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  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Entomologia experimentalis et applicata 57 (1990), S. 143-150 
    ISSN: 1570-7458
    Schlagwort(e): Bruchidae ; Callosobruchus maculatus ; competition ; development ; evolution ; fecundity ; growth rates ; host preferences ; life tables ; mortality ; natural selection ; net reproductive rate ; oviposition traits
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Beschreibung / Inhaltsverzeichnis: Résumé Le taux partiel de reproduction nette (R inf0 sup* ) dépend de l'espèce de la plante sur laquelle les œufs sont pondus et du nombre de larves entrant dans la graine. La survie larvaire est réduite par 1/(le nombre de larves par graine) parce qu'une seule larve se développe dans une graine. La fécondité n'est pas modifiée par la compétition subie par les larves, la mortalité larvaire a l'effet le plus important sur R inf0 sup* . Les femelles éliminent ou réduisent la compétition larvaire en dispersant leurs œufs uniformément et font si peu d'erreurs avec une hyperdispersion que l'évolution d'un comportement plus précis n'accroîtrait R inf0 sup* que de 4% au maximum. Des femelles retournant à une distribution des œufs au hasard provoqueraient une réduction de R inf0 sup* de 25% au moins. Les légumineuses généralement cultivées dans l'Inde du Sud sont des hôtes acceptables quand elles sont présentées seules. Le choix des femelles entre 2 hôtes élève R inf0 sup* de 30% ou plus par rapport à une distribution au hasard. Les préférences les plus nettes concernent des combinaisons présentant la plus grande différence de R inf0 sup* . Les femelles qui hyperdispersent leurs œufs, choisissent leurs hôtes et évitent les pertes par compétition en empêchant que les œufs ne donnent plus de descendants que ne le ferait une ponte au hasard. Les particularités de la ponte sont variables et héritables. Les lignées se sélectionnent bien, en fonction de la dispersion de leurs œufs sur les graines, de la discrimination des plantes hôtes, et de la modulation de leur taux de ponte. La sélection naturelle maintient ces particularités du comportement d'une façon sédentaire.
    Notizen: Abstract The deposition of eggs by this strain of Callosobruchus maculatus (Fab.) (Bruchidae: Coleoptera) departs from randomness in three ways; eggs are uniformly dispersed, oviposition rates drop when beans begin to carry 2 or more eggs, and there are sharp host preferences. Using random egg placement for the unspecialized condition, these traits are evaluated for their effect on a female's contributions of offspring to the next generation (R0, the net reproductive rate). The major increases in R0 result from females dispersing eggs so uniformly that larval competition is either reduced or eliminated. Females reduce their oviposition rate when the larva from an egg added to a bean is almost certain to die in competitive encounters. Host preferences and larval survival in a host are positively associated with the abundance of the host in South India. The three oviposition traits act together to give and R0 that is 25–50% than that of eggs placed at random. These traits are known to be variable and heritable, hence, the conditions necessary for natural selection are statisfied.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Entomologia experimentalis et applicata 80 (1996), S. 163-165 
    ISSN: 1570-7458
    Schlagwort(e): olfaction ; EAG ; sensory physiology ; antennal sensitivity ; interspecies hybrids ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Entomologia experimentalis et applicata 91 (1999), S. 359-368 
    ISSN: 1570-7458
    Schlagwort(e): Barbarea vulgaris ssp. arcuata ; Cruciferae ; Phyllotreta nemorum ; Chrysomelidae ; Alticinae ; flea beetle ; plant defence ; host plant range ; near-isogenic ; Y-linkage ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract A Y-linked gene (R-gene) in the flea beetle Phyllotreta nemorum L. (Coleoptera: Chrysomelidae: Alticinae) confer the ability of larvae to survive on types of the plant Barbarea vulgaris R.Br. (Brassicaceae) which are immune to attack by susceptible conspecifics. Two near-isogenic flea beetle lines were developed. The YE-line contained the Y-linked R-gene, and male larvae from this line survived on B. vulgaris. The ST-line did not contain the gene and did not survive on the plant. The YE-line had been developed through 8–9 generations of backcrosses (YE-males with ST-females) and the two lines were considered to be isogenic except for genes located on the Y-chromosome. A single copy of the Y-linked gene is sufficient to transfer a susceptible genotype (ST) into a resistant genotype (YE) which is able to utilize a plant that is immune to attack by specimens without R-genes. The Y-linked gene had no effects on survival on other plant species tested. The gene did not have any effect on developmental times and weights of adult beetles reared on other plants than B. vulgaris. Developmental times of larvae with the Y-linked gene were longer on B. vulgaris than on normal host plants, R. sativus and S. arvensis, but the adults obtained the same size on these plant species. No trade-offs of the Y-linked gene were discovered. The results suggest that the occurrence of the Y-linked gene is a derived trait which has enabled the flea beetle to expand its host plant range. The evolution of a host shift to B. vulgaris seems not to be favoured by the presence of this single gene.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Acta biotheoretica 46 (1998), S. 141-156 
    ISSN: 1572-8358
    Schlagwort(e): locomotion ; Squamata ; lizards ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract In lower quadrupedal vertebrates locomotor efficiency seems to result from the associate movements of the axial and appendicular systems, which are totally independent in structure and embryological origin. The curvature of the trunk, produced by a standing wave, magnifies the propulsive action of the limbs. In intermediate forms, the association of an elongate trunk with limbs reduced in size brings about functional consequences which may be noticeably diverse according to the degree of trunk elongation and limb reduction. According to environmental constraints, animals search for better locomotor efficiency, which implies the maintenance or breakage of this association of both locomotor systems. In some cases, limb action on the ground is added to the axial wave action through a perfect mutual adjustment of rhythmic activity, until mechanical inefficiency of the limbs is reached by possible loss of contact with the ground. In other cases, the limbs dragged on the ground during the stance phase act against the axial action or, on the contrary, are inhibited by the axial system. A review of available data tries to contribute to an understanding of the respective roles of both systems in the transition to limblessness.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    Springer
    Entomologia experimentalis et applicata 80 (1996), S. 7-13 
    ISSN: 1570-7458
    Schlagwort(e): host-plant selection ; sensory physiology ; neural coding ; deterrents ; peripheral interactions ; receptor sites ; genetics of insects ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Recent advances in our understanding of the relationship between chemosensory and behavioural responses to phytochemicals come from a number of studies on ovipositional and food selection behaviour of flies, butterflies, moths and beetles. Establishing input-output relationships has provided insight into the way in which the activity of chemoreceptors is translated into host-plant selection behaviour. This was achieved for both the qualitative contrast acceptance/rejection and for quantifiable preference hierarchies. By now it is clear that the subtlety of coding the complex phytochemical profiles offered by potential host plants relies on across-fibre patterns or ensemblefiring of taste neurons. Progress along these lines depends on unravelling processing pathways in the central nervous system, still a largely unexplored area in herbivorous insects. Increased interest can be noted for the mechanisms operating during the most peripheral events of chemoreception: the interaction of phytochemical and chemoreceptor, determining the specificity of recognition. Evidence for ‘peripheral integration’ has accumulated. Deterrent receptors have an especially puzzling nature. Although such cells respond to a wide array of structurally diverse secondary plant metabolites, their sensitivity profile differs between closely related species. To what extent membrane-bound receptor molecules are involved and what degree of specificity is conferred by these, is largely unknown. Sensitivity to a certain group or class of compounds is determined by single genes in several cases. This allows for a scenario in which single gene mutations affect stimulus-receptor interactions, which might concurrently affect host-plant selection behaviour.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    Entomologia experimentalis et applicata 80 (1996), S. 320-324 
    ISSN: 1570-7458
    Schlagwort(e): multitrophic interactions ; phylogeny ; evolution ; fitness
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    Entomologia experimentalis et applicata 91 (1999), S. 29-35 
    ISSN: 1570-7458
    Schlagwort(e): chemoreception ; deterrents ; Pieris ; Brassicaceae ; cardenolides ; host-plant selection ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Pieris butterflies (Lepidoptera: Pieridae) are specialist herbivores of cruciferous plants. They exploit glucosinolates, secondary plant metabolites chemotaxonomically characteristic for this plant family, as token stimuli. In addition to particular glucosinolates, some genera of the Cruciferae contain cardenolides, steroidal allelochemicals that act as potent feeding and oviposition deterrents to several Pieris species. We investigated the sensory mechanisms by which these compounds are perceived in larvae. Pieris caterpillars and many other lepidopterous species are endowed with so-called generalist deterrent receptors, that respond to a broad spectrum of secondary plant substances. In Pieris caterpillars we found a second type of deterrent chemoreceptor in maxillary styloconic taste sensilla. This neuron is very sensitive to cardenolides (threshold 0.1–0.3 μM). The generalist deterrent receptor also responds to these substances but its threshold lies at 50–100× higher concentrations. In behavioural preference experiments Pieris brassicae L. caterpillars preferred cardenolide-treated cabbage leaf discs when confronted with a choice between them and a deterrent substance that does not occur in the Brassicaceae. The cardenolides acted as potent deterrents when offered against untreated cabbage leaf discs. This demonstrates that the balance of activity elicited in the two types of deterrent chemoreceptors determines the behavioural decision.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 8
    Digitale Medien
    Digitale Medien
    Springer
    Acta biotheoretica 47 (1999), S. 29-40 
    ISSN: 1572-8358
    Schlagwort(e): Sexual selection ; mate selection ; gamete selection ; evolution ; ploidy ; asssortative mating
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Results of an agent-based computer simulation of the evolution of diploid sexual organisms showed that several mate selection strategies confer much higher average fitness to the simulated populations, and higher evolutionary stability to the alleles coding for these strategies, than random mating. Strategies which select for 'good genes' were very successful, and so were strategies based on assortative mating. The results support the hypothesis that mating is not likely to be random in nature and that the most successful mate selection strategies are those based on assortative mating or on advantageous genes.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 9
    Digitale Medien
    Digitale Medien
    Springer
    Entomologia experimentalis et applicata 60 (1991), S. 173-182 
    ISSN: 1570-7458
    Schlagwort(e): Genetics ; evolution ; host adaptation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract When populations are exposed to different environments, evolutionary processes can lead either to genetically differentiated strains or to the appearance of increased generalism at the individual level. For evolution to occur, genetic variability in performance in different environments is required. Here, intraspecific genetic variation across environments was estimated in the flour beetle Tribolium castaneum (Herbst) by comparing the responses of two strains of T. castaneum to different flour types. Replicated groups from each strain were allowed to develop on either the standard whole wheat medium or on one of four novel flours (wheat, rice, corn and oat). In several of the novel flours, clear differences in mean development time or population size of one or both strains were seen relative to performance in the standard medium. Moreover, the strains differed significantly in their phenotypic responses to the flours. One strain did particularly poorly on oat flour. Reduced oviposition, reduced larval survivorship and increased larval cannibalism were examined as possible causes of the low productivity on oat flour. These three factors accounted for about 70% of the reduction in population size when this strain oviposited and developed in oat flour. The difference between these two outbred strains in response to these five flours suggests that genetic variation in resource use is present within T. castaneum and may also be present within strains and natural populations in grain storage facilities. Such variation would permit an evolutionary response to selection in multiple environments (flours). This process has agricultural implications when several types of grain are stored in a single location because it could eventually lead to the evolution of highly generalized populations of T. castaneum, an important pest of stored products.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 10
    Digitale Medien
    Digitale Medien
    Springer
    Entomologia experimentalis et applicata 82 (1997), S. 37-44 
    ISSN: 1570-7458
    Schlagwort(e): Barbarea vulgaris ; Cruciferae ; Phyllotreta nemorum ; Chrysomelidae ; Alticinae ; flea beetle ; plant defence ; genetics ; sex-linkage ; X- and Y-chromosome ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract A polymorphism in host plant exploitation has been discovered in the flea beetle, Phyllotreta nemorum L. (Coleoptera: Chrysomelidae: Alticinae) where one resistant population is able to use Barbarea vulgaris R.Br. ssp. arcuata (Opiz.) Simkovics (Brassicaceae) as a host plant while a susceptible population is not. Crosses (F1, F2, and backcrosses) between the two flea beetle populations were made, and survival of the progeny on B. v. ssp. arcuata was measured. The ability of P. nemorum larvae to survive in this plant species depended on the presence of major, dominant genes (R-genes). The two most abundant R-genes in the resistant flea beetle population were X- and Y-linked, respectively. The use of B. v. ssp. arcuata as a natural host plant by the resistant population of P. nemorum seems to be an extension of the host plant range of the species. The role of sex-linked genes in the evolution of host range is discussed.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 11
    Digitale Medien
    Digitale Medien
    Springer
    Entomologia experimentalis et applicata 82 (1997), S. 25-35 
    ISSN: 1570-7458
