be analysed directly after a ten-fold dilution step. Arsenic compound concentrations were determined in urine samples from a volunteer who consumed a portion of tuna fish high in arsenobetaine. It was found that arsenobetaine was excreted rapidly via the urine with maximum concentrations after 12 h. Nearly complete arsenobetaine excretion was reached after 48 h. Background levels of arsenic compounds were determined in 61 urine samples from non-exposed inhabitants of The Netherlands. © 1998 John Wiley & Sons, Ltd.
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  • 73
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    Applied Organometallic Chemistry 12 (1998), S. 763-770 
    ISSN: 0268-2605
    Keywords: siloxane network ; contact angle ; sol-gel reaction ; polydimethylsiloxane ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polydimethylsiloxane (PDMS) hybrid networks have been prepared by the reaction of PDMS(OH)2, average molecular weight 26 × 103, 43.6 × 103 and 58 × 103, and methyltriethoxysilane (MeTEOS, 10-60 wt%) using a dibutyltin dilaurate or dibutyltin diacetate catalyst. By hydrolysis and homo- and co-condensation, MeTEOS forms a siliceous domain (MeSD) and acts as a crosslinker for the PDMS domain. Kinetic studies showed that high MeTEOS and catalyst concentrations and reduction of free surface area favor fast gelation and efficiency in converting MeTEOS to the MeSD. Under the water-sparse conditions utilized, cure was slow and substantial evaporative loss of MeTEOS occurred. © 1998 John Wiley & Sons, Ltd.
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  • 74
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    Applied Organometallic Chemistry 12 (1998), S. 375-379 
    ISSN: 0268-2605
    Keywords: granular films ; pulsed laser deposition ; giant magnetoresistance ; microstructure ; magnetic properties ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An investigation into the microstructural properties of CoxAg1 - x films, grown by pulsed laser deposition, as a function of deposition and post-deposition annealing temperature is reported. Surface morphology and microstructure were investigated by XPS, SEM and TEM measurements. Magnetic measurements were used to gain further information on particle size distributions through the analysis of the temperature dependence of the irreversible magnetization. Depending on cobalt content, deposition and post-deposition annealing temperature, the maximum of the cobalt grains diameter distribution was estimated to be in the range 2-6 nm. © 1998 John Wiley & Sons, Ltd.
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  • 75
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    Applied Organometallic Chemistry 12 (1998), S. 381-386 
    ISSN: 0268-2605
    Keywords: nanoparticles ; magnetic susceptibility ; magnetic anisotropy ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dynamical behavior of γ-Fe2O3 particles dispersed in a polymer have been investigated by a.c. susceptibility and Mössbauer spectroscopy measurements. The effect of interparticle interactions on the relaxation time is satisfactorily described by a superparamagnetic model where the dipolar energy is determined by a statistical calculation for a disordered arrangement of particles with volume distribution and easy axes in random orientations. The results indicate that the single particle anisotropy energy is mainly determined by surface anisotropy and that the energy barrier increases with the interaction strength. © 1998 John Wiley & Sons, Ltd.
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  • 76
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    Applied Organometallic Chemistry 12 (1998), S. 881-881 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract
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  • 77
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    Applied Organometallic Chemistry 12 (1998), S. 881-882 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract
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  • 78
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    Applied Organometallic Chemistry 12 (1998), S. 883-884 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract
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  • 79
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    Applied Organometallic Chemistry 12 (1998), S. 827-842 
    ISSN: 0268-2605
    Keywords: Scopulariopsis brevicaulis ; hydride generation ; antimony ; biomethylation ; biotransformation ; solid-phase extraction ; sudden infant death syndrome (SIDS) ; volatile antimony ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cultures of the fungus Scopulariopsis brevicaulis were grown in antimony-rich media. Although volatile compounds of other elements were readily detected in the culture headspace, volatile antimony compounds were formed irreproducibly and at only ultratrace levels. In order to monitor the media for nonvolatile methylantimony compounds, a method of sample preparation was developed, based on solid-phase extraction. This enabled the separation of large quantities of soluble inorganic antimony species from trace amounts of organoantimony compounds before speciation by HG-GC-AAS. By this methodology methylated antimony compounds were detected at concentrations of 0.8- 7.1 µg Sbl-1 in all media in which S. brevicaulis was grown in the presence of antimony(III) compounds. These methylantimony species were not detected in any of the nonliving or medium-only controls. Methylated compounds were not detected where S. brevicaulis was grown in the presence of antimony(V) compounds. This is the first study to show that antimony(III) compounds are biomethylated by S. brevicaulis under aerobic-only growth conditions. Copyright © 1998 John Wiley & Sons, Ltd.
