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  • Articles  (193)
  • evolution  (102)
  • kinetics  (91)
  • Springer  (193)
  • American Chemical Society
  • 1995-1999  (193)
  • 1997  (118)
  • 1995  (75)
  • 1
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    Entomologia experimentalis et applicata 82 (1997), S. 37-44 
    ISSN: 1570-7458
    Keywords: Barbarea vulgaris ; Cruciferae ; Phyllotreta nemorum ; Chrysomelidae ; Alticinae ; flea beetle ; plant defence ; genetics ; sex-linkage ; X- and Y-chromosome ; evolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: 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.
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  • 2
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    Entomologia experimentalis et applicata 82 (1997), S. 25-35 
    ISSN: 1570-7458
    Keywords: Barbarea vulgaris ; Cruciferae ; Phyllotreta nemorum ; Chrysomelidae ; Alticinae ; flea beetle ; plant defence ; resistance ; host plant ; variation ; evolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: 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.
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  • 3
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    Adsorption 1 (1995), S. 133-151 
    ISSN: 1572-8757
    Keywords: PSA process ; sensitivity ; equilibria ; kinetics ; heats
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: 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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  • 4
    ISSN: 1572-8757
    Keywords: characterisation ; equilibria ; kinetics ; micropore size distribution ; n-butane ; nutshell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: 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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  • 5
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    Cellulose 4 (1997), S. 1-5 
    ISSN: 1572-882X
    Keywords: paper ; degradation ; ageing ; kinetics ; modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
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  • 6
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    Cellular and molecular life sciences 51 (1995), S. 454-464 
    ISSN: 1420-9071
    Keywords: Quantitative genetics ; life history ; evolution ; cladocera ; heritability ; Daphnia ; zooplankton
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: 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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  • 7
    ISSN: 1572-8773
    Keywords: aromatic donor molecules ; horseradish peroxidase ; kinetics ; lactoperoxidase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: 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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  • 8
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    Catalysis letters 31 (1995), S. 431-438 
    ISSN: 1572-879X
    Keywords: partial hydrogenation of benzene ; production of cyclohexene ; kinetics ; reaction mechanism ; ruthenium catalyst
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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  • 9
    ISSN: 1573-0417
    Keywords: colonization ; evolution ; lakes ; Norway ; deglaciation ; land uplift ; invertebrates ; Chironomidae ; Porifera ; Bryozoa ; diatoms ; Charophyta ; tsunami
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: 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.
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  • 10
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    Antonie van Leeuwenhoek 71 (1997), S. 159-178 
    ISSN: 1572-9699
    Keywords: aromatic pathways ; chlorobenzenes ; evolution ; genes ; plasmids ; pseudomonas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Chlorobenzenes are substrates not easily metabolized by existing bacteria in the environment. Specific strains, however, have been isolated from polluted environments or in laboratory selection procedures that use chlorobenzenes as their sole carbon and energy source. Genetic analysis indicated that these bacteria have acquired a novel combination of previously existing genes. One of these gene clusters contains the genes for an aromatic ring dioxy-genase and a dihydrodiol dehydrogenase. The other contains the genes for a chlorocatechol oxidative pathway. Comparison of such gene clusters with those from other aromatics degrading bacteria reveals that this process of recombining or assembly of existing genetic material must have occurred in many of them. Similarities of gene functions between pathways suggest that incorporation of existing genetic material has been the most important mechanism of expanding a metabolic pathway. Only in a few cases a horizontal expansion, that is acqui sition of gene functions to accomodate a wider range of substrates which are then all transformed in one central pathway, is observed on the genetic level. Evidence is presented indicating that the assembly process may trigger a faster divergence of nearby gene sequences. Further ‘fine-tuning’, for example by developing a proper regulation, is then the next step in the adaptation.
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  • 11
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    Antonie van Leeuwenhoek 71 (1997), S. 265-270 
    ISSN: 1572-9699
    Keywords: bacteria ; DNA ; evolution ; genome ; RNA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract This review examines evolution of bacterial genomes with an emphasis on RNA based life, the transition to functional DNA and small evolving genomes (possibly plasmids) that led to larger, functional bacterial genomes.
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  • 12
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    Antonie van Leeuwenhoek 71 (1997), S. 257-263 
    ISSN: 1572-9699
    Keywords: bacteria ; energy ; evolution ; genome ; metabolism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract This article examines the relationship between (or dependence of) bacterial evolution in prokaryotes and metabolism, and the changing physical-chemical conditions present during early evolution.
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  • 13
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    Antonie van Leeuwenhoek 71 (1997), S. 363-368 
    ISSN: 1572-9699
    Keywords: assembly ; anode ; bacteria ; cathode ; DNA ; evolution ; genetics ; molecular ; surfaces
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Molecular evolution is examined in bacteria with an emphasis on mineral surfaces, membranes, cathodes and anodes. In early molecular evolution, cathode-anode system may have been naturally occurring on a nm to µm scale. Secondly, the cathode-anode system could have been separated by a primitive, permeable lipid or microsphere on a mineral surface, that was a precursor of a more advanced membrane with a charge differential on either side of the membrane. These aspects will be considered from a theoretical evolutionary perspective.
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  • 14
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    Antonie van Leeuwenhoek 72 (1997), S. 251-259 
    ISSN: 1572-9699
    Keywords: bacteria ; catalysis ; DNA ; enzyme ; evolution ; microorganisms ; optimization ; RNA ; time
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Microbial populations (and life) not only evolve, they optimize. The transition from a random, unorganized, lifeless Earth to the present situation, where the Earth is virtually covered with nucleic acids and diverse and complex species, required numerous molecular changes and the integration of metabolic pathways over billions of years. Primitive prokaryotic life was dependent on and constrained by the physical-chemical conditions on the Earth, while slowly reshaping conditions present. In this review, molecular evolution and molecular optimization are examined with an emphasis on the order in which evolutionary events occurred.
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  • 15
    ISSN: 1572-9729
    Keywords: bacteria ; degradation ; denitrification ; kinetics ; stoichiometry ; toluene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Batch experiments were carried out to investigate the stoichiometry and kinetics of microbial degradation of toluene under denitrifying conditions. The inoculum originated from a mixture of sludges from sewage treatment plants with alternating nitrification and denitrification. The culture was able to degrade toluene under anaerobic conditions in the presence of nitrate, nitrite, nitric oxide, or nitrous oxide. No degradation occurred in the absence of Noxides. The culture was also able to use oxygen, but ferric iron could not be used as an electron acceptor. In experiments with14C-labeled toluene, 34%±8% of the carbon was incorporated into the biomass, while 53%±10% was recovered as14CO2, and 6%±2% remained in the medium as nonvolatile water soluble products. The average consumption of nitrate in experiments, where all the reduced nitrate was recovered as nitrite, was 1.3±0.2 mg of nitrate-N per mg of toluene. This nitrate reduction accounted for 70% of the electrons donated during the oxidation of toluene. When nitrate was reduced to nitrogen gas, the consumption was 0.7±0.2 mg per mg of toluene, accounting for 97% of the donated electrons. Since the ammonia concentration decreased during degradation, dissimilatory reduction of nitrate to ammonia was not the reductive process. The degradation of toluene was modelled by classical Monod kinetics. The maximum specific rate of degradation, k, was estimated to be 0.71 mg toluene per mg of protein per hour, and the Monod saturation constant, K s , to be 0.2 mg toluene/l. The maximum specific growth rate, μ max , was estimated to be 0.1 per hour, and the yield coefficient, Y, was 0.14 mg protein per mg toluene.
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  • 16
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    Insectes sociaux 42 (1995), S. 57-69 
    ISSN: 1420-9098
    Keywords: Hindgut ; alkalinity ; evolution ; symbionts ; gut morphology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The pH of the gut contents was measured in 52 species of higher termites (Termitidae), representing 36 genera in all four subfamilies. A statistically significant trend was shown from lower termites with low mean gut pH through to the Termitinae with higher mean gut pHs. Elevation of the pH occurred principally in the first and third proctodaeal segments, reaching values as high as 10.5 in 8 soil-feeding genera and 1 wood-feeding genus of Termitinae. Elevation of gut pH within the Termitidae appears to be independent of the general nature of the feeding substrate.
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  • 17
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    European journal of clinical pharmacology 52 (1997), S. 505-506 
    ISSN: 1432-1041
    Keywords: Key words Ibuprofen; effervescent tablets ; kinetics ; bioavailability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
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  • 18
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    Ecological research 10 (1995), S. 321-325 
    ISSN: 1440-1703
    Keywords: body temperature ; brood parasitism ; cuckoo ; evolution ; telemetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Body temperatures of 11 bird species, including cuckoos, were measured in an artificial meteorological room. Ratios of change in body temperature to that in air temperature were thereby obtained for each species. Cuckoos demonstrate a remarkably high value, indicating a particularly low ability to regulate body temperature. Viewed in this light, the cuckoo's parasitic behavior is very likely an adaptation to overcome a physiological disadvantage. This in turn might be expected to reinforce delay in evolution of temperature homeostasis.
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  • 19
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    Journal of thermal analysis and calorimetry 48 (1997), S. 917-923 
    ISSN: 1572-8943
    Keywords: copper compound ; coupled technique ; kinetics ; macrocyclic complex ; non-isothermal
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition process of the complex [Cu(NBOCTB)][Cu(NO3)4] H2O has been studied by TG and DTG technique, and possible intermediates of the thermal decomposition have also been conjectured from the TG and DTG curves. The results suggest that the decomposition of the complex involves five steps: The non-isothermal kinetics of steps 1, 2 and 3 have been studied by means of the Achar and Coats-Redfern method based on TG and DTG curves. Step 1 is a ‘Coring and Growth’ mechanism (n= 1), its kinetic equation may be expressed as: dα/dt=Ae−E/RT(1−α). Steps 2 and 3 are both ‘two order chemical reaction’ mechanisms, their kinetic equations can be expressed as: dα/dt=Ae−E/RT(1−α)2.
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  • 20
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    Journal of thermal analysis and calorimetry 49 (1997), S. 87-94 
    ISSN: 1572-8943
    Keywords: kinetics ; poly(di-propyl itaconates) ; polymer structure ; thermal degradation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Non-isothermal thermogravimetry was performed in a dynamic nitrogen atmosphere, on a series of poly(di-n-propyl itaconates) (PDnPI) and poly(di-iso-propyl itaconates) (PDiPI) which had been prepared in the presence of various amounts of the chain transfer agentn-dodecyl mercaptan (DDM). Differential thermogravimetry (DTG) showed that both polymers degraded in two stages. The DTG curve of PDnPI had a large first peak followed by a smaller shoulder, whereas the DTG curve of PDiPI was composed of two peaks of almost equal heights. The addition of DDM during the polymerisations in both cases resulted in a similar decrease in the relative area of the first peak.