    Schlagwort(e): Barbarea vulgaris ; Cruciferae ; Phyllotreta nemorum ; Chrysomelidae ; Alticinae ; flea beetle ; plant defence ; resistance ; host plant ; variation ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Several sorts of variation in the interaction between the insect, Phyllotreta nemorum L. (Coleoptera:Chrysomelidae:Alticinae), and the plant, Barbarea vulgaris R.Br. (Brassicaceae), have been discovered: 1) genetic differences in the levels of defences in the plant, 2) genetic differences in the ability of insects to cope with the plant defences, 3) seasonal variation in levels of defences in the plant, and 4) differences between leaf types in levels of defences. Two plant accessions were suitable for larval development throughout the season while the remaining nine accessions were more or less unsuitable for larvae from the ‘susceptible’ T-population at least at certain times of the year. All accessions were suitable for the ‘resistant’ E-population throughout the year. There was a seasonal variation in levels of defences in some accessions which were unsuitable for the T-population during the summer period when beetles were present, but not during autumn and spring when the beetle were hibernating. Upper (younger) cauline leaves of these accessions had higher levels of defences than lower (older) cauline leaves. The resistant E-population used B. vulgaris as a natural host plant while the susceptible T-population did not. The use of B. vulgaris as a natural host plant by the E-population of P. nemorum seems to be an extension of the host plant range of the species. Variation in plant defences may have facilitated the switch in host plant use by the resistant flea beetle population.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Journal of applied electrochemistry 29 (1999), S. 1171-1176 
    ISSN: 1572-8838
    Schlagwort(e): alloys ; cyclic voltammetry ; electrodeposition ; electroless deposition ; nickel ; phosphorus ; zinc
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Elektrotechnik, Elektronik, Nachrichtentechnik
    Notizen: Abstract Electroless Ni–Zn–P alloy deposition from a sulphate bath, containing sodium hypophosphite as reducer, was investigated. To increase the plating rate, the deposition parameters were optimized. The effect of process parameters (T, pH and [Zn2+]) on the plating rate and deposit composition was examined and it was found that the presence of zinc in the bath has an inhibitory effect on the alloy deposition. As a consequence, the percentage of zinc in the electroless Ni–Zn–P alloys never reaches high values. Using cyclic voltammetry the electrodeposition mechanism of Ni–Zn–P alloys was investigated. It was observed that the zinc deposition inhibits the nickel discharge and, as a consequence, its catalytic activity on hypophosphite oxidation. It was also found that increase in temperature or pH leads to the deposition of nickel rich alloys.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 13
    ISSN: 1572-8854
    Schlagwort(e): Octahedral ; phosphorus ; chloride
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Geologie und Paläontologie , Physik
    Notizen: Abstract The title compound [P(tpp)Cl2]+Cl− crystallizes in the space group P21/n witha=10.701(2),b=24.860(2),c=14.799(2), β=94.24(2)°,Z=4. The phosphorus atom has an octahedral coordination geometry formed by the four nitrogen atoms (Np) of the porphyrinato group and the two chloride ions. The average phosphorus-chloride distance is 2.150(1) Å, with phosphorus situated 0.006 Å below the porphyrin ring.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 14
    Digitale Medien
    Digitale Medien
    Springer
    Journal of insect behavior 6 (1993), S. 715-735 
    ISSN: 1572-8889
    Schlagwort(e): Aphrodisiac ; cockroach ; evolution ; mating behavior ; sex pheromone ; sternal glands ; tergal glands
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Two chemical signals are essential in all cockroach sexual behavioral sequences: the sex pheromone released by one partner, generally the female (for long distance attraction), and an aphrodisiac sex pheromone produced exclusively by male tergal glands (for female mounting and tergal contact or “feeding” behavior). Unlike the other cockroach groups, the males of the Oxyhaloinae species produce both chemical signals: the pheromone and the aphrodisiac. The occurrence of three patterns of mating behavior (A, B, and C), the production of male sex pheromones, and the existence in the male of developed sternal and tergal glands in seven related Oxyhaloinae species, make these cockroaches a useful model for studying the evolution of mating behavior patterns. The various types of mating behavior were not classified in the previous studies by Roth and Barth. In this report, they have been named type A (female in upper position), B (male in upper position), and C (male and female end to end). In type A mating, the male tergal glands, which are licked by the females, are well developed, whereas in types B and C, there is no licking of the male's tergal secretion by the females and the tergal glands are much less developed; the aphrodisiacs secreted by the tergal glands may no longer act in this case through contact chemoreception, but through an olfactory process involving volatile components. One common sex pheromone component seems to be acetoin. I suggest that the mating behavior tends from A toward B and C during the evolutionary process with a concomitant regression of the tergal glands and changes in the aphrodisiac emission levels. The mating behavioral sequences of cockroaches (Dictyoptera) and crickets (Orthoptera) show a striking degree of similarity and are probably examples of convergent evolution.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 15
    Digitale Medien
    Digitale Medien
    Springer
    Journal of applied electrochemistry 27 (1997), S. 1198-1206 
    ISSN: 1572-8838
    Schlagwort(e): alloy ; amorphous ; anomalous ; hydrogen ; iron ; nickel ; phosphorus ; plating
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Elektrotechnik, Elektronik, Nachrichtentechnik
    Notizen: Abstract In this study we have investigated the electrodeposition of amorphous iron–nickel–phosphorus alloys from a sulfate electrolyte. Fe-Ni alloys are known to exhibit an ’anomalous‘ type of plating behaviour in which deposition of the less noble metal is favoured. We have found that the codeposition of phosphorus from hypophosphite in the electrolyte led to a reversal to a ’normal‘ behaviour. This reversal was due both to the suppression of iron and enhancement of nickel partial currents. The overall deposition process is dominated by the hydrogen evolution reaction. This is exacerbated by the low pH needed to codeposit sufficient phosphorus to achieve an amorphous structure.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 16
    ISSN: 1572-8838
    Schlagwort(e): alloys ; electroless ; microstructure ; morphology ; nickel ; phosphorus ; zinc
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Elektrotechnik, Elektronik, Nachrichtentechnik
    Notizen: Abstract Electroless Ni–Zn–P alloy coatings were obtained on an iron substrate from a sulfate bath at various pH values. The effects of changes in bath pH on alloy composition, morphology, microstructure and corrosion resistance were studied. Scanning electron microscopy was performed to observe the morphological change of the deposits with bath pH. Coating crystallinity was investigated by grazing incidence asymmetric Bragg X-ray diffraction and transmission electron microscopy. A transition from an amorphous to polycrystalline structure was observed on increasing the bath alkalinity, and thus decreasing the phosphorus content of the alloys. A single crystalline phase corresponding to face-centred-cubic nickel was identified in the alloys obtained from a strong alkaline solution. An increase in zinc percentage up to 23% in the deposits does not change the f.c.c. nickel crystalline structure. Corrosion potential and polarization resistance measurements indicated that the corrosion resistance of electroless Ni–Zn–P alloys depends strongly on the microstructure and chemical composition. The deposits obtained at pH 9.0–9.5 and with 11.4–12.5% zinc and 11.8–11.2% phosphorous exhibited the best corrosion resistance.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 17
    Digitale Medien
    Digitale Medien
    Springer
    Journal of insect behavior 6 (1993), S. 93-106 
    ISSN: 1572-8889
    Schlagwort(e): Belostomatidae ; giant water bugs ; paternal care ; eggs ; reproduction ; behavior ; brooding ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Males of the giant water bug Lethocerus medius(Guerin) typify their monobasic subfamily, the Lethocerinae, in that they do not brood eggs attached to their backs as do males of all members of the subfamily Belostomatinae. Exclusive male parental investment as expressed in the Belostomatinae is extremely rare behavior among animals, and evolution of the trait is obscure. Lethocerus mediusmales apparently remain with their mates through oviposition and are consistently found in attendance of eggs after the female has departed. This behavior may enhance paternity assurance at no cost in opportunity for polygyny. Two double clutches of eggs were found, from which we infer the potential for polygynous matings and shared parental investment. Male L. mediusbrood attended egg clutches above the surface of the water, where they may moisten them, shade them, and defend them against predation. Egg attendance/brooding by L. mediusand other Lethocerusspecies may represent a plesiomorphic state from which paternal back- brooding evolved in the Belostomatinae.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 18
    ISSN: 1572-8927
    Schlagwort(e): Solvolysis ; kinetics ; aqueous solvent mixtures ; Co(III) complexes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The kinetics of the solvolysis of [Co(CN)5Cl]3− have been investigated in water +2-methoxyethanol and water + diethylene glycol mixtures. Although the addition of these linear hydrophilic cosolvent molecules to water produces curvature in the variation of log(rate constant) with the reciprocal of the dielectric constant, their effect on the enthalpy and entropy of activation is minimal, unlike the effect of hydrophobic cosolvents. The application of a Gibbs energy cycle to the solvolysis in water and in the mixtures using either solvent-sorting or TATB values for the Gibbs energy of transfer of the chloride ion between water and the mixture shows that the relative stability of the emergent solvated Co(III) ion in the transition state compared to that of Co(CN)5Cl3− in the initial state increases with increasing content of cosolvent in the mixture. By comparing the effects of other cosolvents on the solvolysis, this differential increase in the relative stabilities of the two species increases with the degree of hydrophobicity of the cosolvent.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 19
    Digitale Medien
    Digitale Medien
    Springer
    Journal of applied electrochemistry 29 (1999), S. 191-200 
    ISSN: 1572-8838
    Schlagwort(e): cyclic redox reaction ; dissolution ; kinetics ; manganese dioxide ; mechanism ; pyrite
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Elektrotechnik, Elektronik, Nachrichtentechnik
    Notizen: Abstract This paper describes a study of the kinetics and mechanism of MnO2 dissolution in H2SO4 in the presence of pyrite through leaching and electrochemical parameters. Manganese(iv) was found to dissolve mainly through reduction by the ferrous ion generated during oxidation of pyrite by the ferric ion. The oxidation which is slower and rate controlling may proceed through two different reactions, one producing S0 and the other SO42−. Manganese dissolution runs at the same rate as that of pyrite oxidation by maintaining ferrous ion concentration at a much lower level than that of ferric. Kinetic equations based on corrosion coupling principles are developed to explain the observed leaching behaviour.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 20
    Digitale Medien
    Digitale Medien
    Springer
    Journal of chemical crystallography 28 (1998), S. 69-72 
    ISSN: 1572-8854
    Schlagwort(e): Co(III) complex ; crystal structure ; kinetics ; steric effects
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Geologie und Paläontologie , Physik
    Notizen: Abstract The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I〉2σ(I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH3)4(NH2CH3)Cl](ClO4)2 molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results.
    Materialart: Digitale Medien
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  • 21
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 19 (1990), S. 1073-1084 
    ISSN: 1572-8927
    Schlagwort(e): Solvolysis ; kinetics ; mixtures of water+cosolvent
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Rates of solvolysis of the complex cation [Co(4tBupy)4Cl2]+ have been determined in mixtures of water with the hydrophobic solvent, t-butyl alcohol. The solvent composition at which the extremum is found in the variation of the enthalpy ΔH* and the entropy ΔS* of activation correlates well with the extremum in the variation of the relative partial molar volume of t-butyl alcohol in the mixture and the straight line found for the variation of ΔH* with ΔS* is coincident with the same plot for water + 2-propanol mixtures. A free energy cycle is applied to the process initial state (C n+) going to the transition state [M(n+1)+...Cl−] in water and in the mixture using free energies of transfer of the individual ionic species, ΔG t o (i), from water into the mixture. Values for ΔG t o (i) are derived from the solvent sorting method and from the TATB/TPTB method: using data from either method, changes in solvent structure on going from water into the mixture are found to stabilize the cation in the transition state, M(n+1)+, more than in the initial state, C n+. This is compared with the application of the free energy cycle to the solvolysis of complexes [Co(Rpy)4Cl2]+ and [Coen2LCl]+ in mixtures of water with methanol, 2-propanol or t-butyl alcohol: the above conclusion regarding the relative stabilization of the cations holds for all these complexes in their solvolyses in water+alcohol mixtures using values of ΔG t o (Cl−) from either source.
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  • 22
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 2 (1973), S. 217-238 
    ISSN: 1572-8927
    Schlagwort(e): Cation ; energies ; H. S. Frank ; M. Eigen ; R. G. Wilkins ; kinetics ; ligand substitution ; mechanism ; mixed solvents ; nonaqueous ; solvation ; solvent ; solvent structure ; solvent exchange ; transition metal
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The role of the solvent in reactions involving ions is considered in relation to the structure of liquids. The rate constants and activation parameters for ligand substitutions at divalent transition metal cations in various solvents are compared with those for solvent exchanges. The differences are related to structural properties of the solvents, represented by their heats of evaporation and fluidities, and interpreted with the aid of a model developed from that of Frank and Wen. Water is not a typical solvent.
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  • 23
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 21 (1992), S. 1271-1287 
    ISSN: 1572-8927
    Schlagwort(e): Cu(II) ; kinetics ; reduction ; temperature dependence ; H2O2, NaCl, NaBr, NaClO4
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The rates of reduction of Cu(II) with H2O2 have been measured in NaCl and NaBr solutions and mixtures with NaClO4 as a function of pH (6 to 9), temperature (5 to 45°C) and ionic composition (0.1 to 6M). The effect of pH on the rates was found to be independent of temperature and ionic composition. The rates increased as a function of [H+] raised to the power of 1.3 to 1.6. Speciation calculations indicate that this pH dependence can be attributed to Cu(OH)2 being the reactive species. The rate constants in NaCl and NaBr and mixtures with NaClO4 were independent of ionic strength, but proportional to the halide concentration raised to the power of 2.0 (0.2 to 2.6M). These results can be attributed to Cu(OH)2Cl 2 2− being the reactive species to reduction with H2O2. The Cu(I) halide complexes formed from the reduction are not easily oxidized with O2 or H2O2. The faster rates in Br− solutions, which form stronger complexes with Cu+, support this contention. Measurements made in NaCl with added NaHCO3, NaB(OH)4 EDTA, NTA and glycine were also made. These measurements indicate that the CuL complexes (L=B(OH) 4 − , CO 3 2− , EDTA, NTA, and glycine) are not very reactive to reduction with H2O2. The addition of Mg2+ or Ca2+ caused the rates to increase due to the formation of MgL or CaL complexes and the resultant release of reactive Cu2+.
