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  • kinetics  (94)
  • Springer  (94)
  • Institute of Physics
  • 1995-1999  (58)
  • 1990-1994  (36)
  • 1940-1944
  • 1997  (58)
  • 1993  (36)
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  • 1995-1999  (58)
  • 1990-1994  (36)
  • 1940-1944
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  • 1
    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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  • 2
    ISSN: 1572-879X
    Keywords: Fischer-Tropsch synthesis ; reaction activation barrier ; carbon chain growth and termination ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A method is established, by which the difference of the reaction activation barriers of carbon chain growth and termination in Fischer-Tropsch (FT) synthesis can be determined from experiments. A FT synthesis is carried out on Fe/Zn catalyst. We apply the method to analyze the experimental result and obtain the difference of reaction activation barriers of carbon chain growth and termination of α-olefins on the catalyst.
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  • 3
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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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  • 4
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    Cellular and molecular life sciences 49 (1993), S. 110-117 
    ISSN: 1420-9071
    Keywords: Polymerization ; sickle hemoglobin ; sickle cell disease ; kinetics ; thermodynamics ; polymer domains ; nucleation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The polymerization of sickle hemoglobin occurs by the same mechanisms in solutions and in cells, and involves the formation of 14 stranded fibers from hemoglobin molecules which have assumed a deoxy quaternary structure. The fibers form via two types of highly concentration-dependent nucleation processes: homogeneous nucleation in solutions with hemoglobin activity above a critical activity, and heterogeneous nucleation in similarly supersaturated solutions which also contain hemoglobin polymers. The latter pathway is dominant, and creates polymer arrays called domains. The individual polymers bend, but also cross-link, and the resulting mass behaves as a solid. The concentration of polymerized hemoglobin increases exponentially unless clamped by rate limiting effects such as oxygen delivery.
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  • 5
    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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  • 6
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    Biodegradation 4 (1993), S. 163-170 
    ISSN: 1572-9729
    Keywords: factorial analysis ; kinetics ; methane ; methanotrophs ; nutrients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The effect of different mineral nutrients on the kinetics of methane biodegradation by a mixed culture of methanotrophic bacteria was studied. The substrate factors examined were ammonia, iron, copper, manganese, phosphate, and sulphide. The presence of iron in the growth medium had a strong effect on the yield coefficient. Yield coefficients up to 0.49 mg protein per mg methane were observed when iron was added at concentrations of 0.10–5.0 mg/l. Iron addition also increased the maximum methane utilization rate. The same effect was observed after addition of ammonium to a medium where nitrate was the only nitrogen source. The observed Monod constant for methane utilization increased with increasing concentration of ammonia. This shows that ammonia is a weak competitive inhibitor as observed by other researchers. Relatively high levels of both ammonia (70 mg/l) and copper (300 µg/l) inhibited the methane degradation, probably due to the toxic effect of copper-amine complexes.
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  • 7
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    Aquatic sciences 55 (1993), S. 103-111 
    ISSN: 1420-9055
    Keywords: iron(III) (hydr)oxide ; fulvic acid ; iron redox cycling ; dissolution ; surface reactivity ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10−4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the 〉 FeIII-OH/Fe(II) “wheel” coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)3(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.
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  • 8
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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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  • 9
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    European journal of clinical pharmacology 44 (1993), S. 231-235 
    ISSN: 1432-1041
    Keywords: Carbamazepine ; kinetics ; population pharmacokinetics ; bioavailability ; controlled release ; non-linear model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The absorption properties of a conventional tablet of carbamazepine (T) and a controlled release form of carbamazepine (TCR) have been compared using a nonlinear mixed effect model (NONMEM). Plasma carbamazepine concentration data were obtained from an open, steady-state, crossover bioavailability study in which 494 measurements were obtained from 13 patients, with an equal number of samples per patient for each dosage form. The pharmacokinetic model used was a one-compartment open model with first-order absorption and elimination. The objective function was used as a measure of the goodness of fit of the model to the data. Body weight was an important determinant of carbamazepine clearance (CL) but not volume of distribution (V). Accounting for the interindividual variability in volume of distribution did not significantly influence the objective function. Including different rates of absorption (ka) for the two dosage forms resulted in a significant improvement in the objective function, as well as reducing the interindividual variability in the rate of absorption. Adding a parameter for relative bioavailability (f) of TCR improved the objective function statistically, but an unrealistic value for V was obtained, and the absorption and elimination rates appeared to be transposed in the classical “flip-flop” manner. Fixing V to the value obtained before introducing f did not change the objective function and permitted estimation of f without the confounding influence of excessive parameters. The final population parameter estimates (standard error of estimate) were: CL, 0.0522 (0.0019) l·h−1·kg−1; V, 63.7 (FIXED)l; kaT, 0.312 (0.064) h−1; kaTCR, 0.149 (0.016) h−1; f, 1.01 (0.0326); variance (additive) in CL, 0.291 (0.083) (l·h−1·kg−1)2; residual intrasubject error variance (additive), 0.572 (0.082) (mg·l−1)2. The 95% confidence interval of the extent of absorption (f) of 93.6%–107.4% was well within the generally accepted range of ±20%, while the rate of absorption of Tegretol CR was significantly slower than that of Tegretol, as expected for a controlled release product.