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  • 21
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    Journal of thermal analysis and calorimetry 49 (1997), S. 183-191 
    ISSN: 1572-8943
    Keywords: kinetics ; thermooxidative degradation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The results of non-isothermal kinetic analysis of the thermooxidative degradation in air and oxygen of an unsaturated polyester resin are presented. It has been shown that the thermooxidative degradation in oxygen occurs at lower temperatures than the thermooxidative degradation in air. The kinetic parameters of the thermooxidative degradation depend on the heating rate and the oxygen pressure. Two straight lines of InAvs. E (A is the preexponential factor andE is the activation energy), characteristic for the compensation effect, have been obtained for the thermooxidative degradation in air and in oxygen respectively. The difference between the intercepts of these straight lines can be explained by dependence of the pre-exponential factor on the oxygen pressure.
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  • 22
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    Journal of thermal analysis and calorimetry 49 (1997), S. 857-862 
    ISSN: 1572-8943
    Keywords: analytical methods ; kinetics ; powder milk ; temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This work present comparative results on powder milk storage quality, obtained from analytical methods. Protein content was determined conventional (Kjeldahl) and colorimetric with biuret reagent at 540 nm and integral quality by thermogravimetric and biological methods. A method was developed for the protein separation of powder milk. Powder milk was submitted to degradation processes at 45, 60 and 80°C for 20 days. The results indicated that protein content values were inconsistent if determinations by Kjeldahl and colorimetric methods and biological tests were compared. There is evidence of thermal decomposition of powder milk as detected by biological and thermogravimetric methods.
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  • 23
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    Journal of thermal analysis and calorimetry 49 (1997), S. 937-941 
    ISSN: 1572-8943
    Keywords: kinetics ; mebendazole ; quality control ; technology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A study was made of the thermal behavior of the starting materials, their mixtures and the resulting mebendazole tablets. The thermal curves were obtained with a Shimadzu thermobalance, model TGA-50, using an air flow of 50 mL min−1 and a heating rate of 10°C min−1 in the temperature interval 30–900°C. The reaction constant velocities for the mebendazole salt and tablets were determined isothermally, using the Arrhenius expression. The thermal stability of mebendazole tablets is lower than that of the mebendazole salt, due to the presence of starch and lactose in the composition. Analysis of the data reveals that thermogravimetry is a powerful tool in pharmaceutical technology and quality control.
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  • 24
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    Journal of thermal analysis and calorimetry 48 (1997), S. 343-348 
    ISSN: 1572-8943
    Keywords: activation energy ; combustion ; crude oil ; differential scanning calorimetry ; kinetics ; thermogravimetric analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A weighted mean activation energy method was applied to describe the reactivity and combustibility of crude oils via simultaneous TG/DTG. Thermal experiments were conducted with a non-isothermal method at a heating rate of 10
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  • 25
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    Journal of thermal analysis and calorimetry 48 (1997), S. 385-401 
    ISSN: 1572-8943
    Keywords: dehydration and decomposition ; kinetics ; Fe(III) chloride
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Fe(III) chloride hydrate (FeCl3·xH2O) undergoes simultaneous dehydration and dehydrochlorination from its molten phase in the temperature range 100–200
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  • 26
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    Journal of thermal analysis and calorimetry 48 (1997), S. 413-425 
    ISSN: 1572-8943
    Keywords: alcoholic fermentation ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The control of alcoholic fermentation is necessary to obtain a quality wine. The overall dynamic and phenomenological modelling already applied to the simulation of this type of reaction enables us to suggest, in this study, a simple model (of which two variants), are relatively satisfactory. The first variant does not take into account the variation of the ambient temperature; the model translates exactly the first phase of the experimental curve or the moment when highest temperatures are measured. The relaxation phase is less well described because of influence of variation of the ambient temperature is relatively important. The second one considers the system depending on the ambient temperature, the model is correct for the relaxation phase too (the reaction temperature decreases, it nears the ambient temperature). The advantage of this model: It permits one to determine the reaction enthalpy and the kinetic parameters.
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  • 27
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    Journal of thermal analysis and calorimetry 48 (1997), S. 623-634 
    ISSN: 1572-8943
    Keywords: bismalleimide/carbon fiber composite ; DMA ; kinetics ; TSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The correlation between structure/microstructure and thermomechanical properties has been investigated by the Thermally Stimulated Creep (TSC) technique in a high performance thermostable thermoset matrix composite. The high resolving power of this technique allows us to analyse the α retardation mode. The kinetics of molecular movements liberated at the glass transition has been investigated by the technique of fractional loading: the analysis of each elementary process gives the real compliance and the retardation time as a function of temperature. The values of the activation parameters show the existence of a compensation phenomenon which characterizes the microstructure. It also gives access to the loss compliance of the composite material as a function of temperature and frequency. The predictive calculation of loss compliance has been validated by the results obtained by dynamic mechanical analysis (DMA).
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    Journal of thermal analysis and calorimetry 48 (1997), S. 769-782 
    ISSN: 1572-8943
    Keywords: kinetics ; non-linear optimization ; reactor time constants ; software ; time constants of sensors
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract All temperature sensors have a finitely time constant. The influence of the sensor time constant gts on the results of kinetic evaluation is demonstrated at four reaction types. The ignorance of the sensor indolence gives incorrect activation parameters. Therefore the determination of Τs is necessary. For the estimation of parameters the nonlinear evaluation program TA-kin was used. With its help it is possible to find the real parameters, also when Τs=32 s, if the real Τs-value was entered.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1517-1525 
    ISSN: 1572-8943
    Keywords: β-cyclodextrin ; cinnamyl alcohol ; kinetics ; thermal analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The stability of β-cyclodextrin-cinnamyl alcohol inclusion complex (β-CD·C9H10·8H2O) was investigated using TG and DSC. The mass loss took place in three stages: the dehydration occurred between 50–120°C; the dissociation of β-CD·C9H10O occurred in the range of 210–260°C; and the decomposition of β-CD began at 280°C. The dissociation of β-CD·C9H10O was studied by means of thermogravimetry, and the results showed: the dissociation of β-CD·C9H10O was dominated by a two-dimensional diffusion process (D2). The activation energyE was 161.2 kJ mol−1, the pre-exponential factorA was 4.5×1013 min−1. Cyclodextrin is able to form inclusion complexes with a great variety of guest molecules, and the interesting of studies focussed on the energy binding cyclodextrin and the guest molecule. In this paper, β-cyclodextrin-cinnamyl alcohol inclusion complex was studied by fluorescence spectrophotometry and infrared absorption spectroscopy, and the results show: the stable energy of inclusion complexes of β-CD with weakly polar guest molecules consists mainly of Van der Waals interaction.
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  • 30
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1553-1564 
    ISSN: 1572-8943
    Keywords: deconvolution ; differential scanning calorimetry ; feedforward neural networks ; kinetics ; signal filtering ; simulations ; thermal analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Feedforward neural networks have been used for kinetic parameters determination and signal filtering in differential scanning calorimetry. The proper learning function was chosen and the network topology was optimized, using an empiric procedure. The learning process was achieved using simulated thermoanalytical curves. The resilient-propagation algorithm have led to the best minimization of the error computed over all the patterns. Relative errors on the thermodynamic and kinetic parameters were evaluated and compared to those obtained with the usual thermal analysis methods (single scan methods). The errors are much lower, especially in presence of noisy signals. Then, our program was adapted to simulate thermal effects with known thermodynamic and kinetic parameters, generated electrically, using a PC computer and an electronic interface on the serial port. These thermal effects have been generated by using an inconel thread.
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  • 31
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1467-1475 
    ISSN: 1572-8943
    Keywords: CRTA ; DSC ; kinetics ; synthetic brochantite ; TG-DTA ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The reaction pathway of the thermal decomposition of synthetic brochantite, Cu4(OH)6SO4, to copper(II) oxide was investigated through the detailed kinetic characterization of the thermal dehydration and desulferation processes. The dehydration process was characterized by dividing into two overlapped kinetic processes with a possible formation of an intermediate compound, Cu4O(OH)4SO4. The dehydrated sample, Cu4O3SO4, was found first to be amorphous by means of XRD, followed by the crystallization to a mixture of CuO and CuO-CuSO4 at around 776 K. The specific surface area and the crystallization behaviour of the amorphous dehydrated compound depend largely on the dehydration conditions. The thermal desulferation process is influenced by the gross diffusion of the gaseous product SO3, which is governed by the advancement of the overall reaction interface from the top surface of the sample particle assemblage to the bottom.
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  • 32
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    Journal of thermal analysis and calorimetry 50 (1997), S. 455-462 
    ISSN: 1572-8943
    Keywords: kinetics ; statistical analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A statistical technique based on the Wilcockson criterion is suggested for estimation of the reproducibility of thermoanalytical experiments. Reduction of the whole physicochemical process to a quasi-one-stage process is described.
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  • 33
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    Journal of thermal analysis and calorimetry 50 (1997), S. 425-430 
    ISSN: 1572-8943
    Keywords: decomposition ; kinetics ; non-isothermal
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The authors present the results concerning the thermal behaviour of three polynuclear coordination compounds of Nd(III) and Co(II) or Fe(III) with triptophan. For the dehydration steps the values of the non-isothermal kinetic parameters have been determined.
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  • 34
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1227-1241 
    ISSN: 1572-8943
    Keywords: inorganic sulphates ; kinetics ; mechanism ; thermodynamics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal decomposition of different inorganic sulphates are presented. A number of techniques, but mainly TG and DTA, are used to prove the mechanism and kinetics of CaSO4, BaSO4, FeSO4·xH2O, Al2(SO4)3·xH2O under various gas atmospheres. It is shown how the partial pressure of gas components and heating rate may effect the mechanism and kinetic parameters. There are also examples on the effects of some additives and initial treatment on the thermal processes. On the base of the results obtained some recommendations are given concerning the precautions to be taken into account in the thermal decomposition studies and the sulphur recovering.
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  • 35
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1477-1484 
    ISSN: 1572-8943
    Keywords: CRTA ; kinetics ; particle size distribution ; rate jump method
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetic curves at infinite temperature for the solid-state reactions of the interface shrinkage type were drawn theoretically by taking account the particle size distribution in the sample mixture. The CRTA curves for the reactions with the particle size distribution can be drawn by utilizing the universal kinetic curves at infinite temperature. The proper kinetic treatment for the CRTA curves with the particle size distribution is discussed in connection with the property of the kinetic equation with respect to the particle size distribution. The present kinetic consideration is taken as a simulation for the reactions with a certain distribution in α among the reactant particles, produced preferably by the mass and heat transfer phenomena during the thermoanalytical measurements. The merit of the rate jump method by a single cyclic CRTA curve is also discussed on the basis of the present results.
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  • 36
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1161-1170 
    ISSN: 1572-8943
    Keywords: basicity ; dinitramides ; kinetics ; oxidation ; tanδ ; transition temperatures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The dinitramide salts of ammonia (ADN), hexamethylenetetramine (HDN), potassium (KDN), and sodium (NaDN) showed a linear relationship between the DSC rate of decomposition at the peak maximum and the DEA tanδ value at the low temperature transition peak. As the cation basicity increased in the series ADN〈HDN〈KDN〈NaDN, there was an increase in the low temperature transition peak, the energy barrier for relaxation, and the decomposition peak temperature, and a decrease in the tanδ value at the low temperature transition peak, specific heat capacity, and the rate and enthalpy of decomposition. The more basic salts were more thermally stable (i.e., higher decomposition temperature) and less energetic (i.e., lower enthalpy of decomposition). The more internal free volume (disorder) present in these salts, the higher the rates of relaxation and decomposition. Five aluminum powders of different surface areas were analyzed by DSC in platinum sample pans, and it was found that the enthalpy and rate of oxidation increased as the particle size of Al decreased while the enthalpy of the Al melt decreased. TG showed a two-step weight gain in the oxidation of Al with plateaus in the 650 and 1130°C regions and the percent weight gain increased as the particle size of Al decreased. Variable DSC and TG heating rate studies showed that the activation energies for the first step in the oxidation process increased as the particle size of Al increased.