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  • 24
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 23 (1994), S. 483-500 
    ISSN: 1572-8927
    Schlagwort(e): Thermodynamics ; kinetics ; chemical relaxation ; temperature-jump ; amplitudes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Amplitudes of chemical relaxation signals can provide useful information as to the thermodynamics of coupled chemical reactions. The temperature-jump technique has been used to investigate the thermodynamic behavior of the Nickel(II)-3,5-dinitrosalicylate system in buffer solution, where complex formation steps are coupled to proton transfer steps. The analysis of the relaxation curves is based on the transformation of a set of coupled elementary reactions into a set of uncoupled ‘normal reactions.’ By analogy with classical titrations, the experiments have been performed by changing the metal ion concentration at constant ligand concentration and pH. Each measured amplitude is associated in this way to a point of a ‘dynamic titration’ and a procedure is formulated by which the values of the equilibrium constants and enthalpies of the normal reactions are simultaneously obtained by simple linear plots. From the dependence of these parameters on suitable functions of the concentrations of the reactants the values of ΔG° and ΔH° of the individual steps are derived. It is shown that the addition of a buffer (instead of an indicator) influences the stoichiometric coefficients of the normal reaction in such a way that measurable amplitudes are produced in systems that, as the presently investigated, in unbuffered solution would remain insensitive to the external perturbation. The circumstances under which the dynamic method offers advantages over the classical techniques are discussed.
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  • 25
    Digitale Medien
    Digitale Medien
    Springer
    Adsorption 1 (1995), S. 133-151 
    ISSN: 1572-8757
    Schlagwort(e): PSA process ; sensitivity ; equilibria ; kinetics ; heats
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract Mathematical models for pressure swing adsorption (PSA) processes essentially require the simultaneous solutions of mass, heat and momentum balance equations for each step of the process using appropriate boundary conditions for the steps. The key model input variables needed for estimating the separation performance of the process are the multicomponent adsorption equilibria, kinetics and heats of adsorption for the system of interest. A very detailed model of an adiabatic Skarstrom PSA cycle for production of high purity methane from a ethylene-methane bulk mixture is developed to study the sensitivity of the process performance to the input variables. The adsorption equilibria are described by the heterogeneous Toth model which accounts for variations of isosteric heats of adsorption of the components with adsorbate loading. A linear driving force model is used to describe the kinetics. The study shows that small errors in the heats of adsorption of the components can severely alter the overall performance of the process (methane recovery and productivity). The adsorptive mass transfer coefficients of the components also must be known fairly accurately in order to obtain precise separation performance.
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  • 26
    Digitale Medien
    Digitale Medien
    Springer
    Adsorption 2 (1996), S. 265-277 
    ISSN: 1572-8757
    Schlagwort(e): frequency response ; diffusion cell ; kinetics ; diffusion ; heat effects
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract This paper deals with frequency response (FR) analysis of a closed diffusion cell system with two resonators, that is both the LHS and RHS volumes are modulated. The analysis is made for a homogeneous particle described by a single effective diffusivity as well as a biporous pellet described by macropore and micropore diffusions. It is shown that if the perturbation of the volume of the reservoir #2 is lagged behind that of the reservoir #1 by 3π/2, the pressure response in reservoir #1 is significantly enhanced with larger amplitude as well as phase angle. When the perturbations of the two reservoirs are out of phase, the heat effect is reduced and can become insignificant when the two perturbations are completely out of phase (ψ = π). Under such a condition, the pressure difference between the two reservoirs could be doubled. In the case of biporous pellets, it is shown that the FR behaviours obtained for micropore diffusion control and macropore diffusion control are well distinguished. In the former case, the FR system reduces to a traditional batch adsorber one while in the latter case, the FR behaviour is the same as for a two resonator system with homogeneous particles. This difference can be used for the discrimination of micropore and macropore diffusion processes.
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  • 27
    Digitale Medien
    Digitale Medien
    Springer
    Adsorption 3 (1997), S. 267-275 
    ISSN: 1572-8757
    Schlagwort(e): characterisation ; equilibria ; kinetics ; micropore size distribution ; n-butane ; nutshell
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract Adsorption equilibria and dynamics ofn-butane on two activated carbon samples prepared from the physical activation of nutshell are studied in this paper. The micropore size distribution (MPSD) is considered as the main source of solid heterogeneity. Lennard-Jones' potential theory and Dubinin's theory (TVFM) are used in the equilibria data to derive the MPSD, which is well fitted by a Gamma distribution function. The adsorption energy distribution derived from the MPSD is very asymmetric for both the samples studied, and this energy distribution used in the HMSD/HMSMD kinetics models for the study of adsorption dynamics ofn-butane.
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  • 28
    Digitale Medien
    Digitale Medien
    Springer
    BioMetals 12 (1999), S. 1-10 
    ISSN: 1572-8773
    Schlagwort(e): acidophilic ; strain ; oxidation ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Recovery of metal values from sulfide ores by use of acidophilic microorganisms is gaining importance. A number of commercial/pilot plants are setup to find out the techno-economic feasibility of the overall process. The main drawback in the process is the slow kinetics of dissolution of metal values from the sulfide ores. To make the technology e attractive the kinetics should be improved considerably. There are various factors which determine the overall kinetics such as bacterial activity and concentration, iron and sulfur oxidation, oxygen consumption, reactor design and nature of ore. A brief review has been made dealing with the above parameters
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  • 29
    ISSN: 1572-879X
    Schlagwort(e): Fischer-Tropsch synthesis ; reaction activation barrier ; carbon chain growth and termination ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A method is established, by which the difference of the reaction activation barriers of carbon chain growth and termination in Fischer-Tropsch (FT) synthesis can be determined from experiments. A FT synthesis is carried out on Fe/Zn catalyst. We apply the method to analyze the experimental result and obtain the difference of reaction activation barriers of carbon chain growth and termination of α-olefins on the catalyst.
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  • 30
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 37 (1996), S. 167-172 
    ISSN: 1572-879X
    Schlagwort(e): dissociation ; kinetics ; Co-Mo sulphide ; H2S
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract In this study, a high surface area 4Co∶6Mo∶100γ-Al2O3 sulphide prepared using precipitation from homogeneous solution (PFHS) has been used for the catalytic splitting of hydrogen sulphide into H2 and elemental sulphur. The activity of this new formulation was significantly better than previously reported recipes. Kinetic data collected over a wide range of H2S partial pressures between 883 and 983 K revealed that, although the decomposition followed a first-order law, a mechanism involving H2S adsorption on co-ordinative unsaturation sites of the Co-Mo sulphide catalyst gave a Langmuir-Hinshelwood rate expression that yielded satisfactory model parameters. In particular, the scission of the surface H-S bond appeared to be the rate determining step.
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  • 31
    ISSN: 1572-879X
    Schlagwort(e): selective catalytic reduction ; nitric oxide reduction ; phosphorus ; acid property
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract To examine the influence of phosphorus on the commercial V2O5(WO3)/TiO2 SCR catalyst, measurements were carried out by means of infrared and Raman spectroscopy, XPS, and NO reduction measurement as a function of phosphorus loading. Phosphorus added to the catalyst was found to disperse well over the catalyst without a significant agglomeration up to 5 wt% P2O5 addition. The number of the hydroxyl groups bonded to the vanadium and titanium species decreased readily with increasing amount of phosphorus. Correspondingly, the hydroxyl groups bonded to the phosphorus species were formed. NH3 adsorbed on both hydroxyl groups bonded to vanadium and phosphorus as ammonium ions, implying that the P–OH groups formed are also responsible for the Brønsted acidity. The NO reduction activity was found to be decreased with increasing amount of phosphorus; however, the influence of phosphorus was relatively small irrespective of the large amount of phosphorus addition. The deactivation might be caused by the change in the nature of the surface hydroxyl groups as Brønsted acid sites. Phosphorus species might partially wrap the surface V=O and W=O groups, which might also contribute to the deactivation.
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  • 32
    Digitale Medien
    Digitale Medien
    Springer
    Cellulose 1 (1994), S. 26-56 
    ISSN: 1572-882X
    Schlagwort(e): low-temperature degradation ; kinetics ; mechanisms ; electrical insulation ; transformers
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract A critical review is given of the degradation of cellulose in the low-temperature region (below about 300°C) of power transformer operation. The large number of kinetic studies, under a variety of environmental conditions from Kraft paper in insulating oil, to cotton and paper in oxygen, are considered in terms of a first-order polymer chain scission model. In many cases, the data are replotted to suit the model. A common activation energy of 111±6 kjmol−1 is calculated and it is shown that the pre-exponential factor, rather than the activation energy, is sensitive to the oxidizing nature of the environment and the susceptibility to degradation of the material. The chemical mechanisms of degradation are reviewed, and conclusions and recommendations are made regarding chemical condition monitoring and life prediction of electrical insulation.
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  • 33
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 37 (1996), S. 173-179 
    ISSN: 1572-879X
    Schlagwort(e): ammonia synthesis ; iron catalysts ; potassium promotion ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Measurements were performed of reaction rate in the process of ammonia synthesis (T=370–470°C) on doubly promoted (DP) (Al2O3, CaO) and triply promoted (TP) (K2O, Al2O3, CaO) iron catalysts. The latter were obtained by impregnation of the reduced and subsequently passivated DP precursors with alcoholic solution of KOH. The studies were carried out under high total pressure (10 MPa) in a wide range of ammonia partial pressure in the gas phase: from 0.25 to about 7 bar. The results are shown to be authoritative for the so-called kinetic regime. The effect of the presence of K+ cations in the catalyst was the stronger, as the temperature of the reaction was the lower and, in particular, the ammonia pressure in the gas phase the higher. The obtained results are in good accordance with the results of Somorjai's studies on activity of iron single crystal surfaces both clean and covered with (K+O) adlayer.
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  • 34
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 27 (1994), S. 79-90 
    ISSN: 1572-879X
    Schlagwort(e): kinetics ; carbon ; oxygen ; recombination ; rhodium ; surface characterisation ; XPS ; AES
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Different mechanisms of atomic carbon and oxygen recombination on a rhodium surface are studied with Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The kinetics of adsorbed carbidic carbon oxidation (carbon coverageθ c ≈ 0.1–0.3 ML) by gas-phase oxygen that proceeds by a Langmuir-Hinshelwood reaction mechanism, provides the value of the activation energy for recombination (E rec ⇂t ≈ 170±20 kJ/mol).E rec ⇂t depends slightly on the carbon coverage. An Eley-Rideal type of reaction was observed for adsorbed oxygen and atomic gas-phase carbon recombination which occurs in a dynamic regime. The low value found for the activation energy (near zero) is consistent with the mechanism that this exothermic reaction is too fast for energy dissipation into the substrate; the energy is mainly transferred into translational, vibrational and rotational energy of CO.
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  • 35
    ISSN: 1572-882X
    Schlagwort(e): accelerated tests ; aging tests ; cellulose degradation ; durability ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract Accelerated aging tests are credible and useful to predict paper permanence only if such tests can be shown to correlate with natural aging. In the first part of this study, a kinetic model was developed based on the accelerated aging results. In this report, we have shown that this kinetic model can indeed predict the natural aging results of lignin-free sheets with a statistical confidence. This is the first quantitative comparison of accelerated aging with natural aging.
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  • 36
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 27 (1998), S. 1123-1138 
    ISSN: 1572-8927
    Schlagwort(e): Sol–gel processing ; hydrolysis ; condensation ; kinetics ; methoxydimethyloctylsilane ; copper nitrate hydrate ; phase diagram
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The reaction rate was determined for copper nitrate hydrate with methoxydimethyloctylsilane (MDOS) in methanol. The rate constants of hydrolysis and condensation were established by quantitative measurement of the product and Karl Fischer water determination. The reaction with the hydrated copper salt resulted in the phase separation of an insoluble product from the reaction mixture. The structure of the product was determined, by Fourier Transform Infrared Spectrometry (FTIR) and Nuclear Magnetic Resonance (NMR) to be a dimer of the MDOS. The results showed the alcohol, producing condensation reaction was negligible in the formation of the dimer. contrary to the case for the well-known reaction by trialkoxysilanes and tetraalkoxysilanes.