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  • 10
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    Journal of thermal analysis and calorimetry 39 (1993), S. 15-20 
    ISSN: 1572-8943
    Keywords: alloys ; high-temperature sulphidation ; kinetics ; new thermobalane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird ein neue Apparat zur Untersuchung der Hochtemperatur-Sulfidierung von Metallen in H2/H2S Atmosphare beschrieben. Der Unterschied zwischen diesem Apparat und dem fruher benutzten, besteht im Gasdosierungsystem. Wasserstoff reagiert teilweise mit Schwefel, was eine stabile Zusammensetzung des Gasgemisches beim niedrigen Schwefeldampfdruck sichert. Gewichtsmessungen von Metallen und Legierungen konnen in diesem System bei Temperaturen von 1073 bis 1473 K mit einer Genauigkeit von 10−6 g ausgefuhrt werden.
    Notes: Abstract A new thermogravimetric apparatus for studying the kinetics of metal sulphidation in a H2/H2S gas mixture is described. The main difference between this device and other equipment is the application of hydrogen to obtain a H2/H2S mixture at suitable sulphur partial pressures at a total mixture pressure of 1 atm. The use of the carrier gas allows the measurement of sulphidation kinetics under dynamic conditions and consequently over a much wider pressure range of sulphur vapour, down to 10−12 atm.
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  • 11
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    Journal of thermal analysis and calorimetry 39 (1993), S. 65-74 
    ISSN: 1572-8943
    Keywords: electrical conductivity ; hydrazone complexes ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Bei zwei verschiedenenpH-Werten wurden die Zn-, Cd- und Hg-Komplexe von Isatinisonicotinoylhydrazon hergestellt. Diese wurden thermisch untersucht (TG, DTG, DTA) und die Gleichstromleitfähigkeit von gepreßten Pulverproben als eine Funktion der Temperatur untersucht. Sowohl für die Liganden als auch für die Komplexe wurden die Aktivierungsenergien (ΔE) berechnet, wobei sich für die Liganden niedrigere Werte ergaben. Man fand, daß die Größe von ΔE durch die Art des Metalles und denpH-Wert bei der Herstellung beeinflußt wird.
    Notes: Abstract The complexes of Zn, Cd and Hg of isatin isonicotinoyl hydrazone were prepared at two differentpHs. Their thermal studies (TG, DTG and DTA) have been made and the DC electrical conductivity of compressed powder samples as a function of temperature was investigated. The activation energies (ΔE) were calculated for the ligand and the complexes which showed that the ligand has a lower value of ΔE than the complexes. The magnitude of ΔE was found to be affected by the nature of the metal and thepH of preparation.
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  • 12
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    Journal of thermal analysis and calorimetry 39 (1993), S. 75-86 
    ISSN: 1572-8943
    Keywords: chlorination ; kinetics ; WO3+CCl4 reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels Thermogravimetrie wurde die Chlorierungskinetik von alkaliversetztem (K und Li) Wolframtrioxid untersucht, wobei CCl4 als Chlorierungsreagens fungierte. Die Reaktivität der modifizierten Proben wurden mit der von reinem WO3 verglichen. Für die reinen und für die alkaliversetzten Proben wurden ähnliche scheinbare Aktivierungsenergien gefunden. Der Zusatz von Kalium verursacht jedoch eine starke Abnahme der ursprünglichen Reaktionsgeschwindigkeit, während oberflächiges Lithium keinen Effekt zeigt. Während der Chlorierung wurde eine ständige Senkung der linearen Reaktionsgeschwindigkeit für beide Proben festgestellt, was mit Rückhalteeffekten von oberflächigen Nebenprodukten und Alkalizusätzen erklärt wird. Zur Beschreibung der isothermen TG-Kurven wurde ein entsprechendes kinetisches Modell angenommen, welches auf einer monoton steigenden Inhibition dieser Proben basiert. Die auf der Grundlage dieses Modelles berechnete Kurve stimmt recht gut mit den experimentellen Ergebnissen überein.