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  • 37
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    Journal of thermal analysis and calorimetry 50 (1997), S. 33-50 
    ISSN: 1572-8943
    Keywords: Ba[Cu(C2O4)2(H2O)]·5H2O ; decomposition ; dehydration ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal behaviour of Ba[Cu(C2O4)2(H2O)]·5H2O in N2 and in O2 has been examined using thermogravimetry (TG) and differential scanning calorimetry (DSC). The dehydration starts at relatively low temperatures (about 80°C), but continues until the onset of the decomposition (about 280°C). The decomposition takes place in two major stages (onsets 280 and 390°C). The mass of the intermediate after the first stage corresponded to the formation of barium oxalate and copper metal and, after the second stage, to the formation of barium carbonate and copper metal. The enthalpy for the dehydration was found to be 311±30 kJ mol−1 (or 52±5 kJ (mol of H2O)−1). The overall enthalpy change for the decomposition of Ba[Cu(C2O4)2] in N2 was estimated from the combined area of the peaks of the DSC curve as −347 kJ mol−1. The kinetics of the thermal dehydration and decomposition were studied using isothermal TG. The dehydration was strongly deceleratory and the α-time curves could be described by the three dimensional diffusion (D3) model. The values of the activation energy and the pre-exponential factor for the dehydration were 125±4 kJ mol−1 and (1.38±0.08)×1015 min−1, respectively. The decomposition was complex, consisting of at least two concurrent processes. The decomposition was analysed in terms of two overlapping deceleratory processes. One process was fast and could be described by the contracting-geometry model withn=5. The other process was slow and could also be described by the contracting-geometry model, but withn=2. The values ofE a andA were 206±23 kJ mol−1 and (2.2±0.5)×1019 min−1, respectively, for the fast process, and 259±37 kJ mol−1 and (6.3±1.8)×1023 min−1, respectively, for the slow process.
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  • 38
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    Journal of thermal analysis and calorimetry 48 (1997), S. 359-366 
    ISSN: 1572-8943
    Keywords: decomposition ; kinetics ; non-isothermal
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Results are presented on the thermal behaviour of two derivatives of malic acid. The decomposition intermediates obtained at about 400
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  • 39
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    Journal of thermal analysis and calorimetry 49 (1997), S. 45-56 
    ISSN: 1572-8943
    Keywords: accommodation function ; fractional reaction ; kinetics ; solid-state reaction ; thermal analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The physico-geometric kinetics for the solid-state reactions by thermoanalytical (TA) measurements were reexamined by focusing some fundamental aspects: (1) the fundamental kinetic equation, (2) the kinetic model function, (3) the fractional reaction α, and (4) the apparent kinetic parameters. It was pointed out that some pitfalls in the practical kinetic study are originated by the disagreement between the kinetic information from the TA measurements and the theory of the physico-geometric kinetics. In order to increase the degree of coordination between the theory and practice, several attempts were made from both the theoretical and experimental points of views. The significance of the apparent kinetic parameters was discussed with a possible orientation for obtaining the reliable kinetic parameters.
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  • 40
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    Journal of thermal analysis and calorimetry 49 (1997), S. 255-260 
    ISSN: 1572-8943
    Keywords: catalytic degradation ; kinetics ; polyethylene
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    Topics: Chemistry and Pharmacology
    Notes: Abstract HZSM-5 zeolite was screened as catalyst for high density polyethylene degradation at 450
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  • 41
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    Journal of thermal analysis and calorimetry 49 (1997), S. 261-268 
    ISSN: 1572-8943
    Keywords: kinetics ; phenol-formaldehyde resins ; pyrolysis-GC ; thermal degradation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Phenol-formaldehyde resins (I andII), synthesised at a monomer feed ratio of F/P = 1.0 and 1.5, were cured at 130
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  • 42
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    Journal of thermal analysis and calorimetry 49 (1997), S. 17-32 
    ISSN: 1572-8943
    Keywords: Arrhenius equation ; compensation ; distinguishability ; kinetics ; mechanisms ; nonisothermal
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper is a review of some of the controversial kinetic aspects of thermal analysis, starting from the ‘šesták questions’ posed in 1979 and looking at developments in some areas since that time. Aspects considered include: temperature programmes and variations, models and mechanisms, kinetic parameters, distinguishability and extent of fit of kinetic models, complementary evidence for kinetic models, the Arrhenius equation and the compensation effect. The value of the ideas of non-isothermal kinetics in chemical education is emphasized.
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  • 43
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1025-1037 
    ISSN: 1572-8943
    Keywords: crystallographic evaluation ; evaluation with difference procedure ; kinetics ; Rietveld refinement ; X-ray diffraction ; temperature resolved
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Time and temperature resolved X-ray diffraction was used for thermal analysis. Series of diffraction patterns were measured, while the samples are heated/cooled stepwise or isothermally with freely selectable temperature programs. The method was applied for the investigation of the phase transitions of ammonium nitrate and HMX (1,3,5,7-tetranitro-1,3,5,7-tetraaza-cyclooctane), when the identification of phases was required. Its capability in the field of kinetics is demonstrated with the isothermal investigation of the solid state reaction of ammonium nitrate with copper oxide and the non-isothermal investigation of the high temperature corrosion of nickel, which was performed by means of a difference procedure. For obtaining structural details peak fitting and Rietveld refinement were applied for the investigation of ammonium nitrate and HMX.
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  • 44
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    Journal of thermal analysis and calorimetry 49 (1997), S. 617-625 
    ISSN: 1572-8943
    Keywords: combustion ; kinetics ; lignite ; thermal analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Beypazari lignite was investigated by differential scanning calorimetry (DSC), thermogravimetry (TG), high pressure thermogravimetry (HPTG) and combustion cell experiments. All the experiments were conducted at non-isothermal heating conditions with a heating rate of 10°C min−1, in the temperature range of 20–700°C. DSC-TG data were analysed using an Arrhenius-type reaction model assuming a first-order reaction. For the HPTG data the Coats and Redfern equation was used for kinetic analysis. In the combustion cell experiments the Fassihi and Brigham approach was used in order to calculate kinetic data. Finally a comparison is made between the kinetic results.
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  • 45
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    Journal of thermal analysis and calorimetry 49 (1997), S. 609-615 
    ISSN: 1572-8943
    Keywords: combustion ; crude oil ; kinetics ; thermogravimetric analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract High pressure thermogravimetric analysis (HPTG) was used in order to study the oxidation of crude oil in a porous medium under pressurised conditions for simulation of in-situ combustion during oil recovery. Three distinct reaction regions were observed from the HPTG curves in an oxidising environment subjected to a constant heating rate. These were low temperature oxidation, fuel deposition and high temperature oxidation. The method of Coats and Redfern was used to obtain kinetic parameters and the results are discussed.
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  • 46
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1527-1533 
    ISSN: 1572-8943
    Keywords: β-cyclodextrin ; cinnamic aldehyde ; kinetics ; thermal analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The stability of the inclusion complex of β-CD with cinnamic aldehyde was investigated by means of TG and DSC. The mass loss takes place in three stages: dehydration occurs at 50–120°C; dissociation of β-CD·C9H8O proceeds in the range 200–260°C; and decomposition of β-CD begins at 280°C. The kinetics of the dissociation of β-CD·C9H8O was studied by means of thermogravimetry both at constant temperature and with linearly increasing temperature. The results demonstrate that the dissociation of β-CD·C9H8O is dominated by a one-dimensional diffusion process. The activation energyE is 160 kJ mol−1, and the pre-exponential factorA is 5.8×1014 min−1. Scanning electron microscope observations and the results of crystal structure analysis are in good agreement with those of thermogravimetry.
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  • 47
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1485-1492 
    ISSN: 1572-8943
    Keywords: bias ; constant temperature stability ; isothermal crystallization ; kinetics ; oxidative induction time
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Oxidative induction time (OIT), constant temperature stability (CTS) and isothermal crystallization are examples of isothermal time-to-event (TTE) measurements obtained using differential scanning calorimetry. In TTE experiments, a test specimen is heated/cooled at a constant rate from the setup temperature to an isothermal test temperature. Once the test temperature is achieved, a clock is started and the time to the thermal event (e.g., onset to oxidation, thermal decomposition or crystallization exotherm peak) is measured. Such TTE values may be used to rank stability of the material at the test temperature. Some portion of the reaction of interest, however, takes place during the pre-isothermal period as the test specimen approaches the test temperature. This amount of reaction is unmeasured and represents a bias in the resultant TTE value. An equation has been derived and numerically integrated to estimate this bias. This approach shows that the bias is dependent upon the activation energy of the test reaction, the heating/cooling rate used and the temperature range between the melting temperature and the test temperature. For commonly used heating rates, the bias for OIT and CTS tests is small. Further, the myth that isothermal crystallization kinetics determinations required high cooling rates is dispelled with the bias of less than 0.9 min resulting from heating rates as low as 10°C min−1. Knowledge of magnitude of this bias permits the selection of experimental conditions without the expense of high heating/cooling rate apparatus or extra cost cooling accessories.
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  • 48
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    Journal of thermal analysis and calorimetry 50 (1997), S. 533-545 
    ISSN: 1572-8943
    Keywords: Cu-19 at% Al ; dislocations ; kinetics ; segregation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A model is proposed to describe the kinetics of solute segregation to partial dislocations in solid solutions of cold-rolled alloys. The case when half edge and half screw dislocations are present is considered. The model gives account of the kinetic behaviour observed in a deformed Cu-19 at% Al alloy where two unknown processes could be assessed during calorimetric isothermal experiments. The faster process corresponds to segregation to screw dissociated dislocations while the slower one corresponds to segregation to edge dissociated dislocations. Experimental activation energies, larger for edge dislocations, are close to that for pipe diffusion along the partials corrected by pinner binding energy terms. It is also predicted that segregation occurs faster as the dislocation density is increased. A quantitative comparison of experimental results with model predictions is given.
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  • 49
    ISSN: 1573-1421
    Keywords: calcite ; precipitation ; dissolution ; kinetics ; reaction mechanism
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    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Calcite dissolution rates were measured using a free-drift technique at 25°C, 1 atm total pressure, and various $$P_{CO_2 } $$ in deionized water. The data were corrected for gas phase disequilibrium and fitted to a kinetic expression derived by coupling the mechanistic models of Plummeret al. (1987a) and Chouet al. (1989) to the surface complexation model of Van Cappellenet al. (1993). Corrected dissolution and precipitation rate measurements from previous investigations were combined to our data set and fitted to the same expression. The following reactions provide an adequate description of the calcite dissolution and precipitation mechanism in dilute solutions: for which the overall reaction rate is given by where 〉i are the densities of surface complexes (mol/m2),a i are the activities of dissolved species and,k i are the rate constants corresponding to the above reactions. This rate equation satisfies the principle of microscopic reversibility and applies to both dissolution and precipitation reactions over a wide range of $$P_{CO_2 } $$ , pH and saturation states. The rate constants obtained from fitting the data set to Equation (3) are compatible with values reported by Plummeret al. and Chouet al., as well as yielding a very good estimate of the thermodynamic solubility constant of calcite, K 0 sp .