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  • 37
    Digitale Medien
    Digitale Medien
    Springer
    Cellulose 4 (1997), S. 1-5 
    ISSN: 1572-882X
    Schlagwort(e): paper ; degradation ; ageing ; kinetics ; modelling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
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  • 38
    Digitale Medien
    Digitale Medien
    Springer
    Cellulose 3 (1996), S. 243-267 
    ISSN: 1572-882X
    Schlagwort(e): aging tests ; cellulose degradation ; durability ; kinetics ; paper properties
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract The validity of accelerated aging tests to predict and rank papers on their permanence has been under question, preventing the development of performance-based standards for permanent paper. We conducted a general kinetic analysis to investigate the aging process of paper. A general kinetic model is proposed to describe the depolymerization of cellulose. Experimentally it was shown that in the case of aging, cellulose degradation follows classic first-order kinetics as a special case of our general kinetic model. The Arrhenius equation was critically re-examined for the case of a multiple reaction system. It was shown analytically that the Arrhenius equation is still applicable when certain conditions are met. This was convincingly supported by experimental results. We also analysed the dependence of the degradation rate on the moisture content and hydrogen ion concentration. By conducting systematic experiments on these two factors, a general and quantitative relationship was established to explain the contribution of each factor and their interactions. Finally, based on this kinetic analysis, the effects of storage conditions on the life expectancy of paper were estimated.
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  • 39
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 3 (1974), S. 881-887 
    ISSN: 1572-8927
    Schlagwort(e): Binary aqueous mixtures ; solubilities ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A treatment which predicts the solubilities of gases in solvent mixtures is examined in the context of the analysis of kinetic data for reactions in aqueous mixtures. The treatment is qualitatively successful to some extent in resolving the effects of changes in the initial state of the reacting substrate in the activation parameters.
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  • 40
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inorganic and organometallic polymers and materials 8 (1998), S. 111-117 
    ISSN: 1572-8870
    Schlagwort(e): Organosiloxane ; kinetics ; poly(phenylmethylsiloxane) ; catalyst ; anionic ; ring-opening
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract It is well known that the rate of polymerization for an anionic mechanism is dependent on the ability of the bulk material or solvent system to disassociate the ion pair at the propagating chain end. In the anionic ring-opening polymerization of cyclic organosiloxanes in particular, the larger and softer the counter ion, the more rapidly the reaction proceeds. A recently developed phosphazene initiator system provides a large, soft counter ion relative to other traditional initiators used for the polymerization of poly(dimethylsiloxane) (PDMS). This novel initiator system was used in this investigation for the ring-opening polymerization of tetraphenyltetramethylcyclotetrasiloxane (P4) and the reaction kinetics under bulk and solution conditions were investigated. The new initiator system showed a dramatic increase in the rate of polymerization over the conventional potassium hydroxide-catalyzed system. Furthermore, this initiator was sufficiently reactive to be useful for the ring-opening polymerization of P4 at 293 K.
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  • 41
    ISSN: 1572-8900
    Schlagwort(e): Cellulose ; alkaline degradation ; peeling off ; degree of polymerization ; kinetics ; (gluco)isosaccharinic acid
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Energietechnik , Maschinenbau
    Notizen: Abstract The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are α- and β-(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.
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  • 42
    Digitale Medien
    Digitale Medien
    Springer
    Topics in catalysis 5 (1998), S. 133-147 
    ISSN: 1572-9028
    Schlagwort(e): NMR ; catalysis ; high pressure ; dynamic equilibria ; magnetization transfer ; sapphire tube ; gas phase ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract High resolution NMR techniques are applicable to a variety of aspects of catalysis. Methods for studying homogeneously-catalyzed systems under high gas pressure are described along with approaches for obtaining mechanistic and dynamic information. Many of the same techniques may be applied to heterogeneous catalysis by following the reaction chemistry by gas phase NMR.
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  • 43
    ISSN: 1572-9028
    Schlagwort(e): nonlinear temperature behavior ; Eyring plot ; modified Eyring plot ; selectivity ; selection process ; enantioselectivity ; selection level ; isoinversion principle ; isoinversion temperature ; inversion temperature ; kinetics ; catalysis ; asymmetric hydrogenation ; dihydroxylation ; cocyclization
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The influence of the temperature on selectivity is described under special consideration of nonlinearities in the corresponding modified Eyring plots. Reasons for the experimentally well-known behavior are discussed. Furthermore, the conditions for nonlinear temperature behavior are quantified and a concept is described which allows the determination of the temperature dependence of a single reaction pathway in a selection process.
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  • 44
    Digitale Medien
    Digitale Medien
    Springer
    Topics in catalysis 1 (1994), S. 305-314 
    ISSN: 1572-9028
    Schlagwort(e): non-Langmuir ; kinetics ; non-linear dynamics ; oscillations ; chaos ; self-organization
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The kinetics of a catalytic reaction is frequently formulated in terms of simple concepts of the Langmuir type. Apart from limitations arising from the non-uniformity of the catalyst's surface and from the coverage dependence of the rate “constants”, several other complications may come into play. These may arise on the “quantum level” where energy flow between the various degrees of freedom may cause failure of simple transition state theory, as well as on the “continuum level” where formulation of rate equations in terms of coupled non-linear differential equations may give rise to a rich scenario of spatio-temporal self-organization, including kinetic oscillations, chaos, and formation of concentration patterns. Several of these phenomena are illustrated by selected examples.
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  • 45
    Digitale Medien
    Digitale Medien
    Springer
    Aquatic sciences 53 (1991), S. 263-272 
    ISSN: 1420-9055
    Schlagwort(e): Lake ecosystem ; chl-a ; phosphorus ; nitrogen ; river flow ; thermocline ; simulation model ; multiple regression
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract The management variables which primarily affect phytoplankton biomass (as chl-a) in Lake Mjøsa, Norway, are total phosphorus loading (TP) and the timing and volume of water through flow (by active storage reservoirs). The response of the lake to changes in these factors is studied using a simulation model of the lake ecosystem. Chl-a responses from both observed data and the simulated results are extracted by multiple regression. Results show that decreasing TP load decreases chl-a, but less at low TP levels (〈 10 mg TP · m−3). There is also a certain time period for peak river flow which gives the least yield of chl-a per unit TP. This time period occurs in early summer (i.e., around June 10) if the total phosphorus load is low, and later if the load is high. Both observations and simulation results show that a high water flow increases chl-a at low epilimnion depths (〈 15 m), but that the same high water flow decreases chl-a when epilmnion is deep.
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  • 46
    Digitale Medien
    Digitale Medien
    Springer
    Cellular and molecular life sciences 50 (1994), S. 521-523 
    ISSN: 1420-9071
    Schlagwort(e): Ancient DNA ; evolution ; conservation ; biology ; anthropology ; plant biology ; PCR (polymerase chain reaction)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 47
    Digitale Medien
    Digitale Medien
    Springer
    Cellular and molecular life sciences 52 (1996), S. 14-24 
    ISSN: 1420-9071
    Schlagwort(e): Lycaenidae ; Formicidae ; symbiosis ; mutualism ; parasitism ; communication ; ecology ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract Associations with ants, termed myrmecophily, are widespread in the butterfly family Lycaenidae and range from mere co-existence to more or less specific mutualistic or even parasitic interactions. Secretions of specialized epidermal glands are crucial for mediating the interactions. Transfer of nutrients (carbohydrates, amino acids) from butterfly larvae to ants plays a major role, but manipulative communication with the help of odour signals is also involved. By means of myrmecophily, lycaenid butterflies largely escape ant predation, and certain species gain protection through attendant ants or achieve developmental benefits from ant-attendance. Benefits to the ants range from minimal to substantial food rewards. While most lycaenid species maintain facultative relationships with a variety of ant genera, highly specific and obligatory associations have convergently evolved in a number of butterfly lineages. As a corollary, communication systems are largely unspecific in the former, but may be highly specialized in the latter. The sophisticated communication between obligate myrmecophiles and their host ants is tightly connected with the evolutionary rise of specialized life-cycles and thus is a source of augmenting diversity within the butterflies.
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  • 48
    Digitale Medien
    Digitale Medien
    Springer
    Cellular and molecular life sciences 50 (1994), S. 63-71 
    ISSN: 1420-9071
    Schlagwort(e): Insect ; behaviour ; high-speed cinematography ; jumping ; electrophysiology ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract The Indian antHarpegnathos saltator may be unique among insects in using its jumping capacity not only as an escape mechanism but also as a normal means of locomotion, and for catching its prey in flight. High-speed cinematography used to analyse the various phases of the jump suggests thatHarpegnathos employs a novel jumping mechanism to mediate these behaviours: namely the synchronous activation of its middle and hindlegs. Electrophysiological recordings from muscles or nerves in pairs of middle and hindlegs show remarkably synchronous activity during fictive jumping, supporting the synchronous activation hypothesis.Harpegnathos is not the only ant to jump, and a cladistic analysis suggests that jumping behaviour evolved independently three times during ant evolutionary history.
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  • 49
    Digitale Medien
    Digitale Medien
    Springer
    Aquatic sciences 52 (1990), S. 199-220 
    ISSN: 1420-9055
    Schlagwort(e): Eutrophication ; lake management ; phosphorus ; ecosystem ; chlorophyll-a ; mathematical modelling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract We compare results of a new model for predicting the short term inter annual changes in chlorophyll-a (chl-a) in lakes after reductions in total phosphorus (TP) to predictions made by least squares regression models. In the new method, slopes of chl-a/TP graphs (both axes in mg · m−3) are depicted in frequency diagrams and used to extract information on the expected, short term chl-a/TP response. The short term response for nine shallow (〈 10 m deep) and nutrient rich lakes to changes in TP was found to be: Chl-a = 0.49 · TP + 17.3, and for nine deep, P-limited lakes: Chl-a = 0.08 · TP + 3.5. If the TP-reduction is known to be greater than 10 mg · m−3, the expected slope increases to 0.58 for shallow lakes and to 0.26 for deep lakes. The slope, 0.58, is 8% lower than the slope for the long term response calculated by regression for the shallow lakes. For deep lakes the slope, 0.26, is 2 to 3 times higher than that calculated by regression, indicating that reductions in TP for deep lakes give greater effects than least squares regression equations suggest. We have also calculated the reduction in TP which will give about 80% probability that a reduction in chl-a will be observed next year. For shallow, P-limited lakes this reduction is about 30 mg · m−3 (5% of average initial in-lake TP concentration), and for deep lakes about 14 mg · m−3 (35% of average initial in-lake TP concentration).
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  • 50
    Digitale Medien
    Digitale Medien
    Springer
    Aquatic sciences 52 (1990), S. 256-268 
    ISSN: 1420-9055
    Schlagwort(e): Vertical mixing ; stratification ; phosphorus ; Lake Constance
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Depth variable vertical eddy diffusion coefficients for heat (K z) were calculated from continuously measured temperature profiles in Überlinger See (western part of Lake Constance). The temperatures were averaged over vertical intervals of 10 m yielding 14 discrete values (maximum depth of Überlinger See: 147 m). A linear fit from 10 June to 29 September 1987 was used to smooth the significant temperature fluctuations caused by internal seiches of Lake Constance. Assuming horizontal homogeneity for the smoothed data the Gradient-Flux-Method was applied to compute vertical diffusion coefficientsK z at different depths using the depth variable volumes and surfaces of the 14 layers. The resulting mean diffusion coefficients for the period from June to September are 0.04 cm2/s near the thermocline and up to 0.8 cm2/s in deeper strata (accuracy: ± 50%). It is shown that horizontal mixing between Überlinger See and Obersee (main lake) alters the computation ofK z by less than 50%. A relationship betweenK z and stability (Brunt-Väisälä) frequencyN is found which corresponds well to the theory of internal wave induced turbulence. Combining the diffusion coefficients with measured phosphorus profiles, a phosphorus flux from the hypolimnion to the epilimnion of (0.7 ± 0.4) mg P m−2 d−1 was calculated, corresponding to about 20% of the average external loading per area of Lake Constance in 1986.
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  • 51
    ISSN: 1420-9055
    Schlagwort(e): Sediment ; interstitial water ; phosphorus ; iron ; persulfate digestion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract It is shown that sorption of orthophosphate to iron compounds, formed during persulfate digestion, can cause a significant underestimation of total dissolved phosphorus in interstitial waters rich in iron and poor in phosphorus. Labelling the samples with carrier free32PO4 before digestion allows to correct for these losses.
    Materialart: Digitale Medien
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  • 52
    Digitale Medien
    Digitale Medien
    Springer
    Cellular and molecular life sciences 46 (1990), S. 1106-1117 
    ISSN: 1420-9071
    Schlagwort(e): Genetic code ; eucaryotic cell ; evolution ; code ambiguity ; code universality ; convergence
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary This article is a review of the rules used by eucaryotic cells to translate a nuclear messenger RNA into a polypeptide chain. The recent observation that these rules are not identical in two species of a same phylum indicates that they have changed during the course of evolution. Possible scenarios for such changes are presented.