    Notes: Abstract The chlorination kinetics of alkali-added (K and Li) tungsten trioxide were studied by thermogravimetry, using gaseous CCl4 as chlorinating agent. The reactivity of the modified samples was compared to the results on the chlorination of pure WO3. Similar apparent activation energies were found for the pure and alkali-added samples. However, potassium additive resulted in a strong decrease of the initial reaction rate, while surface lithium has no influence on it. During the chlorination a continuous decrease of the linear reaction rate was observed for both samples, which was explained by retarding effects of surface by-products and alkali additives. For describing the isothermal TG curves an appropriate kinetic model, based on the monotonously increasing inhibition of these species was assumed. The curve calculated with this model fits well to the experimental results.
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  • 13
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    Journal of thermal analysis and calorimetry 39 (1993), S. 229-238 
    ISSN: 1572-8943
    Keywords: epoxy resins ; kinetics ; thermal stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die Vernetzungsreaktionen der Epoxidharze Tetraglycidyl-diamino-diphenyl-methan (TGDDM) und Tetraglycidyl-methylen-bis(o-toluidin) (TGMBT) unter Verwendung von Diaminodiphenylsulfon (DDS), Diaminodiphenylmethan (DDM) und Diethylentriamin (DETA) als Vernetzungsmittel wurden kinetisch mittels DSC untersucht. Die dynamischen Scans im Temperaturbereich 20°–300°C wurden analysiert, um unter Anwendung einiger empirischer Gleichungen die Aktivierungsenergie und die Reaktionsordnung des Vernetzungsprozesses zu ermitteln. Die Aktivierungsenergie der einzelnen Epoxy-Systeme liegt im Bereich 71.9–110.2 kJ·mol−1. An der ausgehärteten Harze wurde mittels TG in einer statischen Luftatmosphäre un deiner Aufheizgeschwindigkeit von 10 Grad/min die Kinetik des termischen Abbaues untersucht. Man fand, daß die thermiscehn Abbaureaktionen in einem Schritt ablaufen und ihre Aktivierungsenergie im Intervall 27.6–51.4 kJ·mol−1 liegt.
    Notes: Abstract The curing reactions of the epoxy resins tetraglycidyl diaminodiphenyl methane (TGDDM) and tetraglycidyl methylenebis (o-toluidine) (TGMBT) using diaminodiphenyl sulfone (DDS), diaminodiphenyl methane (DDM) and diethylenetriamine (DETA) as curing agents were studied kinetically by differential scanning calorimetry. The dynamic scans in the temperature range 20°–300°C were analyzed to estimate the activation energy and the order of reaction for the curing process using some empirical relations. The activation energy for the various epoxy systems is observed in the range 71.9–110.2 kJ·mol−1. The cured epoxy resins were studied for kinetics of thermal degradation by thermogravimetry in a static air atmosphere at a heating rate of 10 deg·min−1. The thermal degradation reactions were found to proceed in a single step having an activation energy in the range 27.6–51.4 kJ·mol−1.