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  • 50
    ISSN: 1573-4889
    Keywords: oxidation ; Incoloy 909 ; superalloy ; scale ; high temperature ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of an Fe-38Ni-13Co-4.7Nb-1.5Ti-0.4Si superalloy (Incoloy 909 type alloy), was investigated at temperatures between 1000 K and 1400 K in Ar-(1, 10%)H20 atmosphere using metallographic, electron probe microanalysis, and X-ray diffraction techniques. The oxide scales consist of an external scale and an internal scale which has an intergranular scale (above 1200 K) and an intergranular scale. The oxide phases in each scale are identified asα-Fe2,O3 (below 1200 K) or FeO (above 1300 K) and CoO · Fe2O3 and FeO · Nb2O5, respectively. The morphologies, the oxide phases and the oxidation rates do not depend on the partial pressure of H2O in the range between one and ten percent in Ar gas. The rate constants for the intergranular-scale formation in this alloy are about one-tenth as large as those in Fe-36%Ni alloy reported previously. At all the temperatures the scales grow according to a parabolic rate law and the apparent activation energies for the processes are estimated.
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  • 51
    ISSN: 1573-4889
    Keywords: oxidation ; kinetics ; iron ; iron-nitride
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of α-Fe and ɛ-Fe2N1−z at 573 K and 673 K in O2 at 1 atm was investigated by thermogravimetrical analysis, X-ray diffraction, light-optical microscopy, scanning electron microscopy and electron probe X-ray microanalysis. Upon oxidation at 573 K and 673 K, on α-Fe initially α-Fe2O3 develops, whereas on ɛ-Fe2N1−z initially Fe3O4 develops. In an early stage of oxidation the oxidation rate of ɛ-Fe2N1−z appears to be much larger than of α-Fe. This can be attributed largely to an effective surface area available for oxygen uptake, which is much larger for ɛ-Fe2N1−z than for α-Fe due to the porous structure of ɛ-Fe2N1−z as prepared by gaseous nitriding of iron. The development of a magnetite layer in-between the hematite layer and the α-Fe substrate, at a later stage of oxidation, enhances layer-growth kinetics. After 100 min oxidation at 673 K the (parabolic) oxidation rates for α-Fe and ɛ-Fe2N1−z become about equal, indicating that on both substrates the oxide growth is controlled by the same rate limiting step which is attributed to short-circuit diffusion of iron cations. Oxidizing ɛ-Fe2N1−z increases the nitrogen concentration in the remaining ɛ-iron nitride, because the outward flux of iron cations, necessary for oxide growth, leads to an accumulation of nitrogen atoms left behind.
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  • 52
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    Oxidation of metals 48 (1997), S. 171-184 
    ISSN: 1573-4889
    Keywords: TiAl, corrosion ; high-temperature ; kinetics ; nitrogen dependence
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxide scale formation on γ-TiAl at 800 and 900°C was studied using high temperature X-ray diffraction as anin situ-method. The experiments were performed in air and in He with 20 vol.% O2. The formation of alumina in the form of α-Al2O3 and of TiO2 in the form of rutile was observed in both atmospheres and the formation of TiN was detected in air. Depending on the atmosphere the diffraction peaks of two different additional phases were detected, which do not exist in any data base nor in the Ti-Al-O phase diagram. One of them, the Z-phase, appears in He with 20 vol.% O2 and the other, the X-phase, in air. The Zphase was also found at room temperature after oxidation at 900°C in air. The growth of both phases, X and Z, starts immediately with the oxidation process and follows the parabolic rate law.
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  • 53
    ISSN: 1573-4889
    Keywords: oxidation ; titanium ; rutile ; scale ; high temperature ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of pure titanium has been investigated in the temperature range of 1000 K to 1300 K in CO2 or Ar-10%CO2. Optical microscopy, electron probe microanalyses, and X-ray measurements on the oxide scales formed during oxidation indicate that their structures are nearly independent of temperature and the corrosion atmosphere. The scales consisted of two layers, an external one and an internal one, having a rutile (TiO2) structure. The parabolic rate law was confirmed for growth of the external scale and the permeation depth of oxygen in titanium with apparent activation energies of 266 and 226 kJ/mol, respectively. The rate-determining diffusion species in the oxidation processes are discussed.
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  • 54
    ISSN: 1573-4919
    Keywords: acetylcholinesterase ; optimization ; kinetics ; venom ; turnover number
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Acetylcholinesterase (AChE) was investigated inWalterinnesia aegyptia venom and characterized with respect to its kinetic properties. It was found that 4.0 ug of crude venom protein and an incubation time of 4.0 min were suitable conditions for linearity of AChE activity at 25°C. The optimum strength of the sodium phosphate buffer was 0.05 M, and the optimum pH was 7.75. The optimum temperature was 30°C. The activation energy and the heat of activation were observed to be 6510 and 5922 cal/mole. The AChE was specific for acetylthiocholine but it did not hydrolyse butyrylthiocholine. The optimum substrate concentration was 3.0 mM but at higher substrate concentrations, the AChE activity declined. The ASCh concentration ranges for different orders of the reactions were determined and kinetic parameters (Km, Vmax, kcat, and ksp) were established at each order of the reaction.
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  • 55
    ISSN: 1573-4927
    Keywords: glycophorins ; gorilla ; evolution ; gene family ; gene expression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Homologues of MN blood group antigens, encoded by members of the glycophorin A (GPA) gene family, are expressed in man, anthropoid apes, and some species of Old World monkeys. Previous studies had shown that a three-gene framework, most closely related to that in man, is present in the chimpanzee. Here we report the genomic structure, transcript map, and protein expression of the GYPA locus in gorillas. Compared to the corresponding human and chimpanzee homologues, gorilla GPA, GPB, and GPB/E genes each showed a high degree of sequence identity, with the same exon-intron organization. However, the expression of exons III, IV, or V encoding the extracellular or membrane domains of homologous glycophorins varied among the three species. Gorilla GPA and GPB/E genes were unique in that the former occurred in two allelic forms with or without the expression of exon III, whereas the latter contained one (ψ exon III) instead of two silenced exons (ψ exons III and IV). Differences from human but not chimpanzee GPA also included the presence of a hybrid M/N epitope and the absence of the sequon for N-glycosylation. Owing to the retention of a functional exon III, gorilla GPB was more similar to chimpanzee GPB than human GPB. A transspecies allele was identified in the gorilla that gave rise to the Henshaw (He)-like antigen similar to that found in man. These results provide further insight into the model for evolution of the GPA gene family, indicating that the mechanisms underlying inter- and intraspecific polymorphism of glycophorins could predate the divergence of gorillas as the consequence of gene duplication and diversification.
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  • 56
    ISSN: 1573-4846
    Keywords: zirconium butoxide ; titanium butoxide ; kinetics ; hydrolysis ; condensation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A continuous flowing-rapid mixing technique was combined with FTIR, SAXS and electrical conductivity to study the early stages of polymer formation and growth during the acid-catalyzed hydrolysis and condensation of titanium and zirconium alkoxides. Reaction times as short as 80 milliseconds were investigated. FTIR spectroscopy was used to monitor the water and M–OR concentrations during the reaction. Hydrolysis of ∼25–50% of the alkoxy groups was facile. The FTIR and SAXS data showed that condensation was also very rapid. The activity and mobility of the ions in the solution were monitored by electrical conductivity measurements. The decrease in the normalized solution conductivity during the reaction correlated with the loss of [M–OR]. Furthermore, the radius of gyration of the growing polymers increased rapidly in regimes where the conductivity and [M–OR] decreased fastest. This finding suggests that the mobility of some of the charge carrying species decreases because of the growth in size of the polymers.
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  • 57
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    Oxidation of metals 43 (1995), S. 509-526 
    ISSN: 1573-4889
    Keywords: oxidation ; kinetics ; tantalum ; oxide ; suboxide ; impurities ; diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The kinetics, structural aspects, and phase morphologies were studied for tantalum oxidation in air from 600 to 1000°C for samples of different purity (99.15%, 99.76%, and 99.95% Ta). Regardless of purity, tantalum oxidation in the temperature range of 600–800°C as a rule is governed by a linear rate law. From 900 to 1000°C the initial-stage oxidation is governed by the parabolic rate law, which changes to the linear rate law with time. TGA, XRD, SEM, and AES methods were used. The, effect of purity on tantalum oxidation was shown to be determined by the mechanism of intermediate-oxide formation. They are TaO z (Ta2O) at 600–800°C and TaO at 900–1000°C. The final product of oxidation was β-Ta2O5.
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  • 58
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    Oxidation of metals 43 (1995), S. 543-560 
    ISSN: 1573-4889
    Keywords: stainless steel ; sulfidation ; hydrogen sulfide ; sulfur vapor ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The sulfidizing behavior of Fe−22Cr−4Al−0.15Zr (wt.%) was studied in two atmospheres: S2 vapor over the range 4.4–25.4 Pa and H2−H2S mixtures corresponding to aP S 2 range 0.2–1.297 Pa in the temperature range 973–1373 K. It was found that the constitution of the gaseous phase is of great importance on the corrosion kinetics and the morphology of the corrosion products. Furthermore, a stratification phenomenon during scale growth was observed during the initial sulfidation stage in H2−H2S mixtures containing a sufficiently high H2S partial pressure. This behavior was not observed during tests in puresulfur vapor.
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  • 59
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    Oxidation of metals 44 (1995), S. 63-79 
    ISSN: 1573-4889
    Keywords: scale growth ; oxidation mechanism ; kinetics ; scale adherence ; reactive element effect ; intertacial segregation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Recent studies of the structure and dynamics of solid-solid interfaces have provided some understanding about the role of the scale-metal interface in the growth of reaction product scales on pure metals. The action of interfacial defects (misfit dislocations, misorientation dislocations and disconnections) in the creation and annihilation of the point defects suporting the diffusional growth of scales is considered. Anion point defects (vacancies/interstitials) supporting scale growth by anion diffusion are annihilated/created by the climb of misorientation dislocations or disconnections in the scale at the interface. For scale growth by cation diffusion, cation point defects (vacancies/interstitials) can be annihilated/created by the climb of interfacial misfit or misorientation dislocations in the metal. Because of their necessarily high density, in most cases, the dominant climb of misfit dislocations would be favored. The blocking of interfacial reaction steps can be a means to retard the scaling kinetics and to alter the fundamental scaling mode. For instance, the interfacial segregation of large reactive element ions can pin the interface dislocations, an action which poisons the usual interfacial reaction step. Such considerations are consistent with the well-known phenomena ascribed to the reactive element effect (REE).