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  • 53
    Digitale Medien
    Digitale Medien
    Springer
    Cellular and molecular life sciences 49 (1993), S. 1027-1036 
    ISSN: 1420-9071
    Schlagwort(e): Archaea (archaebacteria) ; extreme halophiles ; archaeol phospholipids ; archaeol glycolipids ; membrane function ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract Archaebacteria (archaea) are comprised of three groups of prokaryotes: extreme halophiles, methanogens and thermoacidophiles (extreme thermophiles). Their membrane phospholipids and glycolipids are derived entirely from a saturated, isopranoid glycerol diether,sn-2,3-diphytanylglycerol (‘archaeol’) and/or its dimer, dibiphytanyldiglyceroltetraether (‘caldarchaeol’). In extreme halophiles, the major phospholipid is the archaeol analogue of phosphatidylglycerolmethylphosphate (PGP-Me); the glycolipids are sulfated and/or unsulfated glycosyl archaeols with diverse carbohydrate structure characteristic of taxons on the generic level. Biosynthesis of these archaeol-derived polar lipids occurs in a multienzyme, membrane-bound system that is absolutely dependent on high salt concentration (4 M). The highly complex biosynthetic pathways involve intermediates containing glycerol ether-linked C20-isoprenyl groups which are reduced to phytanyl groups to give the final saturated polar lipids. In methanogens, polar lipids are derived both from archaeol and caldarchaeol, and thermoacidophiles contain essentially only caldarchaeol-derived polar lipids. The function of these membrane polar lipids in maintaining the stability, fluidity and ionic properties of the cell membrane of extreme halophiles, as well as the evolutionary implications of the archaeol and caldarchaeol-derived structures will be discussed.
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  • 54
    Digitale Medien
    Digitale Medien
    Springer
    Cellular and molecular life sciences 49 (1993), S. 110-117 
    ISSN: 1420-9071
    Schlagwort(e): Polymerization ; sickle hemoglobin ; sickle cell disease ; kinetics ; thermodynamics ; polymer domains ; nucleation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract The polymerization of sickle hemoglobin occurs by the same mechanisms in solutions and in cells, and involves the formation of 14 stranded fibers from hemoglobin molecules which have assumed a deoxy quaternary structure. The fibers form via two types of highly concentration-dependent nucleation processes: homogeneous nucleation in solutions with hemoglobin activity above a critical activity, and heterogeneous nucleation in similarly supersaturated solutions which also contain hemoglobin polymers. The latter pathway is dominant, and creates polymer arrays called domains. The individual polymers bend, but also cross-link, and the resulting mass behaves as a solid. The concentration of polymerized hemoglobin increases exponentially unless clamped by rate limiting effects such as oxygen delivery.
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  • 55
    Digitale Medien
    Digitale Medien
    Springer
    Cellular and molecular life sciences 48 (1992), S. 729-731 
    ISSN: 1420-9071
    Schlagwort(e): Urea cycle ; leech ; botryoidal tissue ; hirudineans ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract Ornithine carbamoyltransferase (OCT) and arginase, but not arginine synthetase (AS), were detected in the body wall and gut tissues of the leech. The activities of these enzymes were not altered by starvation. The high activity of arginase in body wall is probably due to the association of the latter with botryoidal tissue. Hirudineans, which evolved from oligochaete ancestors, appear to have lost the citrulline-arginine segment of the urea cycle due to their ammonotelic mode of nitrogen excretion.
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  • 56
    Digitale Medien
    Digitale Medien
    Springer
    Cellular and molecular life sciences 50 (1994), S. 987-1001 
    ISSN: 1420-9071
    Schlagwort(e): Hsp70 ; evolution ; gene duplication ; gene homology
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract The family of genes encoding heat shock proteins of about 70 kDa (hsp70) in vertebrates is reviewed under genetic aspects. After a detailed description of the various hsp70 genes more general characteristics of the organization and evolution of the multigene family are discussed.
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  • 57
    Digitale Medien
    Digitale Medien
    Springer
    Cellular and molecular life sciences 49 (1993), S. 317-319 
    ISSN: 1420-9071
    Schlagwort(e): Chitin ; cuticle ; evolution ; vertebrates ; bony fish ; Blenniidae ; Paralipophrys trigoides
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract Lectin binding, endo-chitinase binding and enzymatic degradation studies show that the epidermal cuticle of the bony fishParalipophrys trigloides (Blenniidae) is chitinous. This is the first evidence that a vertebrate species possesses a chitinous tissue. Recently aXenopus gene has been identified which has significant sequence similarity to the catalytic domain of yeast chitin synthase III, a chitin producing enzyme1,2. Taken together these two findings imply that chitin synthesis capability may be a basic vertebrate feature.
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  • 58
    Digitale Medien
    Digitale Medien
    Springer
    Cellular and molecular life sciences 50 (1994), S. 429-437 
    ISSN: 1420-9071
    Schlagwort(e): Genetics ; ecology ; DNA-transfer ; conjugation ; transformation ; transduction ; transposons ; dormant cells ; epilithon ; microbial colonisation ; symbiosis ; virus resistance ; biosafety ; release of genes ; insults to humanity ; evolution ; biodiversity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract Genetic ecology is the extension of our modern knowledge in molecular genetics to studies of viability, gene expression and gene movements in natural environments like soils, aquifers and digestive tracts. In such milieux, the horizontal transfer of plasmid-borne genes between phylogenetically distant species has already been found to be much more frequent than had been expected from laboratory experience. For the study of exchanges involving chromosomally-located genes, more has to be learned about the behaviour of transposons in such environments. The results expected from studies in genetic ecology are relevant for considerations of evolution, biodiversity and biosafety. The role of this new field of research in restoring popular confidence in science and in its biotechnological applications is stressed.
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  • 59
    Digitale Medien
    Digitale Medien
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    Cellular and molecular life sciences 51 (1995), S. 454-464 
    ISSN: 1420-9071
    Schlagwort(e): Quantitative genetics ; life history ; evolution ; cladocera ; heritability ; Daphnia ; zooplankton
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract Quantitative genetic techniques are powerful tools for use in understanding the microevolutionary process. Because of their size, lifespan, and ease of culture, many zooplankton species are ideal for quantitative genetic approaches. As model systems, studies of zooplankton life histories are becoming increasingly used for examination of the central paradigms of evolutionary theory. Two of the fundamental empirical questions that zooplankton quantitative genetics studies can answer are: 1) How much genetic variance exists in natural populations for life history traits? 2) What is the empirical evidence for trade-offs that permeate life history theory based on optimality approaches? A review of existing data onDaphnia indicates substantial genetic variance for body size, clutch size, and age at first reproduction. Average broad-sense heritabilities for these three characters across 19 populations of 6 species are 0.31, 0.31, and 0.34, respectively. Although there is some discrepancy between the two pertinent studies that were designed to decompose the total genetic variance into its additive and non-additive components, a crude average seems to suggest that approximately 60% of the total genetic variance has an additive basis. The existing data are somewhat inconsistent with respect to presence/absence of trade-offs (negative genetic correlations) among life history traits. A composite of the existing data seems to argue against the existence of strong trade-offs between offspring size and offspring number, between present and future reproduction, and between developmental rate and fecundity. However, there is some evidence for a shift toward more negative (less positive) covariances in more stressful environments (e.g., low food). Zooplankton will prove to be very useful in future study in several important areas of research, including the genetics and physiology of aging, the importance of genotype-environment interaction for life history traits, and the evolution of phenotypic plasticity.
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  • 60
    Digitale Medien
    Digitale Medien
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    Cellular and molecular life sciences 52 (1996), S. 503-510 
    ISSN: 1420-9071
    Schlagwort(e): Drosophila ; accessory gland ; reproduction ; sexual behavior ; sperm displacement ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract Recent results from biochemical and molecular genetic studies of the accessory gland proteins in maleDrosophila are reviewed. The most prominent feature is the species-specific variability. However, the analysis of the sex peptide inD. melanogaster shows that there is a strong homology in the molecular structure to the closely related sibling species, and that divergence increases with increasing phylogenetic distance. For this reason the sex peptide, after being transferred to the female genital tract during copulation, reduces receptivity and increases oviposition only in virgin females belonging to the same species group and subgroup. Even though studies were hitherto limited to a small number of the secretory components, it is evident that the accessory gland proteins play a key role in reproductive success of the fruit fly by changing female sexual behavior, supporting sperm transfer, storage and displacement. Thus, genes encoding the accessory gland proteins are apparently under strong evolutionary selection.
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  • 61
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    Digitale Medien
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    BioMetals 11 (1998), S. 277-295 
    ISSN: 1572-8773
    Schlagwort(e): evolution ; classification ; EF-hand ; domain ; homology ; chimera ; congruence ; gene duplication ; gene fusion ; eukaryote ; dendrogram ; calmodulin ; troponin C ; light chain of myosin ; S100 ; parvalbumin ; calcineurin ; recoverin ; calpain ; sorcin ; diacylglycerol ; calbindin ; aequorin ; phospholipase C ; BM-40
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Forty-five distinct subfamilies of EF-hand proteins have been identified. They contain from two to eight EF-hands that are recognizable by amino acid sequence as being statistically similar to other EF-hand domains. All proteins within one subfamily are congruent to one another, i.e. the dendrogram computed from one of the EF-hand domains is similar, within statistical error, to the dendrogram computed from another(s) domain. Thirteen subfamilies - including Calmodulin, Troponin C, Essential light chain, Regulatory light chain - referred to collectively as CTER, are congruent with one another. They appear to have evolved from a single ur-domain by two cycles of gene duplication and fusion. The subfamilies of CTER subsequently evolved by gene duplications and speciations. The remaining 32 subfamilies do not show such general patterns of congruence; however, some - such as S100, intestinal calcium binding protein (calbindin 9kd), and trichohylin - do not form congruent clusters of subfamilies. Nearly all of the domains 1, 3, 5, and 7 are most similar to other ODD domains. Correspondingly the EVEN numbered domains of all 45 subfamilies most closely resemble EVEN domains of other subfamilies. Many sequence and chem-ical characteristics do not show systemic trends by subfamily or species of host organisms; such homoplasy is widespread. Eighteen of the subfamilies are heterochimeric; in addition to multiple EF-hands they contain domains of other evolutionary origins.© Kluwer Academic Publishers
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  • 62
    ISSN: 1572-8757
    Schlagwort(e): micropore size distribution ; activated carbon ; adsorption ; desorption ; equilibrium ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract This paper deals with the prediction of adsorption equilibrium and kinetics of hydrocarbons onto activated carbon samples having different micropore size distribution (MPSD). The microporous structure of activated carbon is characterised by the distribution of slit-shaped micropores, which is assumed to be the sole source of surface heterogeneity. The interaction between adsorbate molecule and pore walls is described by the Lennard-Jones potential theory. Different adsorbates have access to different pore size range of activated carbon due to the size exclusion, a phenomenon could have a significant influence on both multicomponent equilibria and kinetics. Activated carbons with three different MPSDs are studied with ethane and propane as the two model adsorbates. The Heterogeneous Macropore Surface Diffusion model (HMSD) is employed to simulate adsorption kinetics. The simulation results show that the MPSD is an important factor affecting both the multicomponent equilibria and kinetics.
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  • 63
    ISSN: 1572-879X
    Schlagwort(e): propane ; oxidation ; platinum ; palladium ; sulfur dioxide ; alumina ; zirconia ; activity ; acidity ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Earlier studies have shown that sulfur dioxide and metal-support interaction can strongly influence propane oxidation over platinum. In particular, oxidation activity is enhanced when platinum is supported on sulfated γ-alumina or zirconia compared to γ-alumina. Therefore, it is of interest to compare the performance of palladium under the same experimental conditions. Four model catalysts were examined: Pt/γ-alumina, Pt/zirconia, Pd/γ-alumina and Pd/zirconia. The metal loading was kept at or below 0.05 wt% to emphasize changes in activity attributable to metal-support interaction. Reaction rates were measured with and without sulfur dioxide. Surface sulfation was analyzed by measuring acid strength and evaluating spectra obtained by Fourier-transform infrared spectroscopy. In contrast to platinum, sulfation does not promote propane oxidation on Pd/γ-alumina, and Pd/zirconia is less active than Pd/γ-alumina.
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  • 64
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    Digitale Medien
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    Catalysis letters 60 (1999), S. 51-57 
    ISSN: 1572-879X
    Schlagwort(e): furfural hydrogenation ; Cu/carbon catalysts ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Furfural hydrogenation over copper dispersed on three forms of carbon – activated carbon, diamond and graphitized fibers – were studied. Only hydrogenation of the C=O bond to form either furfuryl alcohol or 2‐methyl furan occurred at temperatures from 473 to 573 K. Reduction at 573 K gave the most active catalysts, all three catalysts had activation energies of 16 kcal/mol, and turnover frequencies were 0.018–0.032 s-1 based on the number of Cu0 + Cu+ sites, which were counted by N2O adsorption at 363 K and CO adsorption at 300 K, respectively. The Cu/activated carbon catalyst showed no deactivation during 10 h on stream, in contrast to the other two catalysts. A simple Langmuir–Hinshelwood model invoking two types of sites was able to fit all kinetic data quite satisfactorily, thus it was consistent with the presence of both Cu0 and Cu+ sites.
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  • 65
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    Digitale Medien
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    Catalysis letters 60 (1999), S. 167-171 
    ISSN: 1572-879X
    Schlagwort(e): ammonia decomposition ; iron catalyst ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The decomposition of ammonia is a reaction associated with the process of the nitriding of metals. The kinetics of the ammonia decomposition on iron catalysts has been studied using a differential reactor with internal mixing. The balance between the inlet and outlet ammonia quantity has been used to determine the degree of conversion. The rate of ammonia decomposition could be described by the following expression: r = k0 exp (Ea/RT)pNH3. The activation energy of the ammonia decomposition process has been found for samples with potassium as E a= 96 kJ/mol, for samples without potassium as E a= 87 kJ/mol.