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  • 14
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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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  • 15
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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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  • 16
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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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  • 17
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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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  • 18
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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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  • 19
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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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  • 20
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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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  • 21
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    Journal of thermal analysis and calorimetry 48 (1997), S. 413-425 
    ISSN: 1572-8943
    Keywords: alcoholic fermentation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    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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  • 22
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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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  • 23
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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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  • 24
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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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  • 25
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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
    Source: Springer Online Journal Archives 1860-2000
    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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  • 26
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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
    Source: Springer Online Journal Archives 1860-2000
    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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    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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  • 28
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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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  • 29
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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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  • 30
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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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  • 31
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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
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    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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  • 32
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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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  • 33
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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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  • 34
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    Journal of thermal analysis and calorimetry 39 (1993), S. 87-95 
    ISSN: 1572-8943
    Keywords: gamma radiation effects ; graphite-hematite system ; kinetics
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels isothermer und dynamischer TG wurde im Graphit-Eisen(III)oxidsystem in Luft der Einfluß von60Co-Gammastrahlung und von verschiedenen Probenzusammensetzungen auf die Reduktion von Hämatit zu Eisen untersucht. Entsprechend verschiedener theoretischer Modelle heterogener Reaktionen wurde eine kinetische Analyse der isothermen Daten durchgeführt und die Ergebnisse zeigten, daß das dreidimensionale Phasengrenzenmodell die beste Übereinstimmung liefert. Die Analyse der dynamischen TG-Daten wurde mittels der Integralmethode von Ozawa, der Coats-Redfem-Methode und einer zusammengesetzten Methode auf der Grundlage der modifizierten Coats und Redfern Gleichung durchgeführt. Die Aktivierungsparameter wurden berechnet und die Ergebnisse der verschiedenen Methoden miteinander verglichen und diskutiert. Strahlung scheint keine Änderung des Reaktionsmodelles oder des Mechanismus hervorzurufen. Durch Bestrahlung gibt es aber ein Absinken der Aktivierungsenergie und des Frequenzfaktors sowie ein Absinken der Halbwertszeit der Reaktion, was bei höheren Temperaturen und höherer Dosis bemerkenswert groß ist.
    Notes: Abstract The effects of60Co-gamma radiation and of various sample composition on the reduction of hematite to iron in the graphite-iron(III) oxide system in air were studied using isothermal and dynamic TG techniques. Kinetic analysis of isothermal data were performed according to various theoretical models of heterogeneous reactions and the results showed that the three-dimensional phase boundary model gives the best fit of data. Analysis of dynamic TG data were made using Ozawa integral method, Coats-Redfern method and a composite method based on the modified Coats and redfern equation. The activation parameters were calculated and the results of the different methods were compared and discussed. Radiation apparently did not introduce a change in the reaction model or mechanism. However, there is a decrease in activation energy and frequency factor upon irradiation and a decrease in the half-life time of the reaction which is remarkable at the higher temperatures and higher doses.
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  • 35
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    Journal of thermal analysis and calorimetry 39 (1993), S. 217-220 
    ISSN: 1572-8943
    Keywords: DSC ; edible oils ; isothermal method ; kinetics
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Unter Einsatz der isothermen Methode wurden kinetische Untersuchungen der thermooxidativen Zersetzung einiger Speiseöle durchgeführt. Zur Bestimmung des Umwandlungsgrades wurde ein DS-Kalorimeter von DuPont eingesetzt. Grundlage der Untersuchung bildeten Leinöl, Rizinusöl und Olivenöl.
    Notes: Abstract The thermooxidative decompositions of some edible oils were investigated. Isothermal measurements of convention were made with a Du Pont differential scanning calorimeter. Linseed oil, castor oil, olive oil and cod-liver oil were investigated.
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  • 36
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    Journal of thermal analysis and calorimetry 39 (1993), S. 351-358 
    ISSN: 1572-8943
    Keywords: epoxy resin ; kinetics ; polyamide hardener
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels DSC wurde die Optimierung des Einsatzverhältnisses von Epoxidnovolackharz Dobeckot E4 und Polyamidhärtungsmittel EH411 durchgeführt. Die Daten ergaben, daß ein Harz-Polyamid-Verhältnis von 100∶40 bzw. 100∶50 das Optimum zu sein scheint, bei dem die Aushärtung am größten ist. Mittels isothermer und dynamischer DSC-Methoden wurden die kinetischen Parameter für diese Ansätze ermittelt. Unter Anwendung der isothermen DSC-Methode im Temperaturbereich 70°–90°C wurde die Geschwindigkeitskonstante für den Aushärtungsprozeß dieser Ansätze ermittelt. Diese wurden mittels Extrapolation der erhaltenen Angaben für höhere Temperaturen auch für die Temperatur 201°C (Raumtemperatur) vorhergesagt. Vorhergesagte und experimentell ermittelte Werte stehen in guter Übereinstimmung zueinander.