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  • 60
    ISSN: 1573-4889
    Keywords: binary alloys ; oxidation ; transient state ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The initial transient stage in the oxidation of binary alloys forming scales exclusively composed of the most stable oxide is examined by means of a simplified approach which avoids the numerical integration of the diffusion equation for the transport of the metal components in the alloy. At variance with previous solutions to this problem obtained by means of numerical methods, this treatment takes into account also the effect of the gas-scale reaction at the outer surface of the oxide. The concentration of the most-reactive component at the alloy surface changes gradually with time from the initial bulk value towards the corresponding steady-state value without involving any minimum, while the overall rate of the reaction presents a gradual transition from an initial nearly linear towards final parabolic behavior.
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  • 61
    ISSN: 1573-1561
    Keywords: Eriocrania cicatricella ; Eriocrania sparrmannella ; Eriocraniidae ; Lepidoptera ; sex pheromone ; EAG ; GC-EAD ; mass spectrometry ; synthesis ; evolution ; (Z)-4-hepten-2-one ; (2R)-heptan-2-ol ; (2R)-(Z)-4-hepten-2-ol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Extracts from different body parts of adult femaleEriocrania cicatricella (Zett.) were tested for electrophysiological activity on conspecific male antennae. Extracts from the Vth abdominal segment, containing a pair of exocrine glands, elicited the largest electroantennographic response when compared to extracts of other body parts. Female extracts were analyzed by gas chromatography with simultaneous flame ionization and electroantennographic detection (EAD). The EAD active peaks were identified as (Z)-4-hepten-2-one, (2R)-heptane-2-ol, and (2R)-(Z)-4-hepten-2-ol by coinjection on a gas chromatography and by comparison of mass spectra with those of synthetic standards. In field tests, a blend of these three pheromone components was highly attractive to conspecific males, and a subtractive assay confirmed that the unsaturated alcohol is the major pheromone component, whereas no definite behavioral activity could be assigned to the ketone or the saturated alcohol. A bait containing the two alcohols withS-configuration was attractive to maleE. sparrmannella (Bosc), whereas no males ofE. cicatricella were found in these traps. The sex pheromone compounds inE. cicatricella are chemically similar to pheromones reported in Trichoptera and they are produced in homologous glands.
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  • 62
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    Journal of chemical ecology 23 (1997), S. 1527-1547 
    ISSN: 1573-1561
    Keywords: Secondary metabolites ; chemical defense ; evolution ; ascidians ; sponges
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract We used three chemical fractions (spanning a wide range of polarities) from the extracts of four marine invertebrates, the spongesCrambe crambe andHemimycale columella and the ascidiansCystodytes dellechiajei andPolysyncraton lacazei, to test inhibition of cell division, photosynthesis, and settlement. We used assay organisms from the same habitat, seeking to determine whether a species may display diverse, ecologically relevant bioac-tivities and, if so, whether the same types of compound may be responsible for such activities. Cell division was strongly inhibited by the spongeC. crambe. A dichloromethane fraction fromC. crambe prevented development of sea urchinParacentrotus lividus eggs at a concentration of 10 μg/ml, as did the butanolic fraction, but at higher concentrations (50 and 100 μg/ml). At 50 μg/ml, the aqueous fraction ofC. crambe allowed cell division but prevented eggs from developing beyond the gastrula stage. Similar results were recorded with the dichloromethane fraction ofP. lacazei and from the aqueous fraction ofH. columella. Photosynthesis was unaffected by any of the species at 50 μg/ml. Larval settlement was inhibited by one or another fraction from the four species surveyed at a concentration of 50 μg/ml, althoughC. crambe exhibited the greatest amount of activity. We therefore found that various fractions displayed the same type of bioactivity, while compounds from the same fraction were responsible for multiple activities, suggesting that secondary metabolites are multiple-purpose tools in nature, which is relevant to our understanding of species ecology and evolution. Moreover, results showed that the assessment of the role of chemical compounds is significantly influenced by the assay organism, fractionation procedure, concentration, and duration of experiments. All these factors should be carefully considered when testing ecological hypotheses of the roles of chemically-mediated bioactivities.
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  • 63
    ISSN: 1573-2932
    Keywords: fractionation ; redistribution ; saturation ; kinetics ; heavy metals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract Solid-phase transformations of Cd, Cu, Cr, Ni and Zn, added as soluble salts at several levels to two arid-zone soils, were studied over a period of one year. The soils were maintained under a saturated-paste regime and sampled periodically. A selective sequential dissolution procedure was employed to determine the changes in metal distribution among six operationally defined solid-phase fractions. A function, Uts was introduced to measure the fractional attainment of equilibrium of the soils following a perturbation. The direction and rate of redistribution of the added metals in the soils were affected by the nature of the metal, the soil properties and the metal loading level. Cd added to the soils was transferred from the exchangeable (EXC) into the carbonate (CARB) fraction. When soluble Cu, Cr, Ni and Zn were added at low loading levels, metals were transferred from the reducible oxides(RO) bound and easily reducible oxides (ERO) bound fractions and the EXC fraction, into the CARB fraction. However, at the higher loading level, metals were transferred from the EXC and CARB fractions into the organic matter bound (OM), ERO and RO fractions. The Uts function approached lower values as incubation continued but remained removed from 1. The overall flux of metals among fractions was the combined result of the readjustment of the metals in the native soil to changing conditions due to saturation, and the transfer of added soluble metals to the less labile fractions.
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  • 64
    ISSN: 1573-4846
    Keywords: zirconium butoxide ; titanium butoxide ; kinetics ; hydrolysis ; condensation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A continuous flowing-rapid mixing technique was combined with FTIR, SAXS and electrical conductivity to study the early stages of polymer formation and growth during the acid-catalyzed hydrolysis and condensation of titanium and zirconium alkoxides. Reaction times as short as 80 milliseconds were investigated. FTIR spectroscopy was used to monitor the water and M−OR concentrations during the reaction. Hydrolysis of ∼25–50% of the alkoxy groups was facile. The FTIR and SAXS data showed that condensation was also very rapid. The activity and mobility of the ions in the solution were monitored by electrical conductivity measurements. The decrease in the normalized solution conductivity during the reaction correlated with the loss of [M−OR]. Furthermore, the radius of gyration of the growing polymers increased rapidly in regimes where the conductivity and [M−OR] decreased fastest. This finding suggests that the mobility of some of the charge carrying species decreases because of the growth in size of the polymers.
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  • 65
    ISSN: 1573-4927
    Keywords: Akodon ; Cricetidae rodents ; genetic diversity ; biochemical polymorphism ; evolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The present study involved an electrophoretic survey of 22 protein loci in 269 individuals belonging to three species of the genusAkodon, A. aff.cursor (2n=16),A. cursor (2n=14/15), andA. montensis (2n=24/25/26), collected in Eastern Brazil. The joint results of gene diversity, genetic distances, phenetic analyses, and phylogenetic trees suggested thatA. aff.cursor has recently separated fromA. cursor and that the three species have experienced a recent chromosomal divergence followed by low allozyme differentiation. These data are in agreement with their classification as sibling species.
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  • 66
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    Journal of sol gel science and technology 4 (1995), S. 117-133 
    ISSN: 1573-4846
    Keywords: kinetics ; precursor chemistry ; silica ; permeability ; microstructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The molecular-scale species distributions and intermediate-scale structure of silicate sols influence the microstructures of the corresponding thin films prepared by dip-coating. Using multi-step hydrolysis procedures, we find that, depending on the sequence and timing of the successive steps, the species distributions (determined by 29Si NMR) and intermediate scale structure (determined by SAXS) can change remarkably for sols prepared with the same nominal composition. During film formation, these kinetic effects cause differences in the efficiency of packing of the silicate species, leading to thin film structures with different porosities.
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  • 67
    ISSN: 1573-4943
    Keywords: Ribosomal proteins ; protein sequencing ; evolution ; Haloarcula marismortui
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The ribosomal protein HS23 from the 30S subunit of the extreme halophilicHaloarcula marismortui, belonging to the group of archaea, was isolated either by RP-HLPLC or two-dimensional polyacrylamide gel electrophoresis. The complete amino acid sequence was determined by automated N-terminal microsequencing. The protein consists of 123 residues with a corresponding molecular mass of 12,552 Da as determined by electrospray mass spectroscopy; the pI is 11.04. Homology studies reveal similarities to the eukaryotic ribosomal protein S8 fromHomo sapiens, Rattus norvegicus, Leishmania major, andSaccharomyces cerevisiae.
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  • 68
    ISSN: 1573-4943
    Keywords: Hydrolase ; site-directed mutagenesis ; kinetics ; cyclohexane ; butanoic acid esters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract To reveal the functional role of Glu87 and Trp89 in the lid ofHumicola lanuginosa lipase, site-directed mutagenesis at Glu87 and Trp89 was carried out. The catalytic performance of wild-type and mutated lipases was studied in transesterification reactions in cyclohexane at a controlled water activity. Two different acyl donors were used in the investigation: tributyrin, a natural substrate for a lipase, and vinyl butyrate, an activated ester suitable for fast and efficient lipase-catalyzed transformations in preparative organic synthesis. As acyl acceptor 1-heptanol was used. The Glu87Ala mutation decreased theV max,app value with tributyrin and vinyl butyrate by a factor of 1.5 and 2, respectively. TheK m,app for tributyrin was not affected by the Glu87Ala mutation, but theK m,app for vinyl butyrate increased twofold compared to the wild-type lipase. Changing Trp89 into a Phe residue afforded an enzyme with a 2.7- and 2-fold decreasedV max,app with the substrates tributyrin and vinyl butyrate, respectively, compared to the wild-type lipase. No significant effects on theK m,app values for tributyrin or vinyl butyrate were seen as a result of the Trp89Phe mutation. However, the introduction of a Glu residue at position 89 in the lid increased theK m,app for tributyrin and vinyl butyrate by a factor of 〉5 and 2, respectively. The Trp89Glu mutated lipase could not be saturated with tributyrin within the experimental conditions (0–680 mM) studied here. With vinyl butyrate as a substrate theV max,app was only 6% of that obtained with wild-type enzyme.
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  • 69
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    Plant molecular biology 29 (1995), S. 1005-1014 
    ISSN: 1573-5028
    Keywords: evolution ; genome mapping ; isozymes ; oxygen radicals ; powdery mildew
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Clones representing two distinct barley catalase genes, Cat1 and Cat2, were found in a cDNA library prepared from seedling polysomal mRNA. Both clones were sequenced, and their deduced amino acid sequences were found to have high homology with maize and rice catalase genes. Cat1 had a 91% deduced amino acid sequence identity to CAT-1 of maize and 92% to CAT B of rice. Cat2 had 72 and 79% amino acid sequence identities to maize CAT-2 and-3 and 89% to CAT A of rice. Barley, maize or rice isozymes could be divided into two distinct groups by amino acid homologies, with one group homologous to the mitochondria-associated CAT-3 of maize and the other homologous to the maize peroxisomal/glyoxysomal CAT-1. Both barley CATs contained possible peroxisomal targeting signals, but neither had favorable mitochondrial targeting sequences. Cat1 mRNA occurred in whole endosperms (aleurones plus starchy endosperm), in isolated aleurones and in developing seeds, but Cat2 mRNA was virtually absent. Both mRNAs displayed different developmental expression patterns in scutella of germinating seeds. Cat2 mRNA predominated in etiolated seedling shoots and leaf blades. Barley genomic DNA contained two genes for Cat1 and one gene for Cat2. The Cat2 gene was mapped to the long arm of chromosome 4, 2.9 cM in telomeric orientation from the mlo locus conferring resistance to the powdery mildew fungus (Erysiphe graminis f.sp. hordei).