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  • 80
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 81
    ISSN: 0268-2605
    Keywords: carbohydrate-modified phenylsiloxane ; surfactants ; wetting behaviour ; superspreading ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dynamic wetting behaviour on a perfluorinated, low-energy solid has been investigated for a carbohydrate-modified phenylsiloxane surfactant. The surfactant concentration, the rate of interface generation and the [solid/liquid interface area] : [liquid/vapour interface area] ratio were varied systematically. Dynamic data for the liquid/vapour (γlv) and solid/liquid (γsl) interfacial tension as well as their Lifshitz-van der Waals and donor-acceptor contributions were determined under strictly controlled conditions. Since γsl reacts sensitively to variations of the surfactant concentration and the rate of interface generation, the covering of the liquid/non-polar solid interface is assumed to be a spreading limiting factor. The corresponding γlv values remain constant and close to those obtained under equilibrium conditions. Copyright © 1998 John Wiley & Sons, Ltd.
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  • 82
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    Applied Organometallic Chemistry 12 (1998), S. 523-529 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract
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  • 83
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    Applied Organometallic Chemistry 12 (1998), S. 559-563 
    ISSN: 0268-2605
    Keywords: tributyltin ; surface microlayer ; dynamic model ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transport dynamics of tributyltin (TBT) between the surface microlayer and subsurface water were studied in experimental systems which simulated different surface sea states. A dynamic model was derived from a diffusion equation to describe the dynamics of the TBT transport process. With this dynamic model diffusion coefficients were determined, and the effects of surface sea states and temperature on the TBT transport process between the surface microlayer and subsurface water were also studied. Turbulence, breaking waves and elevated temperature can accelerate this transport. © 1998 John Wiley & Sons, Ltd.
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  • 84
    ISSN: 0268-2605
    Keywords: methylmercury ; analysis ; HPLC- ICP MS ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel technique has been developed for the determination of trace amounts of methylmercury in various sample matrices. The newly developed HPLC method makes it possible to separate methylmercury and inorganic mercury with ultrasonic nebulization and detection by ICP MS for different mercury isotopic masses. The isotope-specific detection allows the application of the species-specific isotope addition method for the determination of methylmercury with a correction for artifact formation. The well-known water-vapour distillation method was used in combination with an enriched stable inorganic mercury isotope (200Hg2+) for the separation of methylmercury from various matrices. The subsequent determination of CH3 - 200Hg+ generated from 200Hg2+ was used in the correction for artifact formation during sample preparation. In comparison with a previously developed HPLC coupling technique with HPF-HHPN (high-performance flow/­hydraulic high-pressure nebulization), the stability of the detection procedure was improved considerably. The limit of detection (S/N = 3) for methylmercury was calculated to be about 0.015 μg kg-1. © 1998 John Wiley & Sons, Ltd.