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  • 66
    Digitale Medien
    Digitale Medien
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    Minds and machines 6 (1996), S. 463-480 
    ISSN: 1572-8641
    Schlagwort(e): Human reasoning ; evolution ; deontic reasoning ; transitive reasoning ; non-human primates ; neocortical ratio ; dominance hierarchy
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Informatik , Philosophie
    Notizen: Abstract Research from ethology and evolutionary biology indicates the following about the evolution of reasoning capacity. First, solving problems of social competition and cooperation have direct impact on survival rates and reproductive success. Second, the social structure that evolved from this pressure is the dominance hierarchy. Third, primates that live in large groups with complex dominance hierarchies also show greater neocortical development, and concomitantly greater cognitive capacity. These facts suggest that the necessity of reasoning effectively about dominance hierarchies left an indelible mark on primate reasoning architectures, including that of humans. In order to survive in a dominance hierarchy, an individual must be capable of (a) making rank discriminations, (b) recognizing what is forbidden and what is permitted based one's rank, and (c) deciding whether to engage in or refriin from activities that will allow one to move up in rank. The first problem is closely tied to the capacity for transitive reasoning, while the second and third are intimately related to the capacity for deontic reasoning. I argue that the human capacity for these types of reasoning have evolutionary roots that reach deeper into our ancestral past than the emergence of the hominid line, and the operation of these evolutionarily primitive reasoning systems can be seen in the development of human reasoning and domain-specific effects in adult reasoning.
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  • 67
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    Digitale Medien
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    Minds and machines 9 (1999), S. 309-346 
    ISSN: 1572-8641
    Schlagwort(e): language ; grammar ; syntax ; semantics ; evolution ; emergence ; brain size
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Informatik , Philosophie
    Notizen: Abstract It is commonly argued that the rules of language, as distinct from its semantic features, are the characteristics which most clearly distinguish language from the communication systems of other species. A number of linguists (e.g., Chomsky 1972, 1980; Pinker 1994) have suggested that the universal features of grammar (UG) are unique human adaptations showing no evolutionary continuities with any other species. However, recent summaries of the substantive features of UG are quite remarkable in the very general nature of the features proposed. While the syntax of any given language can be quite complex, the specific rules vary so much between languages that the truly universal (i.e. innate) aspects of grammar are not complex at all. In fact, these features most closely resemble a set of general descriptions of our richly complex semantic cognition, and not a list of specific rules. General principles of the evolutionary process suggest that syntax is more properly understood as an emergent characteristic of the explosion of semantic complexity that occurred during hominid evolution. It is argued that grammatical rules used in given languages are likely to be simply conventionalized, invented features of language, and not the result of an innate, grammar-specific module. The grammatical and syntactic regularities that are found across languages occur simply because all languages attempt to communicate the same sorts of semantic information.
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  • 68
    ISSN: 1572-8757
    Schlagwort(e): kinetics ; isotope-exchange ; nitrogen ; adsorption ; methane ; zeolite ; equilibria
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract The Isotope Exchange Technique (IET) was used to simultaneously measure pure and binary gas adsorption equilibria and kinetics (self-diffusivities) of CH4 and N2 on pelletized 4A zeolite. The experiment was carried out isothermally without disturbing the adsorbed phase. CH4 was selectively adsorbed over N2 by the zeolite because of its higher polarizability. The multi-site Langmuir model described the pure gas and binary adsorption equilibria fairly well at three different temperatures. The selectivity of adsorption of CH4 over N2 increased with increasing pressure at constant gas phase composition and temperature. This curious behavior was caused by the differences in the sizes of the adsorbates. The diffusion of CH4 and N2 into the zeolite was an activated process and the Fickian diffusion model described the uptake of both pure gases and their mixtures. The self-diffusivity of N2 was an order of magnitude larger than that for CH4. The pure gas self-diffusivities for both components were constants over a large range of surface coverages (0 〈 θ 〈 0.5). The self-diffusivities of CH4 and N2 from their binary mixtures were not affected by the presence of each other, compared to their pure gas self-diffusivities at identical surface coverages.
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  • 69
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    BioMetals 10 (1997), S. 23-26 
    ISSN: 1572-8773
    Schlagwort(e): aromatic donor molecules ; horseradish peroxidase ; kinetics ; lactoperoxidase
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Based on kinetic evidence, it has been shown for the first time that the mode of binding of aromatic donor molecules is similar in horseradish peroxidase and lactoperoxidase; also that the nature of the heme plays an important role in the reaction with hydrogen peroxide, and has no effect on the reaction of the intermediate compound II with aromatic substrates.
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  • 70
    Digitale Medien
    Digitale Medien
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    Catalysis letters 31 (1995), S. 431-438 
    ISSN: 1572-879X
    Schlagwort(e): partial hydrogenation of benzene ; production of cyclohexene ; kinetics ; reaction mechanism ; ruthenium catalyst
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A method has been developed for direct measurement of reaction rates in a continuously operated slurry (CST-) reactor. In contrast to the usual procedure in a two-liquid-phase system the reactor contains only one liquid phase, an aqueous zinc chloride solution in which a ruthenium lanthanoxide catalyst is suspended. The selectivity of benzene hydrogenation with respect to cyclohexene is higher when the new one-liquid-phase procedure is applied. With decreasing degree of benzene conversion the selectivity with respect to cyclohexene approaches 100%. The conclusion is that cyclohexane is formed only by consecutive hydrogenation of cyclohexene.
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  • 71
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    Catalysis letters 39 (1996), S. 67-71 
    ISSN: 1572-879X
    Schlagwort(e): non-uniform surface ; kinetics ; ethanol ; oxidation ; molybdenum oxide
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Temkin's theory of rates of catalytic reactions on non-uniform surfaces is extended to the MoO3-catalyzed oxidation of ethanol to acetaldehyde. Two types of sites are assumed to be present, an oxygen atom site that can be modeled with uniform properties and a metal atom site characterized by non-uniform properties both for ethanol chemisorption to an ethoxide intermediate and the conversion of this intermediate to acetaldehyde. The rate-limiting step is the cleavage of a C-H bond in the absorbed ethoxide intermediate. Non-uniform surface kinetics leads to a kinetic rate expression of the form $$v = kP_{C_2 H_5 OH}^{1 - m} P_{O_2 }^{(1 - m)/4} P_{H_2 O}^{ - (1 - m)/2} $$ . Such a rate expression, withm=0.14, is shown to provide a good fit to kinetic data for the selective oxidation of ethanol on a silica supported molybdenum oxide catalyst.
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  • 72
    ISSN: 1572-879X
    Schlagwort(e): Ultraviolet heterogeneous photocatalysis ; oxidation ; trichloroethylene ; titania ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Kinetics of the gas/solid heterogeneous photocatalytic oxidation of dilute trichloroethylene (TCE) vapors by ultraviolet-illuminated titanium dioxide have been determined using a fixed-bed dynamic photoreactor. Reaction rate dependences on inlet TCE, oxygen and water vapor concentrations were found to consist of both reactant sensitive and insensitive regions. In the reactant sensitive regions, measured limiting apparent reaction rate orders for TCE, oxygen and water vapor are 0.8, 1.7 and — 3, respectively. Water vapor in the reactant stream lowersinitial reaction rates relative to corresponding water free conditions, but is required to sustain photocatalytic activity for extended periods of time.
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  • 73
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    Catalysis letters 36 (1996), S. 31-36 
    ISSN: 1572-879X
    Schlagwort(e): ethanol ; kinetics ; oxidation ; oxydehydrogenation ; platinum ; structure sensitivity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m−3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m−3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.
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  • 74
    Digitale Medien
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    Catalysis letters 55 (1998), S. 73-77 
    ISSN: 1572-879X
    Schlagwort(e): enantioselectivity ; hydrogenation of ethyl pyruvate ; Pt/alumina catalyst ; solvent effects ; kinetics ; solvent polarity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The influence of solvent on the kinetics of enantioselective hydrogenation of ethyl pyruvate by Pt/Al2O3/dihydrocinchonidine is reported. In a non‐polar solvent, toluene, the reaction is approximately zero order in substrate at constant hydrogen pressure, while under the same conditions and at the same substrate concentration, in the polar solvents ethanol and propylene carbonate the reaction shows a first‐order substrate concentration dependence. Fits to a Michaelis–Menten rate expression show that these differences are the expression of the relative magnitudes of the adsorption term in the rate expression, which in turn reflects the influence of the solvent on the adsorption–desorption processes which take place at the catalyst surface.
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  • 75
    Digitale Medien
    Digitale Medien
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    Catalysis letters 59 (1999), S. 143-149 
    ISSN: 1572-879X
    Schlagwort(e): hydrogen ; desorption ; copper ; activation energy ; kinetics ; order of desorption
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The kinetics of desorption of hydrogen from the copper component of an alumina-supported polycrystalline copper catalyst has been studied in detail by temperature-programmed desorption (TPD). Line-shape analysis of the hydrogen TPD spectra shows: (i) that the desorption is second order, (ii) that the desorption activation energy is in the range 64–68 kJ mol−1 in the coverage range 7–44% of a monolayer, and (iii) that the desorption pre-exponential term has a value ∼10−5 cm2 s−1 atom−1 consistent with the desorption being second order, involving mobile adsorbates and a mobile desorption transition state.
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  • 76
    Digitale Medien
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    Journal for general philosophy of science 21 (1990), S. 231-257 
    ISSN: 1572-8587
    Schlagwort(e): basic rules ; change ; discipline-neutral ; evolution ; analogy
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Philosophie , Wissenschaftskunde und Wissenschaftsorganisation, Hochschul- und Universitätswesen, Museumswissenschaft
    Notizen: Summary A small step is made in the direction of defining some general basic rules which can serve as a framework for research in several fields of the social sciences. The method of working with analogies asks for a more accurate approach. Starting from the concept of evolution in the form of a basic rule another basic rule is formulated. This rule shows what are the most important factors in long term developments and what types of development one can expect.
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  • 77
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    Journal for general philosophy of science 22 (1991), S. 133-141 
    ISSN: 1572-8587
    Schlagwort(e): evolution ; teleology ; chance ; purpose ; anthropomorphism
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Philosophie , Wissenschaftskunde und Wissenschaftsorganisation, Hochschul- und Universitätswesen, Museumswissenschaft
    Notizen: Summary Revaluation of the problem of natural teleology seems an important precondition for elucidating our environmental crisis and for formulating an ‘ecological ethics’, because it calls for a recognition of an intrinsic value in nature and organisms. Therefore, it is necessary to show that the concept of natural teleology is not in contradiction with scientific theories, in particular not with the theory of evolution. In this paper I shall argue that there is a fundamental misunderstanding about the concepts of teleology and chance in modern thinking. This as a result of a radical transformation of the Aristotelian concept of teleology by Christian theologians during the Middle Ages. This confusion resulted in the rejection of teleology from evolution and in an exaggeration of the role of chance. However, not a solution for the problem of teleology is given here, but only an attempt to prove that neither the fossil-record, nor the role of chance in evolution can give adequate arguments for the negation of teleology in evolution. That is not to say that, therefore there exists teleology in evolution, but the problem of teleology in nature cannot, be solved by the scientific theory of evolution, but only be elucidated by philosophical analysis. At the end of the paper it is argued that teleology must be rather presupposed in evolution.
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  • 78
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    Journal for general philosophy of science 23 (1992), S. 85-103 
    ISSN: 1572-8587
    Schlagwort(e): life ; teleology ; evolution ; reality ; representation ; experience
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Philosophie , Wissenschaftskunde und Wissenschaftsorganisation, Hochschul- und Universitätswesen, Museumswissenschaft
    Notizen: Summary A comprehensive definition of the phenomenon called “life” led to the addition of many dimensions to the natural sciences, and especially the conscious mental dimension. Historical attention is paid not only to those employing the natural philosophical paradigms, but also to evolutionary theories and to the Kantian teleological philosophy. The belief that science can solve the riddle of life is a category of purposal thinking. A revised version of critical teleology is essential for comprehension of life.
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  • 79
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    Entomologia experimentalis et applicata 66 (1993), S. 3-12 
    ISSN: 1570-7458
    Schlagwort(e): evolution ; coevolution ; selection ; insect attack ; plant defense ; competition ; enemy free space ; chemoreception ; specialization ; plant recognition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Most hypotheses concerning the evolution of insect-plant relationships are based on the assumptions that, (1) phytophagous insects reduce plant fitness, and that (2) insect-plant relationships are the result of unconstrained selection. It can be shown, however, that there is little evidence to support these assumptions. As an alternative, it is proposed that the evolution of insect-plant relationships results primarily from autonomous evolutionary events; namely from heritable functional changes within the insects' nervous system that determine plant recognition and ultimately host plant specificity. These changes cannot be evoked by selective ecological agents. They originate from intrinsic changes (mutationssensu lato) within the insect genome. Ecological factors play a secondary role: by either supporting or preventing the establishment of the new genotype with the novel food preference.