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  • 70
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    Plant molecular biology 29 (1995), S. 1057-1070 
    ISSN: 1573-5028
    Keywords: Arabidopsis ; EF-Tu ; evolution ; gene families ; mitochondria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract We have characterized a second nuclear gene (tufM) in Arabidopsis thaliana that encodes a eubacterial-like protein synthesis elongation factor Tu (EF-Tu). This gene does not closely resemble the previously described Arabidopsis nuclear tufA gene, which encodes the plastid EF-Tu, and does not contain sequence elements found in all cyanobacterial and plastid tufA genes. However, the predicted amino acid sequence includes an N-terminal extension which resembles an organellar targeting sequence and shares three unique sequence elements with mitochondrial EF-Tu's, from Saccharomyces cerevisiae and Homo sapiens, suggesting that this gene encodes the Arabidopsis mitochondrial EF-Tu. Consistent with this interpretation, the gene is expressed at a higher level in flowers than in leaves. Phylogenetic analysis confirms the mitochondrial character of the sequence and indicates that the human, yeast, and Arabidopsis tufM genes have undergone considerably more sequence divergence than their cytoplasmic counterparts, perhaps reflecting a cross-compartmental acceleration of gene evolution for components of the mitochondrial translation apparatus. As previously observed for tufA, the tufM gene is present in one copy in Arabidopsis but in several copies in other species of crucifers.
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  • 71
    ISSN: 1573-5028
    Keywords: carbon fixation ; oxidative pentose phosphate pathway ; chloroplasts ; evolution ; endosymbiosis ; isoenzymes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Exploiting the differential expression of genes for Calvin cycle enzymes in bundle-sheath and mesophyll cells of the C4 plant Sorghum bicolor L., we isolated via subtractive hybridization a molecular probe for the Calvin cycle enzyme d-ribulose-5-phosphate 3-epimerase (R5P3E) (EC 5.1.3.1), with the help of which several full-size cDNAs were isolated from spinach. Functional identity of the encoded mature subunit was shown by R5P3E activity found in affinity-purified glutatione S-transferase fusions expressed in Escherichia coli and by three-fold increase of R5P3E activity upon induction of E. coli overexpressing the spinach subunit under the control of the bacteriophage T7 promoter, demonstrating that we have cloned the first functional ribulose-5-phosphate 3-epimerase from any eukaryotic source. The chloroplast enzyme from spinach shares about 50% amino acid identity with its homologues from the Calvin cycle operons of the autotrophic purple bacteria Alcaligenes eutrophus and Rhodospirillum rubrum. A R5P3E-related eubacterial gene family was identified which arose through ancient duplications in prokaryotic chromosomes, three R5P3E-related genes of yet unknown function have persisted to the present within the E. coli genome. A gene phylogeny reveals that spinach R5P3E is more similar to eubacterial homologues than to the yeast sequence, suggesting a eubacterial origin for this plant nuclear gene.
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  • 72
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    The protein journal 14 (1995), S. 695-701 
    ISSN: 1573-4943
    Keywords: Aminoacylase ; metal ion ; reactivation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetic theory of the substrate reaction during irreversible change of enzyme activity previously described by Tsou (Tsou (1988),Adv. Enzymol. Relat. Areas Mol. Biol.61, 381–436] has been applied to a study of the kinetics of the course of reactivation during reconstitution of apo-aminoacylase using Mn2+ or Zn2+. The kinetic parameters for Mn2+-and Zn2+-reconstituted enzymes and the microscopic rate constants for reactivation during reconstitution were determined. The kinetic analysis suggests the presence of a second Mn2+ binding site in Mn2+-reconstituted aminoacylase.
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  • 73
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    Molecular biology reports 22 (1995), S. 139-145 
    ISSN: 1573-4978
    Keywords: chloroplast ; cyanelle ; evolution ; pre-tRNA processing ; ribozyme ; wheat germ
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract RNase P consists of both protein and RNA subunits in all organisms and organelles investigated so far, with the exception of chloroplasts and plant nuclei where no enzyme-associated RNA has been detected to date. Studies on substrate specificity revealed that cleavage by plant nuclear RNase P is critically dependent on a complete and intact structure of the substrate. No clearcut answer is yet possible regarding the order of processing events at the 5′ or 3′ end of tRNAs in the case of nuclear or chloroplast processing enzymes. RNase P from a phylogenetically ancient photosynthetic organelle will be discussed in greater detail: The enzyme from theCyanophora paradoxa cyanelle is the first RNase P from a photosynthetic organelle which has been shown to contain an essential RNA subunit. This RNA is strikingly similar to its counterpart from cyanobacteria, yet it lacks catalytic activity. Properties of the holoenzyme suggest an intermediate position in RNA enzyme evolution, with an eukaryotic-type, inactive RNA and a prokaryotic-type small protein subunit. The possible presence of an RNA component in RNase P from plant nuclei and modern chloroplasts will be discussed, including a critical evaluation of some criteria that have been frequently applied to elucidate the subunit composition of RNase P from different organisms.
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  • 74
    ISSN: 1573-5028
    Keywords: ABA-inducible genes ; coding region repeats ; embryo-specific gene family ; evolution ; Hordeum vulgare L. ; phylogenetic analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The highly conserved Group 1 late embryogenesis abundant (Lea) genes are present in the genome of most plants as a gene family. Family members are conserved along the entire coding region, especially within the extremely hydrophilic internal 20 amino acid motif, which may be repeated. Cloning of Lea Group 1 genes from barley resulted in the characterization of four family members named B19.1, B19.1b, B19.3 and B19.4 after the presence of this motif 1, 1, 3 and 4 times in each gene, respectively. We present here the results of comparative and evolutionary analyses of the barley Group 1 Lea gene family (B19). The most important findings resulting from this work are (1) the tandem clustering of B19.3 and B19.4, (2) the spatial conservation of putative regulatory elements between the four B19 gene promoters, (3) the determination of the relative ‘age’ of the gene family members and (4) the ‘chimeric’ nature of B19.3 and B19.4, reflecting a cross-over or gene-conversion event in their common ancestor. We also show evidence for the presence of one or two additional expressed B19 genes in the barley genome. Based on our results, we present a model for the evolution of the family in barley, including the 20 amino acid motif. Comparisons of the relatedness between the barley family and all other known Group 1 Lea genes using maximum parsimony (PAUP) analysis provide evidence for the time of divergence between the barley genes containing the internal motif as a single copy and as a repeat. The PAUP analyses also provide evidence for independent duplications of Group 1 genes containing the internal motif as a repeat in both monocots and dicots.
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  • 75
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    Biochemical genetics 33 (1995), S. 173-181 
    ISSN: 1573-4927
    Keywords: fragile-X DNA systems ; expandable triplet repeats ; dynamic mutations ; conserved genetic domains ; evolution ; heritable disease mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract A model explaining properties exhibited by fragile-X DNA systems arises from observations that time-dependent base substitutions are expressed at G-C sites but not at A–T sites (Biochem. Genet.32:383, 1994). [CGG]n sequences are classified as most sensitive to evolutionary base substitution processes involving time-dependent populating of G-C sites with enol-imine states having enhanced stability. Increased density of these states in oocyte DNA would introduce a ground-state collapse double-helix of reduced energy that would inhibit strand separation by the replicase. Evolutionarily altered G′ in CG′G triplets allows CG′G to be transcribed as CTG, an initiation codon. And this will cause reinitiation of DNA synthesis, thereby adding additional CGG units to the collapsed double helix. This situation would not occur in slower-evolving male haploid DNA that replicates frequently.
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  • 76
    ISSN: 1573-4927
    Keywords: Akodon ; Cricetidae rodents ; genetic diversity ; biochemical polymorphism ; evolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The present study involved an electrophoretic survey of 22 protein loci in 269 individuals belonging to three species of the genusAkodon, A. aff.cursor (2n=16),A. cursor (2n=14/15), andA. montensis (2n=24/25/26), collected in Eastern Brazil. The joint results of gene diversity, genetic distances, phenetic analyses, and phylogenetic trees suggested thatA. aff.cursor has recently separated fromA. cursor and that the three species have experienced a recent chromosomal divergence followed by low allozyme differentiation. These data are in agreement with their classification as sibling species.
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  • 77
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    Molecular biology reports 21 (1995), S. 165-167 
    ISSN: 1573-4978
    Keywords: 5S ribosomal RNA ; Harpalus rufipes ; evolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The nucleotide sequence of 5S ribosomal RNA from the beetleHarpalus rufipes was determined and compared with primary structures of other insect 5S rRNAs. Sequence differences between two beetle 5S rRNAs may represent phylogenetic markers specific for two groups of Coleoptera — Adephaga and Polyphaga. Analysis of all insect sequences using parsimony allowed us to infer a phylogenetic tree of insects, which is consistent with morphological and paleobiological data.
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  • 78
    ISSN: 1573-5028
    Keywords: Arabidopsis ; evolution ; expression ; genomic clone ; in situ hybridization ; myrosinase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Myrosinase (thioglucoside glucohydrolase, EC 3.2.3.1.) is in Brassicaceae species such as Brassica napus and Sinapis alba encoded by two differentially expressed gene families, MA and MB, consisting of about 4 and 10 genes, respectively. Southern blot analysis showed that Arabidopsis thaliana contains three myrosinase genes. These genes were isolated from a genomic library and two of them, TGG1 and TGG2, were sequenced. They were found to be located in an inverted mode with their 3′ ends 4.4 kb apart. Their organization was highly conserved with 12 exons and 11 short introns. Comparison of nucleotide sequences of TGG1 and TGG2 exons revealed an overall 75% similarity. In contrast, the overall nucleotide sequence similarity in introns was only 42%. In intron 1 the unusual 5′ splice border GC was used. Phylogenetic analyses using both distance matrix and parsimony programs suggested that the Arabidopsis genes could not be grouped with either MA or MB genes. Consequently, these two gene families arose only after Arabidopsis had diverged from the other Brassicaceae species. In situ hybridization experiments showed that TGG1 and TGG2 expressing cells are present in leaf, sepal, petal, and gynoecium. In developing seeds, a few cells reacting with the TGG1 probe, but not with the TGG2 probe, were found indicating a partly different expression of these genes.