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  • 85
    ISSN: 0268-2605
    Keywords: methylmercury ; solid-phase microextraction ; gas chromatography-atomic fluorescence ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An analytical method is described for methylmercury determination in fish and aqueous samples using solid-phase microextraction (SPME) followed by gas chromatography-atomic fluorescence spectrometry (GC-AFS). The procedure involves aqueous-phase derivatization of methylmercury species with sodium tetraethylborate in a sample vial and subsequent extraction with a silica fiber coated with poly-­(dimethylsiloxane). The mercury derivatives are desorbed in the splitless injection port of a gas chromatograph and subsequently analyzed by GC-AFS. The headspace SPME procedure is used and parameters affecting the extraction, adsorption and desorption are evaluated. Results for methylmercury analysis in standard reference material (DORM-2) and fish samples are presented. © 1998 John Wiley & Sons, Ltd.
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  • 86
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    Applied Organometallic Chemistry 12 (1998), S. 635-641 
    ISSN: 0268-2605
    Keywords: arsenobetaine ; arsenocholine ; non-hygroscopic ; NMR ; FAB MS ; ICP MS ; synthesis ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multigram quantities of arsenobetaine bromide and arsenocholine iodide were synthesized from trimethylarsine using uncomplicated techniques. Arsenobetaine bromide and arsenocholine iodide are both non-hygroscopic. Arsenocholine iodide is, however, light-sensitive and should be used with actinic glassware. Both compounds were characterized by elemental and spectroscopic techniques and found to be suitable for use as primary analytical standards. © 1998 John Wiley & Sons, Ltd.
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  • 87
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    Applied Organometallic Chemistry 12 (1998), S. 659-666 
    ISSN: 0268-2605
    Keywords: polymers ; polyphosphazenes ; synthesis ; surfaces ; surface reactions ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The macromolecular substitution approach for the synthesis of polyphosphazenes provides access to many different polymers. However, it precludes the use of reagents that contain two or more functional groups because such compounds would cause extensive crosslinking of the chains. This presents a problem because many of the uses for which polyphosphazenes seem ideally suited require the presence of -OH, -COOH, -NH2, -SO3H, -PR2 and other functional units in the side-chain structure. We have developed two approaches to introduce such active sites: (1) protection-deprotection reactions; and (2) direct reactions of active reagents with the organic side-groups of non-functional poly(organophosphazenes). These methods have been applied both at the molecular level and in the form of reactions carried out only at polymer surfaces. The resultant polymers have special properties that are valuable in the micro-encapsulation of sensitive biological agents; in the formation of hydrophobic, hydrophilic, or adhesive surfaces; in crosslinking reactions; and in the development of solid polymer electrolytes, bio-erodible polymers, pH-triggered hydrogels, polymer blends and interpenetrating polymer networks. Overall, more than 700 different polyphosphazenes are now known, and a large number of these are functional macromolecules targeted for specific property combinations and uses. © 1998 John Wiley & Sons, Ltd.
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  • 88
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    Applied Organometallic Chemistry 12 (1998), S. 707-713 
    ISSN: 0268-2605
    Keywords: polyhedral oligomeric silsesquioxane ; hybrid ; thermoplastic ; polymer ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A diverse and entirely new class of monomer and polymer technology based on polyhedral oligomeric silsesquioxane (POSS) reagents has been developed. POSS reagents are unique in that they are physically large (approx. 15 Å diameter and 1000 amu) and are composed of a robust silicon-oxygen framework that can be easily functionalized with a variety of organic substituents. Appropriate functionalization of POSS cages allows for their incorporation into traditional thermoplastic resins without modification of existing manufacturing processes. The incorporation of POSS segments into linear copolymer systems results in increased glass transition and decomposition temperatures, increased oxygen permeability and reduced flammability and heat evolution, as well as modified mechanical properties relative to conventional organic systems. © 1998 John Wiley & Sons, Ltd.