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  • 80
    ISSN: 1570-7458
    Schlagwort(e): Cryptomyzus ; aphid ; hybridization ; host plant preference ; reproductive performance ; host-alternation ; speciation ; evolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Beschreibung / Inhaltsverzeichnis: Résumé C. galeopsidis Kaltenbach contient plusieurs formes qui ont différentes relations avec des plantes hôtes et des cycles distincts. Des croisements ont permis d'élucider la taxonomie de ces formes et d'étudier l'hérédité de préférences d'hôtes, des performances reproductives et de l'alternance d'hôtes. Une des formes apparaît comme une espèce distincte par suite de la valeur adaptative réduite des hybrides. Les autres formes avec alternance ou non des hôtes sont considérées comme conspécifiques et représentant deux stratégies vitales différentes. Les performances reproductives sont probablement polygéniques puisque les hybrides ont des performances intermédiaires. Les préférences d'hôtes des hybrides montrent certains degrés de dominance et semblent déterminées par quelques gènes seulement. L'alternance des hôtes est envisagée comme ayant une hérédité monofactorielle. Les conséquences sur la spéciation sont discutées.
    Notizen: Abstract The aphid species Cryptomyzus galeopsidis (Kaltenbach) includes several distinct forms which have different host plant relationships and life cycles. Cross breeding was used to elucidate the taxonomic status of these forms and to investigate the inheritance of host preference, reproductive performance and host-alternation. One of the forms appeared to be a distinct species because of the reduced fitness of the hybrids. Other host-alternating and non host-alternating forms are considered conspecific and represent two life cycle strategies. Reproductive performance is probably controlled polygenically, since hybrids show an intermediate performance. Host preference in hybrids showed some degree of dominance and seemed to be determined by only a few genes. Host-alternation is presumed to be inherited monofactorially. The implications for speciation are discussed.
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  • 81
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    Journal for general philosophy of science 30 (1999), S. 37-58 
    ISSN: 1572-8587
    Schlagwort(e): protein ; experimentation ; conceptual variation and selection ; evolution ; Mulder ; Liebig ; Pflüger ; Nägeli
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Philosophie , Wissenschaftskunde und Wissenschaftsorganisation, Hochschul- und Universitätswesen, Museumswissenschaft
    Notizen: Abstract A philosophically comprehended account is given of the genesis and evolution of the concept of protein. Characteristic of this development were not shifts in theory in response to new experimental data, but shifts in the range of questions that the available experimental resources were fit to cope with effectively. Apart from explanatory success with regard to its own range of questions, various other selecting factors acted on a conceptual variant, some stemming from a competing set of research questions, others from an altogether different field of inquiry, and still others from the external environment. These results are best explained on, hence support, an evolutionary model of the progress of experimental investigation, whose outlines are briefly discussed.
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  • 82
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    Minds and machines 6 (1996), S. 481-505 
    ISSN: 1572-8641
    Schlagwort(e): Neuroscience ; evolutionary psychology ; interfield theory ; evolution ; teleology ; function ; functionalism ; brain mapping ; language processing
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Informatik , Philosophie
    Notizen: Abstract The idea of integrating evolutionary biology and psychology has great promise, but one that will be compromised if psychological functions are conceived too abstractly and neuroscience is not allowed to play a contructive role. We argue that the proper integration of neuroscience, psychology, and evolutionary biology requires a telelogical as opposed to a merely componential analysis of function. A teleological analysis is required in neuroscience itself; we point to traditional and curent research methods in neuroscience, which make critical use of distinctly teleological functional considerations in brain cartography. Only by invoking teleological criteria can researchers distinguish the fruitful ways of identifying brain components from the myriad of possible ways. One likely reason for reluctance to turn to neuroscience is fear of reduction, but we argue that, in the context of a teleological perspective on function, this concern is misplaced. Adducing such theoretical considerations as top-down and bottom-up constraints on neuroscientific and psychological models, as well as existing cases of productive, multidisciplinary cooperation, we argue that integration of neuroscience into psychology and evolutionary biology is likely to be mutually beneficial. We also show how it can be accommodated methodologically within the framework of an interfield theory.
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  • 83
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    Biology and fertility of soils 28 (1999), S. 150-155 
    ISSN: 1432-0789
    Schlagwort(e): Key words Phosphorus dynamics ; Olsen ; phosphorus ; Soil phosphorus fractions ; Manure ; Soybean-wheat rotation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie , Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract  Soil P availability and efficiency of applied P may be improved through an understanding of soil P dynamics in relation to management practices in a cropping system. Our objectives in this study were to evaluate changes in plant-available (Olsen) P and in different inorganic P (Pi) and organic P (P0) fractions in soil as related to repeated additions of manure and fertilizer P under a soybean-wheat rotation. A field experiment on a Typic Haplustert was conducted from 1992 to 1995 wherein the annual treatments included four rates of fertilizer P (0, 11, 22 and 44 kg ha–1 applied to both soybean and wheat) in the absence and presence of 16 t ha–1 of manure (applied to soybean only). With regular application of fertilizer P to each crop the level of Olsen P increased significantly and linearly through the years in both manured and unmanured plots. The mean P balance required to raise Olsen P by 1 mg kg–1 was 17.9 kg ha–1 of fertilizer P in unmanured plots and 5.6 kg ha–1 of manure plus fertilizer P in manured plots. The relative sizes of labile [NaHCO3-extractable Pi (NaHCO3-Pi) and NaHCO3-extractable P0 (NaHCO3-P0)], moderately labile [NaOH-extractable Pi (NaOH-Pi) and NaOH-extractable P0 (NaOH-P0)] and stable [HCl-extractable P (HCl-P) and H2SO4/H2O2-extractable P (resisual-P)] P pools were in a 1 : 2.9 : 7.6 ratio. Application of fertilizer P and manure significantly increased NaHCO3-Pi and -P0 and NaOH-Pi, and -P0 fractions and also total P. However, HCl-P and residual-P were not affected. The changes in NaHCO3-Pi, NaOH-Pi and NaOH-P0 fractions were significantly correlated with the apparent P balance and were thought to represent biologically dynamic soil P and act as major sources and sinks of plant-available P.
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  • 84
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    Microchimica acta 119 (1995), S. 13-22 
    ISSN: 1436-5073
    Schlagwort(e): aluminium oxide ; phosphorus ; XRF ; RBS ; FTIR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Phosphorus-doped aluminium oxide thin films were deposited in a flow-type ALE reactor from AlCl3, H2O and from either P2O5 or trimethyl-phosphate. Structural information of the films was obtained from Fourier transform infrared (FTIR) spectra. Rutherford backscattering spectroscopy (RBS) was used to quantitatively determine the composition of the films. The P/Al intensity ratios calculated from X-ray fluorescence (XRF) results were in a linear relation with the P/Al concentration ratios calculated from RBS results. For comparison, the intensity ratios of the phosphorus peak (P=O) at about 1250 cm−1 and the aluminium peak (Al-O) at about 950 cm−1 were determined from the IR absorption spectra. The calibration of FTIR peak intensities was done by plotting the intensity ratios of phosphorus and aluminium peaks against the P/Al concentration ratios measured by RBS. FTIR gave also a linear calibration curve with RBS but the method is less suitable for routine analysis of P/Al ratio than XRF.
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  • 85
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    Microchimica acta 101 (1990), S. 273-279 
    ISSN: 1436-5073
    Schlagwort(e): aluminium analysis ; phosphorus ; sulfur ; chlorine
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Multi-step procedures for the determination of phosphorus, sulfur and chlorine are described and tested against established methods and on reference materials. Phosphorus is separated as hydrogen phosphide, extracted as phosphomolybdic acid, reduced to molydenum blue and measured photometrically (detection limit 0.05 μg/g). Sulfur is separated after reduction as hydrogen sulfide or by means of pyrohydrolysis and measured by ICP-OES (detection limit 0.1 μg/g). Chloride can be measured by ion chromatography after pyrohydrolytic separation (detection limit 0.1 μg/g). The determination of sulfur was also successfully tested on copper and steel samples.
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  • 86
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    Microchimica acta 109 (1992), S. 201-209 
    ISSN: 1436-5073
    Schlagwort(e): phosphonate base scale inhibitor ; brine ; direct current plasma ; inductively coupled plasma atomic emission spectrometry ; phosphorus
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The determination of phosphonate base scale inhibitors in brines by direct current plasma (DCP) and inductively coupled plasma atomic emission spectrometry (ICP-AES) is described. The first method is based on a direct nebulization of the brine samples and plasma using the phosphorus line at 213.618 nm. The second method involves extraction of phosphorus as phospho-antimonyl molybdate complex into methylisobutyl ketone (MIBK) phase and analysis of the extract for molybdenum using the Mo 313.260 nm line. Comparison between the proposed methods and an established recommended method [1] shows excellent agreement between the results in addition to the sensitivity and ease of automation provided by AES.
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  • 87
    ISSN: 1436-5073
    Schlagwort(e): flow injection analysis (FIA) ; mercury ; porphyrin ; kinetics ; spectro-photometry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract 5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine (m-Cl-TPPS4) was synthesized and used for the Spectrophotometric determination of mercury by flow injection analysis. A pseudo-first-order reaction kinetic mechanism was proposed with a rate constant of 0.8 min−1 for Hg(II) withm-Cl-TPPS4 in the presence of 8-hydroxyquinoline in a medium of 1.0M acetic acid and sodium acetate buffer solution (pH 6.22). In the optimum conditions of reaction temperature (85 ° C), stopped-flow time (60 s) and sampling volume (100 μl), the method's relative standard deviation was 0.82% (n = 12) at 5.0 μg ml−1 mercury, with a linear range of 0–12.0 μg ml−1 and an analytical frequency of 60h−1. The detection limit (3σ) was 0.025 μg ml−1. Interference studies showed that most metal ions co-existing with Hg2+ could be tolerated at 100-fold excess levels, but Zn2+, Cu2+ and Mn2+ needed to be masked. The method has been applied to the analysis of water samples with satisfactory results.
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  • 88
    ISSN: 1436-5073
    Schlagwort(e): atrazine ; terbuthylazine ; sequential binding ; kinetics ; cross-reactivity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Immunoassays for triazine herbicides were tested for their reaction to the variation of the tracer incubation time. By application of a sequential technique the measuring range of atrazine could be expanded to five decades and the total duration of the test could be reduced to about 30 min. In an optimized version a lower detection limit of 9 pmol/l (2 ng/l) was achieved. The detection limit of a sensitive immunoassay for terbuthylazine is also below the concentration limit demanded of the German drinking water regulation (100 ng/l) and reaches 130 pmol/l (30 ng/l). Short tracer incubation times did not lead to increased cross-reactivities in contrast to theoretical models [1, 2]. Different mechanisms, which could cause a shift of the center point of the calibration curve, are discussed, including kinetic considerations.
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  • 89
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    Microchimica acta 124 (1996), S. 13-25 
    ISSN: 1436-5073
    Schlagwort(e): kinetics ; rates ; integrating ratemeter ; optimization ; first-order
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The integrating ratemeter is used in concert with the two-rate parameter to form the integrating ratemeter two-rate parameter. Propagation of error theory is applied to the integrating ratemeter two-rate parameter to yield expressions for the precision of rates calculated from the integrating ratemeter two-rate parameter in terms of the precision of the rates measured with the integrating ratemeter. Simulations and experimental results show that in cases where the standard deviation of the rate is relatively constant, the optimum time to make a rate measurement using the integrating ratemeter is also the optimum time to measure either of the rates in the two-rate parameter. If either of the two rates comprising the two-rate parameter is measured at the optimum time, then the precision and accuracy of concentrations measured with this technique are optimized.
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  • 90
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    Biodegradation 4 (1993), S. 163-170 
    ISSN: 1572-9729
    Schlagwort(e): factorial analysis ; kinetics ; methane ; methanotrophs ; nutrients
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Energietechnik , Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract The effect of different mineral nutrients on the kinetics of methane biodegradation by a mixed culture of methanotrophic bacteria was studied. The substrate factors examined were ammonia, iron, copper, manganese, phosphate, and sulphide. The presence of iron in the growth medium had a strong effect on the yield coefficient. Yield coefficients up to 0.49 mg protein per mg methane were observed when iron was added at concentrations of 0.10–5.0 mg/l. Iron addition also increased the maximum methane utilization rate. The same effect was observed after addition of ammonium to a medium where nitrate was the only nitrogen source. The observed Monod constant for methane utilization increased with increasing concentration of ammonia. This shows that ammonia is a weak competitive inhibitor as observed by other researchers. Relatively high levels of both ammonia (70 mg/l) and copper (300 µg/l) inhibited the methane degradation, probably due to the toxic effect of copper-amine complexes.