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  • 79
    ISSN: 1573-5028
    Keywords: evolution ; Chlamydomonas reinhardtii ; chloroplast ; site-specific recombination ; transcription ; transposition
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    Topics: Biology
    Notes: Abstract We have characterized two copies of a 2.4 kb DNA element that we call ‘Wendy’, in the chloroplast chromosome of Chlamydomonas reinhardtii. The two copies of Wendy reside in different single-copy regions at opposite positions in the chloroplast genome. Like many mobile DNA elements, both copies of Wendy are bordered by inverted repeats and contain several additional degenerate copies of these repeat sequences in direct or inverted orientation. In addition, four basepairs are repeated in direct orientation. Two major open reading frames (ORFs) are predicted from the DNA sequence of Wendy I. These ORFs are co-transcribed from a promoter inside the element. The deduced amino acid sequence of the larger of these ORFs shares some weak similarities with sequence motifs of transposases and integrases of other mobile elements. Wendy II appears to be altered relative to Wendy I by point mutations and small deletions and insertions which destroy the ORFs. The leader sequence of the Wendy transcript is nearly identical with the leader sequence of the rbcL transcript of C. reinhardtii, but not of C. moewusii (where the complete Wendy was also undetectable). Furthermore, both copies of Wendy are bracketed by gene clusters that are separated in C. reinhardtii but are contiguous in C. moewusii where they exist in an inverted orientation compared with C. reinhardtii. Wendy was not found in any of the completely sequenced chloroplast genomes of rice, tobacco, pine, Euglena or Marchantia, nor in any other GenBank entry. Our results suggest that Wendy has invaded C. reinhardtii after divergence from other species. Subsequent Wendy-dependent illegitimate homologous or site-specific recombination events or both may have contributed to scrambling of the C. reinhardtii chloroplast genome relative to genomes of other species.
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  • 80
    ISSN: 1573-9171
    Keywords: electrochemistry ; metal complexes ; dichlorocyclopropane ; kinetics ; reduction
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Electrochemical reduction of the complexes Rh(CO)ClL2 [L = (EtO)2PCN (1), Ph2PCN (2)] and Rh2(CO)4L [L = P(CN)3 (3), $$Ph\begin{array}{*{20}c} P \\ | \\ {CN} \\ \end{array} ---\begin{array}{*{20}c} P \\ | \\ {CN} \\ \end{array} Ph$$ (4)] and their catalytic properties in electrochemical reduction of 2-carbomethoxy-2-methyl-1,1-dichloro-cyclopropane were studied. The catalytic electroreduction of a substrate at the reduction potentials of the central ion was developed for complexes2–4. This process is accelerated substantially for complexes2 and3 in the presence of anthracene.
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  • 81
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    Russian chemical bulletin 44 (1995), S. 1907-1913 
    ISSN: 1573-9171
    Keywords: photochemical transformations ; 1-arylcyanomethyl-9 ; 10-anthraquinones ; nucleophilic addition ; oxidation ; kinetics ; quantum-chemical calculations
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Photochemical transformations of 1-arylcyanomethyl-9,10-anthraquinones were studied. It was established that under irradiation, the hydrogen atom of the substituted methyl group is transferred to aperi-quinoid oxygen atom to form the corresponding 9-hydroxy1, 10-anthraquinone-1-arylcyanomethides. Dark transformations of photoinduced quinonemethides result from three competing parallel processes: intramolecular transfer of the hydrogen atom, a reaction with a solvent (alcohol), and oxidation by dissolved oxygen. The kinetics of these reactions were studied.
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  • 82
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    Russian chemical bulletin 44 (1995), S. 847-850 
    ISSN: 1573-9171
    Keywords: fluoroamines, thermal decomposition ; nitrocompounds ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the thermal decomposition of bis(2,2-dinitropropyl)-N-fluoroamine are studied in the liquid phase. The reaction is autocatalytic in a melt. In dilute solution, the reaction rate is described by the first-order law. It is tens of times faster in polar sulfolan than in weakly polar dimethyl phthalate. A mechanism of the decomposition involving the formation of a cyclic transition state at the first, limiting stage of the process is suggested.
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  • 83
    ISSN: 1573-9171
    Keywords: solvomercuration ; mechanism of reaction ; mercury acetate ; salt effect ; alkenes ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the addition of Hg(OAc)2 to strained and unstrained alkenes was studied in MeOH solution in the presence of NaOAc. Based on salt effects, the HgOAc ion was shown to be the actual reagent in the reaction of the unstrained alkenes, whereas Hg(OAc)2 was the reagent in the case of the strained alkenes. The mechanisms of the solvomercuration of alkenes of various structures were proposed.
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  • 84
    ISSN: 1573-9171
    Keywords: photocatalyst ; adsorption ; surfactant ; kinetics ; colloid ; cadmium sulfide
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Photoreduction of Methyl Orange dye (MOr) by sodium sulfide was studied under steady-state photolysis (λ = 365 nm). The reaction was sensitized by the CdS colloid with the characteristic ∼5-nm particle size. The quantum yield of the reaction is independent of the light intensity when the latter is less than 5 mW cm−2. The form of the dependence of the initial quantum yield of the reaction on [MOr] coincides qualitatively with the adsorption isotherm of the dye on the CdS surface. The reaction kinetics under steady-state irradiation were analyzed. The kinetics in solution as a whole are shown to be adequate to those on a single colloidal particle. On the basis of the experimental data, two types of surfaces of the colloidal particles are suggested (“open” and “covered” with macromolecules of a colloid stabilizer), which significantly differ in the rate at which they establish an adsorption-desorption equilibrium with the solution.
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  • 85
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    Russian chemical bulletin 44 (1995), S. 840-843 
    ISSN: 1573-9171
    Keywords: isopentenols, reaction scheme ; Prins reaction ; acid catalysis ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The reactions occurring in an equilibrium mixture of 3-methyl-1-buten-3-ol and 3-methyl-2-buten-1-ol in 24–49 % aqueous solutions of H2SO4 yield isoprene, 3-methyl-3-buten-1-ol, isobutylene, formaldehyde, 3-methylbutane-1,3-diol. Isobutylene is rapidly hydrated to give 2-methylpropan-2-ol. The presence of formaldehyde in the reaction mixture indicates that the transformations involve the reverse Prins reaction. On the basis of experimental and literature data, two most probable reaction schemes were suggested.
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  • 86
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    Russian chemical bulletin 44 (1995), S. 989-991 
    ISSN: 1573-9171
    Keywords: sorption ; kinetics ; mechanism ; polymer ; dibenzo-18-crown-6 ; RbCl ; equilibrium constant ; diffusion coefficients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics and mechanism of the sorption of rubidium chloride from ethanol by granulated polymer containing immobilized dibenzo-18-crown-6 are studied. The sorption of RbCl is controlled by internal diffusion accompanied by complex formation in the polymer. The equilibrium constants of the sorption and diffusion coefficients of the electrolyte in the sorbent are calculated.
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  • 87
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    Plant systematics and evolution 196 (1995), S. 141-151 
    ISSN: 1615-6110
    Keywords: Orchidaceae ; Loroglossum hircinum ; Compound pollen ; pollinium ; pollen tubes ; generative cell ; evolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The structure of the massulae composing the pollinium ofLoroglossum hircinum was studied before pollination and 12 and 24 hours afterwards. The grains are grouped in tetrads closely packed in massulae. The exine is only present on the outside of the massulae. The intine consists of two layers: a compact layer surrounding the pollen grain and a looser layer surrounding the pollen grain and a looser layer surrounding the tetrad. Twelve hours after pollination, pollen volume and the space between the tetrads increase due to vacuolization. Twenty-four hours after pollination, pollen volume and tetrad spacing are higher due to vacuolization and some grains have emitted pollen tubes. Pollen growth due to vacuole formation, and the absence of common walls between adjacent tetrads lead to crumbling of the massulae. The mature pollen grain does not have apertures: the site of pollen tube emission is determined after pollination. The first grains to germinate are those in the centre of the massula. The vegetative cell nucleus is the first to enter the pollen tube; the generative cell elongates and undergoes the second haploid mitosis shortly after entering the pollen tube.
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  • 88
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    Plant systematics and evolution 198 (1995), S. 167-178 
    ISSN: 1615-6110
    Keywords: Fabaceae ; Arachis ; Arachis hypogaea ; RAPD ; systematics ; evolution ; germplasm resources
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    Topics: Biology
    Notes: Abstract Twenty-six accessions of wildArachis species and domesticated peanuts,A. hypogaea, introduced from South America were analyzed for random amplified polymorphic DNA (RAPD). The objective of the study was to investigate inter- and intraspecific variation and affinities among species of sect.Arachis which have been proposed as possible progenitors for the domesticated peanut. Ten primers resolved 132 DNA bands which were useful for separating species and accessions. The most variation was observed among accessions ofA. cardenasii andA. glandulifera whereas the least amount of variation was observed inA. hypogaea andA. monticola. The two tetraploid species could not be separated by using RAPDs.Arachis duranensis was most closely related to the domesticated peanut and is believed to be the donor of the A genome. The data indicated thatA. batizocoi, a species previously hypothesized to contribute the B genome toA. hypogaea, was not involved in its evolution. The investigation showed that RAPDs can be used to analyze both inter- and intraspecific variation in peanut species. Southern hybridization of RAPD probes to blots containing RAPD of theArachis species provided information on genomic relationships and revealed the repetitive nature of the amplified DNA.
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  • 89
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    Plant systematics and evolution 206 (1997), S. 33-45 
    ISSN: 1615-6110
    Keywords: Compositae ; Barnadesioideae ; Doniophyton ; Chuquiraga ; Argentina ; Chile ; evolution ; systematics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract This revision describes, illustrates and documents morphological variation inDoniophyton (Compositae, Barnadesioideae), restricted to Argentina and Chile. Two species are recognized,D. anomalum andD. weddellii (sp. nova), possessing distinct morphological and chromosomal features, elevational tolerances, and nearly allopatric distributions.Doniophyton weddellii occurs primarily in central to northern Andean Chile and Argentina from 1900–4000 m a. s. l.;D. anomalum is found principally in centralwestern Argentina and south into Patagonia at 0–1800 m a. s. l. Close relationship exists withChuquiraga of subfam.Barnadesioideae. It is hypothesized thatDoniophyton evolved out ofChuquiraga in the high central Andes between Chile and Argentina. It is suggested thatD. weddellii differentiated first, correlating with an aneuploid chromosomal decrease from n = 27 (inChuquiraga) to n = 25. Further evolution and chromosomal decrease to n = 24 resulted inD. anomalum, with accompanying migration into southern Andes and Patagonia. Nomenclatural changes result from examination of protologues and type specimens:Doniophyton anomalum replaces the commonly used nameD. patagonicum, and a new species,D. weddellii, is described for the taxon masquerading under the routinely used superfluous nameD. andicola.
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  • 90
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    Biology and philosophy 10 (1995), S. 181-196 
    ISSN: 1572-8404
    Keywords: Biological species concept ; gene flow ; gene circulation ; Ernst Mayr ; stalemates ; typology ; evolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Philosophy
    Notes: Abstract Over the decades, there has been substantial empirical evidence showing that the unity of species cannot be maintained by gene flow. The biological species concept is inconclusive on this point. The suggestion is made that the unity of species is maintained rather by selection constantly spreading new alleles throughout the species, or bygene circulation. There is a lack in conceptual distinction between gene flow and gene circulation which lies at the heart of the problem. The concept of gene circulation also sheds some new light on the problem of typology and on such a broad concept as evolution. A new species definition is proposed.