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  • 89
    ISSN: 0268-2605
    Keywords: organophosphazenes ; liquid crystals ; phase transition ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organophosphazenes with a similar mesogenic moiety were prepared and their mesogenicity was studied by differential scanning calorinetry (DSC) measurements and polarizing microsope observations. In cyclotriphosphazenes with alk-­oxybiphenyl and Schiff base moieties, mesomorphic phase transitions were observed, but no mesomorphic phase was observed for the corresponding cyclotetraphosphazenes. In polyphos-­phazenes with an alkoxybiphenyl moiety, no mesomorphic phase was observed. The molecular structure of cyclotriphosphazenes facilitated the formation of a mesomorphic layer structure; in contrast, the formation of a mesomorphic layer structure did not occur in cyclotetraphosphazenes and polyphosphazenes, even though they bore a similar mesogenic moiety. Moreover, in cyclotriphosphazenes with an optically active alkoxybiphenyl group, a smectic C* phase was observed. The spontaneous polarization of the compound was -190 μ C m-2 at 436 K in 25 μ in cell using the triangular-wave method. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 7 Ill.
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  • 90
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 657-657 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 91
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 781-785 
    ISSN: 0268-2605
    Keywords: phosphonium ; polymer ; monomer ; film ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(arylene ether) main-chain phosphonium ionomers were successfully synthesized and characterized. The reaction scheme involved first preparing the poly(arylene ether phosphine oxide) by a nucleophilic step or condensation polymerization of bisphenolates on activated aryl halides, wherein phenyl phosphine oxide was the activating group. High-molecular-weight, tough, film-forming polymers were produced with glass transition temperatures of 200°C or higher. The resulting materials were successfully reduced using phenylsilane in refluxing chlorobenzene. The derived phosphine or phosphine/phosphine oxide copolymer was reacted with alkyl halides to produce the phosphonium salts. The resulting materials showed enhanced hydrophilicity and in some cases could be successfully dispersed in water. In addition, chromophores such as Methyl Orange and Methyl Red were combined with the backbone ionomer to produce new film-forming, ionically linked species. The materials are of general interest for situations where water-dispersible intermediates, e.g. coatings, fiber sizings etc. are required. The phosphonium salts can be converted back to the phosphine oxide in fairly high yields by simple thermal methods and in quantitative yield by chemical methods (e.g. the Wittig reaction). © 1998 John Wiley & Sons, Ltd.
    Additional Material: 1 Ill.
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  • 92
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 681-693 
    ISSN: 0268-2605
    Keywords: ceramics ; preceramic polymers ; SiNCB composites ; boron nitride ; boron ; silicon ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Our recent work directed at the design, synthesis, characterization and applications of new types of polyborazylene and polyborosilazane polymers is reviewed with a focus on the use of these polymers as processable precursors to BN and SiNCB composites. A design strategy based on the controlled functionalization of preformed polymers with pendant groups of suitable compositions and crosslinking properties has been employed to yield second-generation dipentylamine-polyborazylene (DPA) and pinacolborane-hydridopolysilazane (PIN-HPZ) polymers, which, unlike the parent polyborazylene (PB) and the borazine-hydridopolysilazane (B-HPZ) polymers, are stable as melts and can be easily melt-spun into polymer fibers. Subsequent pyrolyses of these polymer fibers then provide excellent routes to BN and SiNCB ceramic fibers. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 11 Ill.
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  • 93
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 285-291 
    ISSN: 0268-2605
    Keywords: mushroom ; arsenic speciation ; HPLC-ICP-MS ; dimethylarsinic acid ; arsenobetaine ; trimethylarsine oxide ; toxicological evaluation ; soil contamination ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Samples of the edible mushroom Laccaria amethystina, which is known to accumulate arsenic, were collected from two uncontaminated beech forests and an arsenic-contaminated one in Denmark. The total arsenic concentration was 23 and 77 μg  As g-1 (dry weight) in the two uncontaminated samples and 1420 μg As g-1 in the contaminated sample. The arsenic species were liberated from the samples using focused microwave-assisted extraction, and were separated and detected by anion- and cation-exchange high-performance liquid chromatography with an inductively coupled plasma mass spectrometer as arsenic-selective detector. Dimethylarsinic acid accounted for 68-74%, methylarsonic acid for 0.3-2.9%, trimethylarsine oxide for 0.6-2.0% and arsenic acid for 0.1-6.1% of the total arsenic. The unextractable fraction of arsenic ranged between 15 and 32%. The results also showed that when growing in the highly arsenate-contaminated soil (500-800 μg As g-1) the mushrooms or their associated bacteria were able to biosynthesize dimethylarsinic acid from arsinic acid in the soil. Furthermore, arsenobetaine and trimethylarsine oxide were detected for the first time in Laccaria amethystina. Additionally, unidentified arsenic species were detected in the mushroom. The finding of arsenobetaine and trimethylarsine oxide in low amounts in the mushrooms showed that synthesis of this arsenical in nature is not restricted to marine biota. In order to minimize the toxicological risk of arsenic to humans it is recommended not to consume Laccaria amethystina mushrooms collected from the highly contaminated soil, because of a genotoxic effect of dimethylarsinic acid observed at high doses in animal experiments. © 1998 John Wiley & Sons, Ltd.No Abstract.