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  • 91
    ISSN: 1573-0417
    Schlagwort(e): Great Basin ; climatic variations ; productivity ; organic matter ; nitrogen ; phosphorus ; hardwater lake
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie
    Notizen: Abstract Sediment cores from the shallow and deep basins of Pyramid Lake, Nevada, revealed variations in composition with depth reflecting changes in lake level, river inflow, and lake productivity. Recent sediments from the period of historical record indicate: (1) CaCO3 and organic content of sediment in the shallow basin decrease at lower lake level, (2) CaCO3 content of deep basin sediments increases when lake level decreases rapidly, and (3) the inorganic P content of sediments increases with decreasing lake volume. Variations in sediment composition also indicate several periods for which productivity in Pyramid Lake may have been elevated over the past 1000 years. Our data provide strong evidence for increased productivity during the first half of the 20th Century, although the typical pattern for cultural eutrophication was not observed. The organic content of sediments also suggests periods of increased productivity in the lake prior to the discovery and development of the region by white settlers. Indeed, a broad peak in organic fractions during the 1800's originates as an increase starting around 1600. However, periods of changing organic content of sediments also correspond to periods when inflow to the lake was probably at extremes (e.g. drought or flood) indicating that fluctuations in river inflow may be an important factor affecting sediment composition in Pyramid Lake.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 92
    ISSN: 1573-0417
    Schlagwort(e): colonization ; evolution ; lakes ; Norway ; deglaciation ; land uplift ; invertebrates ; Chironomidae ; Porifera ; Bryozoa ; diatoms ; Charophyta ; tsunami
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie
    Notizen: Abstract Invertebrate colonization of lakes following the uplift of land from the sea was studied in four lakes, currently situated between 39 and 24 m a.s.l., on the central Norwegian coast. The lakes were isolated from the sea between 9500 and 7700 years B.P. Animal and algal remains picked from core samples showed that the first colonizers preserved as fossils were usually members of the Chironomidae, Daphnidae/Chydoridae, Acarina, Porifera (Ephydatia mülleri and Spongilla lacustris), Bryozoa (Cristatella mucedo and Plumatella spp.) and Charophyta (Chara sp.). Of the chironomids, the genus Chironomus was present in the oldest lacustrine layers of all four lakes, but other genera recorded at the marine/lacustrine boundary were Dicrotendipes, Procladius (?), Einfeldia, Microtendipes, and Glyptotendipes. Remains of the caddis fly family Limnephilidae were also present in the earliest lacustrine sediments in Kvennavatnet and Kvernavatnet. The oldest invertebrate fauna is typical for mesotrophic lakes. However, chironomids and mites have been present in this area from at least about 10 500 years B.P. A diverse chironomid community was established between 300 and 800 years after isolation from the sea at Kvernavatnet on the island of Hitra, while only between 80 and 120 years passed before a comparably diverse community developed at Kvennavatnet on the mainland coast. A similar development of the invertebrate fauna occurred in Kvennavatnet, Kvernavatnet and Storkuvatnet. However, Litjvatnet deviates greatly from the ‘normal’ pattern because a tsunami disturbed the bottom sediments and fauna. The tsunami, a gigantic sea wave, was caused by a submarine slide from the Norwegian continental slope. It reached Litjvatnet, today located 24 m a.s.l., but was not traced in Storkuvatnet at 30 m a.s.l. This event happened about 7200 years B.P.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 93
    Digitale Medien
    Digitale Medien
    Springer
    Journal of paleolimnology 10 (1994), S. 43-52 
    ISSN: 1573-0417
    Schlagwort(e): Charophyta ; evolution ; gyrogonite morphology ; ecology-paleoecology ; Argentina ; South America
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie
    Notizen: Abstract Charophyta are common algae in limnic waters from many regions and are an interesting group from an evolutionary point-of-view, as they are believed to be related to the Chlorophyceae and land plants. Paleontological-botanical systematics are discussed, taking into consideration some new advances. Charophytes live in all types of inland waters and are sensitive to ecological change, and so they are very useful paleolimnological markers. Gaps concerning gyrogonite morphology in extant taxa and their responses to different environmental conditions must be described. This paper discusses data concerning ecological factors affecting the distribution of Argentinian Charophyta (principally distributed between 30°S and 40°S), gyrogonite morphology related to different ecological conditions, and the way that Charophyta can modify the environment.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 94
    ISSN: 1573-0417
    Schlagwort(e): diatoms ; eutrophication ; lake management ; paleolimnology ; British Columbia ; lakes ; phosphorus ; training sets
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie
    Notizen: Abstract Eighteen lakes were added to a published training set of 46 British Columbia (BC) lakes in order to expand the original range of total phosphorus (TP) concentrations. Canonical correspondence analysis (CCA) was used to analyze the relationship between diatom assemblages and environmental variables. Specific conductivity and [TP] each explained significant (P≤0.05) directions of variance in the distribution of the diatoms. The relationship between diatom assemblages and [TP] was sufficiently strong to warrant the development of a weighted-averaging (WA) regression and calibration model that can be used to infer past trophic status from fossil diatom assemblages. The relationship between observed and inferred [TP] was not improved by the addition of more eutrophic lakes, however the [TP] range and the number of taxa used in the transfer function are now superior to the original model. Diatom species assemblages changed very little in lakes with TP concentrations greater than 85 µg 1−1, so we document the development of a model containing lakes with TP≤85 µg 1−1. The updated model uses 59 training lakes and covers a range of species optima from 6 to 41.9 µg 1−1 TP, and a total of 150 diatom taxa. The updated inference model provided a more realistic reconstruction of the anthropogenic history of a highly eutrophic BC lake. The model can now be used to infer past nutrient conditions in other BC lakes in order to assess changes in trophic status.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 95
    Digitale Medien
    Digitale Medien
    Springer
    Journal of paleolimnology 20 (1998), S. 47-55 
    ISSN: 1573-0417
    Schlagwort(e): diatoms ; spatial variability ; canonical correspondence analysis ; lake eutrophication ; transfer functions ; phosphorus
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie
    Notizen: Abstract Diatom analyses were undertaken of sediment cores covering a range of water depths in a small eutrophic lake (Lough Augher, Co. Tyrone, N. Ireland). The significance of between-core variability in diatom relative frequency stratigraphy was assessed by Canonical Correspondence Analysis (CCA) where the ordination axes were constrained to external environmental variables (sediment depth, core location coordinates, water depth, effective fetch, distance-from-shore and distance-from-inflow). After the removal of the effect of sediment age by partialling it out, the resultant first two axes from the partial-CCA were significantly correlated with water depth and distance-from-shore, indicating non-uniform diatom stratigraphies across the lake. Despite this variability, all cores show the same succession of species and, therefore, record the eutrophication of the lake. Diatom-inferred total phosphorus (DI-TP) was inferred for six cores using weighted averaging regression and calibration. Apart from considerable differences of DI-TP in surficial sediment samples, there was good between-core repeatability of DI-TP profiles. These data support the use of DI-TP for establishing background nutrient concentrations for lakes, and associated implications for lake restoration schemes using single cores. Comparisons of DI-TP profiles and total diatom accumulation rate data for the individual cores indicate that diatom production peaked prior to the maximum TP concentrations in the lake.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 96
    ISSN: 1573-0417
    Schlagwort(e): carbon isotopes ; diatoms ; lake management ; nitrogen isotopes ; phosphorus ; radium-226 ; sediments ; trophic state
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie
    Notizen: Abstract We explored the use of carbon and nitrogen isotopes (δ13C and δ15N) in sedimented organic matter (OM) as proxy indicators of trophic state change in Florida lakes. Stable isotope data from four 210Pb-dated sediment cores were compared stratigraphically with established proxies for historical trophic state (diatom-inferred limnetic total phosphorus, sediment C/N ratio) and indicators of cultural disturbance (sediment total P and 226Ra activity). Diatom-based limnetic total P inferences indicate a transition from oligo-mesotrophy to meso-eutrophy in Clear Lake, and from eutrophy to hypereutrophy in Lakes Parker, Hollingsworth and Griffin. In cores from all four lakes, the carbon isotopic signature of accumulated OM generally tracks trophic state inferences and cultural impact assessments based on other variables. Oldest sediments in the records yield lower diatom-inferred total limnetic P concentrations and display relatively low δ13C values. In the Clear, Hollingsworth and Parker records, diatom-inferred nutrient concentrations increase after ca. AD 1900, and are associated stratigraphically with higher δ13C values in sediment OM. In the Lake Griffin core, both proxies display slight increases before ~1900, but highest values occur over the last ~100 years. As Lakes Clear, Hollingsworth and Parker became increasingly nutrient-enriched over the past century, the δ15N of sedimented organic matter decreased. This reflects, in part, the increasing relative contribution of nitrogen-fixing cyanobacteria to sedimented organic matter as primary productivity increased in these waterbodies. The Lake Griffin core displays a narrow range of both δ13C and δ15N values. Despite the complexity of carbon and nitrogen cycles in lakes, stratigraphic agreement between diatom-inferred changes in limnetic total P and the stable isotope signatures of sedimented OM suggests that δ13C and δ15N reflect shifts in historic lake trophic state.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 97
    ISSN: 1573-0417
    Schlagwort(e): diatoms ; Everglades ; phosphorus ; wetland ; calibration ; multivariate ; Florida
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie
    Notizen: Abstract The relationship between diatom taxa preserved in surface soils and environmental variables at 31 sites in Water Conservation Area 2A (WCA-2A) of the Florida Everglades was explored using multivariate analyses. Surface soils were collected along a phosphorus (P) gradient and analyzed for diatoms, total P, % nitrogen (N), %carbon (C), calcium (Ca), and biogenic silica (BSi). Phosphorus varied from 315-1781 μg g-1, and was not found to be correlated with the other geochemical variables. Canonical correspondence analysis (CCA) was used to examine which environmental variables correlated most closely with the distributions in diatom taxa. Canonical correspondence analysis with forward selection, constrained and partial CCA, and Monte Carlo permutation tests of significance show the most significant changes in diatom assemblages along the P gradient (p 〈 0.01), with additional species differences correlated with soil C, N, Ca, and BSi. Weighted-averaging (WA) regression and calibration models of diatom assemblages to P and BSi were developed. The diatom-based inference model for soil [P] had a high apparent r2 (0.86) with RMSEboot = 218 μg g-1. Indicator diatom species identified by assessing species WA optima and WA tolerance to [P], such as Nitzschia amphibia and N. palea for high [P] (~1300-1400 μ g-1) and Achnanthes minutissima var. scotica and Mastogloia smithii for low [P] (~400-600 μg g-1), may be useful as monitoring tools for eutrophication in WCA-2A as well as other areas of the Everglades. Diatom assemblages analyzed by cluster analysis were related to location within WCA-2A, and dominant taxa within clusters are discussed in relation to the geochemical variables measured as well as hydrology and pH. Diversity of diatom assemblages and a ‘Disturbance Index’ based on diatom data are discussed in relation to the historically P-limited Everglades ecosystem. Diatom assemblages should be very useful for reconstructions of [P] through time in the Florida Everglades, provided diatoms are well preserved in soil cores.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 98
    Digitale Medien
    Digitale Medien
    Springer
    Journal of paleolimnology 10 (1994), S. 53-58 
    ISSN: 1573-0417
    Schlagwort(e): Charophyta ; evolution ; gyrogonite morphology ; ecology-paleoecology ; Argentina ; South America
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie
    Notizen: Abstract The Pleistocene charophytes from Arroyo Perucho Verna, Province of Entre Ríos, were analyzed.Chara contraria Br. ex Kütz.,C. contraria var.longilinea Cáceres,C. globularis Thuill. andTolypella intricata (Trent. ex Roth.) Leonh. var.apiculata (A. Br.) Wood were described and illustrated with scanning electron microscope. The assemblage indicates fresh alkaline to slightly saline waters, not very deep, in a lentic or sometimes lotic environment. Extant assemblages provide data for this paleoecological reconstruction.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 99
    Digitale Medien
    Digitale Medien
    Springer
    Journal of paleolimnology 20 (1998), S. 31-46 
    ISSN: 1573-0417
    Schlagwort(e): phosphorus ; Lake Okeechobee ; lead-210 dating ; eutrophication ; phosphorus loading
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie
    Notizen: Abstract Phosphorus accumulation rates in depositional zone sediments of Lake Okeechobee were determined in 11 mud-zone cores and two peat-zone cores dated by 210Pb. Although difficulties were encountered in interpreting 210Pb data from some sites, reliable dating of sediments from the mud zone of this shallow lake is possible. Sediment accumulation rates in this zone have increased during the present century by an average of about twofold, and accumulation of organic sediments in the lake during pre-settlement times apparently was much slower than during the past century. Concentrations of all forms of sedimentary P but especially nonapatite inorganic-P and organic-P also have increased since pre-settlement times and especially since about 1940. Annual P accumulation rates in the lake's sediments have increased about fourfold during the 1900s, with most of the increase occurring in the past 40–50 years. The recent accumulation rate of sedimentary P (past ~ 10 years) agrees within a factor of 1.5 with the net retention of P in the lake calculated from published input-output mass balances.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 100
    Digitale Medien
    Digitale Medien
    Springer
    Nutrient cycling in agroecosystems 36 (1993), S. 127-133 
    ISSN: 1573-0867
    Schlagwort(e): hydrology ; water balance ; phosphorus ; Streamflow ; Peel-Harvey
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract This paper discusses the land types, hydrologic characteristics and processes, and the major modification of these, in relation to mechanisms and magnitude of phosphorus losses to drains and riverine systems which discharge to the Peel-Harvey estuary. About 75% of the coastal plain part of the catchment is cleared of native vegetation and used for dryland, dairy and beef grazing. There are small areas devoted to irrigated pasture and commercial horticulture. Seventy-five percent of the soils of the catchment are sandy surfaced with a poor capacity to retain phosphorus. Though the area is flat, catchment water yields are high because of a large winter rainfall excess and low soil storage capacity. Drainage schemes have been constructed in much of the catchment to remove excess water quickly. This was required initially to allow agricultural expansion and is now important for protecting a growing infrastructure which serves the most populous region of Western Australia.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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