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    Biology and philosophy 10 (1995), S. 339-356 
    ISSN: 1572-8404
    Keywords: Species ; lineage ; individual ; class ; evolution ; organism ; population
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Philosophy
    Notes: Abstract What are species? One popular answer is that species are individuals. Here I develop another approach to thinking about species, an approach based on the notion of a lineage. A lineage is a sequence of reproducing entities, individuated in terms of its components. I argue that one can conceive of species as groups of lineages, either organism lineages or population lineages. Conceiving of species as groups of lineages resolves the problems that the individual conception of species is supposed to resolve. It has added the virtue of focusing attention on the characteristic of species that is most relevant to understanding their role in evolutionary processes, namely, the lineage structure of species.
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    Biology and philosophy 10 (1995), S. 435-457 
    ISSN: 1572-8404
    Keywords: Functional explanation ; morphology ; ethology ; evolution
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    Topics: Biology , Philosophy
    Notes: Abstract This article deals with a type of functional explanation, viability explanation, that has been overlooked in recent philosophy of science. Viability explanations relate traits of organisms and their environments in terms of what an individual needs to survive and reproduce. I show that viability explanations are neither causal nor historical and that, therefore, they should be accounted for as a distinct type of explanation.
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  • 93
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    Biology and philosophy 10 (1995), S. 389-417 
    ISSN: 1572-8404
    Keywords: Catalysis ; chance ; determinism ; emergence of life ; evolution ; non-equilibrium thermodynamics ; panspermia ; protometabolism ; reduction ; RNA world ; self-organization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Philosophy
    Notes: Abstract This paper calls attention to a philosophical presupposition, coined here “the continuity thesis” which underlies and unites the different, often conflicting, hypotheses in the origin of life field. This presupposition, a necessary condition for any scientific investigation of the origin of life problem, has two components. First, it contends that there is no unbridgeable gap between inorganic matter and life. Second, it regards the emergence of life as a highly probable process. Examining several current origin-of-life theories. I indicate the implicit or explicit role played by the “continuity thesis” in each of them. In addition, I identify the rivals of the “thesis” within the scientific community — “the almost miracle camp.” Though adopting the anti-vitalistic aspect of the “continuity thesis”, this camp regards the emergence of life as involving highly improbable events. Since it seems that the chemistry of the prebiotic stages and of molecular self-organization processes rules out the possibility that life is the result of a “happy accident,” I claim that the “almost miracle” view implies in fact, a creationist position.
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  • 94
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    Biology and philosophy 12 (1997), S. 207-224 
    ISSN: 1572-8404
    Keywords: evolution ; epistemology ; evolutionary epistemology ; naturalized epistemology ; thought experiments ; modality ; utility ; fitness ; adaptation ; reliability ; possible worlds
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Philosophy
    Notes: Abstract Roy Sorensen advances an evolutionary explanation of our capacity for thought experiments which doubles as a naturalized epistemological justification. I argue Sorensen”s explanation fails to satisfy key elements of environmental-selectionist explanations and so fails to carry epistemic force. I then argue that even if Sorensen succeeds in showing the adaptive utility of our capacity, he still fails to establish its reliability and hence epistemic utility. I conclude Sorensen”s account comes to little more than a “just-so story”.
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    Biology and philosophy 12 (1997), S. 385-397 
    ISSN: 1572-8404
    Keywords: morality ; evolution ; error theory
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    Topics: Biology , Philosophy
    Notes: Abstract Michael Ruse‘s Darwinian metaethics has come under just criticism from Peter Woolcock (1993). But with modification it remains defensible. Ruse (1986) holds that people ordinarily have a false belief that there are objective moral obligations. He argues that the evolutionary story should be taken as an error theory, i.e., as a theory which explains the belief that there are obligations as arising from non-rational causes, rather than from inference or evidential reasons. Woolcock quite rightly objects that this position entails moral nihilism. However, I argue here that people generally have justified true beliefs about which acts promote their most coherent set of moral values, and hence, by definition, about which acts are right. What the evolutionary story explains is the existence of these values, but it is not an error theory for moral beliefs. Ordinary beliefs correspond to real moral properties, though these are not objective or absolute properties independent of anyone‘s subjective states. On its best footing, therefore, a Darwinian metaethics of the type Ruse offers is not an error theory and does not entail moral nihilism.
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    Pharmaceutical research 12 (1995), S. 599-604 
    ISSN: 1573-904X
    Keywords: famotidine ; degradation ; isothermal ; nonisothermal ; kinetics ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of hydrolysis of famotidine in aqueous solution was studied by isothermal and nonisothermal method over the pH range of 1.71 to 10.0. Nonisothermal kinetics was studied with the purpose of determining its use in the establishment of the expiration date of pharmaceutical preparations, particularly drugs in solutions and for assessment of stability characteristics of pharmaceutical formulations during the development stage. A comparison of isothermal (55, 70 and 85°C) and nonisothermal kinetics was performed. Aqueous solutions of famotidine were buffered at pH 1.71, 2.24, 2.66, 4.0, 8.5, 9.0 and 10.0 were used. In the nonisothermal studies, the temperature rate of the reaction was continuously varied throughout the experiment. The energies of activation were found to be in close agreement for isothermal and nonisothermal studies, indicating that nonisothermal studies may save considerable amount of time in the early stages of drug development and stability testing. Logk-pH profiles were constructed for 55, 70 and 85°C from the first-order rate constants obtained from isothermal studies at pH values ranging from 1.71 to 10.00. The pH-rate profile indicated that famotidine undergoes specific acid catalysis in the acidic region and general base catalysis in the alkaline region. Hydrolysis in the acidic and alkaline media resulted in the formation of four and five degradation products, respectively. A possible degradation pathway for the acidic and alkaline hydrolysis was discussed.
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  • 97
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    Evolutionary ecology 11 (1997), S. 301-335 
    ISSN: 1573-8477
    Keywords: ecological associations ; evolution ; integrative biology ; Opisthobranchia ; resource tracking ; Sacoglossa ; Ulvophyceae
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Evolution in the opisthobranch order Sacoglossa has been closely linked to their specialized suctorial herbivorous habits. All shelled Sacoglossa (about 20% of the species) feed on one algal genus, Caulerpa. The non-shelled Sacoglossa have 'radiated' to other diets, mainly siphonalean or septate green algae (Class Ulvophyceae). Comparing the phylogeny of sacoglossan genera with the phylogeny of the Ulvophyceae indicates that co-speciation may have taken place at the basal node of the Sacoglossa, and that host switching has taken place several times in the two non-shelled clades. It is suggested that the most important evolutionary process has been speciation by 'resource-tracking'; the resource tracked is most probably cell wall composition of the algal prey. The fossil record of extant sacoglossan genera dates back to the Eocene and, based on the fossil record of siphonalean green algae, the Sacoglossa most likely appeared in the Cretaceous. It is hypothesized that the ancestral sacoglossan was epifaunal, suctorial and herbivorous, and the 'ancestral' food plant was not Caulerpa, but filamentous, calcified, now extinct, Udoteaceae.
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  • 98
    ISSN: 1573-8477
    Keywords: dispersal ; evolution ; evolutionarily stable strategy ; migrant ; resident ; survival
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract We investigate how age-structure and differences in certain demographic traits between residents and immigrants of a single species act to determine the evolutionarily stable dispersal strategy in a two-patch environment that is heterogeneous in space but constant in time. These two factors have been neglected in previous models of the evolution of dispersal, which generally consider organisms with very simple life-cycles and assume that, whatever their origin, individuals in a given habitat have the same bio-demographic characteristics. However, there is increasing empirical evidence that dispersing individuals have different demographic properties from phylopatric ones. We develop a matrix model in which recruitment depends on local population densities. We assume that dispersal entails a proportional cost to immigrant fecundity, which can be compensated by differences in survival rates between immigrants and residents. The evolutionarily stable strategies (ESS) for dispersal are identified using a combination of analytical expressions and numerical simulations. Our results show that philopatry is selected (1) when dispersal rates do not vary in space, (2) when the metapopulation is a source-sink system and (3) when dispersal rates vary in space (asymmetric dispersal) and immigrants do not compensate for their reduced fecundity. We observe that non-zero asymmetric dispersal rates may be evolutionarily stable when (1) immigrants and residents are demographically alike and (2) immigrants compensate totally for their reduced fecundity through an increase in adult survival. Under these conditions, we find that the ESS occurs when the fitnesses at equilibrium in the two habitats, measured in our model by the realized reproductive rates, are each equal to unity. A comparison with previous studies suggests a unifying rule for the evolution of dispersal: the dispersal rates which permit the spatial homogenization of fitnesses are ESSs. This condition provides new insight into the evolutionary stability of source-sink systems. It also supports the hypothesis that immigrants have adapted demographic strategies, rather than the hypothesis that dispersal is costly and immigrants are at a disavantage compared with residents.
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    Hydrobiologia 295 (1995), S. 167-181 
    ISSN: 1573-5117
    Keywords: mangrove ; Avicennia ; evolution ; fossils ; pollen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Without continental drift, the diversity and distribution of many species, including mangrove plants, would be very different today. First, there would be fewer pantropic genera and many more endemics. Second, their characteristics would not be as common and widespread as some are today. Continental drift has brought about the massive mixing and dispersal of genes in geologically recent times, greatly enhancing the evolutionary process; particularly for flowering plants — the angiosperms, which evolved during the period. Mangrove plants are comprised of approximately 70 species from 20 quite different angiosperm families. Most taxa are characterized by special physiological abilities and structural forms, enabling them to live in both seasonally fluctuating saline conditions, and water-saturated soils. Their occurrence is mostly tropical, perhaps because of harsh physiological conditions of intertidal habitats; but distributions of specific taxa do not fully concur with the idea of a completely tropical evolution, at least for some important species. At least one genus of mangrove tree, Avicennia, occurs around the world, chiefly in tropical estuarine habitats, although they also range into temperate latitudes, especially in the south. Around the world, there are no more than ten species of Avicennia recognised today, but their diagnostic determinants were inadequate prior to recent studies using both numerical analyses of morphological parameters and isozymes. Such analyses significantly reduced the number of apparent species, notably around Australia, and provided a basis for the revision of distributional records throughout the Indo West Pacific region. One species, A. marina, was found to be widespread and morphologically variable with genes divided into characteristic groupings of at least three geographic areas in the region. Based on these findings, there are several novel inferences to be made regarding the evolution of this genus. A western Gondwanan origin is proposed, with subsequent radiation of several taxa facilitated via the tectonic dispersal of southern continental fragments.
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    Hydrobiologia 365 (1997), S. 33-46 
    ISSN: 1573-5117
    Keywords: Phylogeny ; cladistics ; taxonomy ; systematics ; classification ; evolution ; history ; chronicle ; Nemertea ; Hoplonemertea
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract I review how some influential nemertean systematistshave perceived and illustrated phylogenetic trees andargue that the nineteenth century nemerteantaxonomists still influence many contemporarynemertean taxonomists to a high degree. By showing hownineteenth century systematics differs from moremodern views on trees, I hope to convey the advantagesof a cladistic approach to tree-thinking and nemerteansystematics. Furthermore I propose a systematizationof the Eureptantia that illustrates the cladisticapproach to tree-thinking but, more importantly, isalso a better representation of eureptantic phylogenythan previous classifications.
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