    Additional Material: 2 Ill.
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  • 94
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 299-299 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 95
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 299-301 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 96
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 301-301 
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 97
    ISSN: 0268-2605
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 98
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 327-335 
    ISSN: 0268-2605
    Keywords: zinc sulphide ; precipitation ; nanocrystallites ; nanopores ; optical transmission spectroscopy ; vibrational spectroscopy ; Raman spectroscopy ; X-ray diffraction ; transmission electron microscopy ; thermogravimetric analysis ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: During the synthesis of ZnS powders by wet chemical precipitation, the formation of nanoporous spheres is observed. The powders have been investigated using thermogravimetric analysis, X-ray diffraction and optical spectroscopies. Nanopore formation can be explained by several stages of growth. The formation of nanoparticles as primary particles is followed by their agglomeration forming secondary particles. These secondary particles are monodispersed spheres with a considerable porosity, because the agglomeration of the nanoparticles is unlikely to be volume-filling. The voids or nanopores formed by this agglomeration process in the secondary particles is estimated to comprise around 35% of the sphere volume. They are mainly filled with water and the residues of the chemical reagents. Water in the pores partially reacts with ZnS and forms hydrated sulphates. The chemical reagents used for the precipitation reactions are also found to be bound to the nanocrystallite's surfaces as ligands in some cases. Depending on the reaction conditions and reagents, the agglomeration of the nanoparticles can also be modified or hindered by the use of complexing agents acting as a sterically stabilizing surface layer on the nanocrystallites. The agglomeration of nanoparticles to larger units being a general phenomenon, this use of complexing agents to control pore formation and agglomerate size should be applicable to other nanocrystalline systems. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 7 Ill.
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  • 99
    ISSN: 0268-2605
    Keywords: α-Fe2O3 ; nanoparticles ; Morin transition ; antiferromagnetism ; weak ferromagnetism ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The magnetic properties of α-Fe2O3 nanoparticles of different shapes (spherical, rhombohedral and acicular), prepared as powders by a chemical route, have been investigated. The particle size effect on the Morin transition (TM = 263 K in the bulk system) have been studied by analyzing the temperature dependence of the zero-field-cooled (ZFC) and field-cooled (FC) magnetization. For spherical (average diameter between 10 and 50 nm) and rhombohedral (edge between 30 and 350 nm) particles, the Morin temperature was found to decrease with decreasing particle size and increasing magnetic field. On the other hand, acicular particles (major axis between 300 and 700 nm, minor axis between 70 and 100 nm) do not show the Morin transition, unless annealed. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 6 Ill.
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  • 100
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 361-365 
    ISSN: 0268-2605
    Keywords: silicon nanoparticles ; optical properties ; CO2 laser ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Silicon nanoparticles have been synthesized by heating reactant gases with a 500 W CO2 laser. A technique based on scattering of He-Ne laser light by particulates in a reaction flame has been developed for probing the particle size evolution during the process, in order to scale down the particle diameter (under 10 nm). The optical and structural properties of laser-synthesized silicon nanopowders obtained in different runs are reported. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 5 Ill.
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