    Notes: Abstract The optimization of proportions of novolac epoxy resin, Dobeckot E4 and polyamide hardener, EH411 has been established by DSC and the data indicates that resin-polyamide, 100∶40 and 100∶50, appear to be optimum where ‘extent of cure’ is maximum. The kinetic parameters for these formulations have been evaluated using isothermal and dynamic modes by employing DSC. The rate constants have been evaluated for curing process of these formulations using isothermal DSC mode in the temperature range of 70°–90°C. These have also been predicted at 20°±1°C (room temperature) by extrapolating the data obtained at elevated temperatures. A comparison of the predicted values with the experimental values shows that there is a good agreement between them.
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    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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    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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  • 39
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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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  • 40
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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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  • 41
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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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  • 42
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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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  • 43
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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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  • 44
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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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  • 45
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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
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    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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  • 46
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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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  • 47
    ISSN: 1573-4889
    Keywords: oxidation ; Incoloy 909 ; superalloy ; scale ; high temperature ; kinetics
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    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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  • 48
    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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  • 49
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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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  • 50
    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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  • 51
    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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  • 52
    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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  • 53
    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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  • 54
    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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  • 55
    ISSN: 1573-4943
    Keywords: Sulphydryl groups ; multiple ; hemoglobin ; kinetics ; ionizable groups
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Pigeon hemoglobin has eight reactive sulphydryl groups per (tetramer) molecule, as determined by Boyer titration with p-chloromercuribenzoate. However, only four of these are titra-table with 5,5′-dithiobis(2-nitrobenzoate) under the same experimental conditions. The time course of the reaction of pigeon hemoglobin with 5,5′-dithiobis(2-nitrobenzoate) is biphasic. In thepH range 6–9, the fast phase is between one and two orders of magnitude faster than the slow phase. For the fast phase,k app, the apparent second-order rate constant, increases monotonously withpH. Quantitative analysis reveals that the reactionof the sulphydryl group responsible for this phase is coupled to the ionization of two groups with pK a values of 6.15±0.1 and 8.5±0.1. These pK a values are assigned to HisHC3(146)β and to the CysF9(93)β sulphydryl group, respectively. For the slow phase thek app vs.pH profiles are bowl-shaped. Analysis reveals that the reaction of the sulphydryl group to which this phase may be attributed is coupled to the ionization of two groups with mean pK a values of 6.53±0.1 and 8.25±0.1. Examination of the structure of hemoglobin allows us to assign these values to HisG19(117)β and CysB5(23)β, respectively. The CysB5(23)β sulphydryl is in the region of the molecule where amino acid substitutions have been found to give rise to significant changes in the oxygen affinity of hemoglobin [Huanget al. (1990),Biochemistry 29, 7020–7023.
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  • 56
    ISSN: 1573-4943
    Keywords: Hemoglobin ; sulphydryl group ; ionizable groups ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Dog hemoglobin has four sulphydryl groups per (tetramer) molecule located at the G18(111)a and F9(93)β positions. The two sulphydryls at the G18(111)a positions are unreactive toward nonmercurial sulphydryl reagents, but those at the F9(93)β positions are reactive toward these reagents. We have studied the kinetics of the reaction of dog hemoglobin with 5,5′-dithiobis (2-nitrobenzoic acid) as a function ofpH. At allpH values studied, the reaction is kinetically monophasic. Quantitative analysis of thepH dependence of the apparent second-order rate constant shows that two ionizable groups are linked to the reaction of the sulphydryl group. TheirpK a values are 5.57 and 9.0. These values are assigned to HisHC3(146)β and to the CysF9(93)β sulphydryl. We find that dog carbonmonoxyhemoglobin is significantly—almost an order of magnitude—less reactive than the aquomet, azidomet, and oxy derivatives. This result may be due to a greater tendency (at acidpH) for the salt bridge between HisHC3(146)β and AspFG1(94)β to form in the carbonmonoxy than in the other derivatives. Formation of this salt bridge is known to hinder access to the CysF9(93)β sulphydryl [Perutz, M. F. (1970),Nature 228, 734–739].
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  • 57
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    The journal of membrane biology 132 (1993), S. 167-178 
    ISSN: 1432-1424
    Keywords: red cell ; glucose transport protein ; GLUT1 ; kinetics ; rapid reactions ; tryptophan
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary The kinetics of the initial phases of d-glucose binding to the glucose transport protein (GLUT1) of the human red cell can be followed by stopped-flow measurements of the time course of tryptophan (trp) fluorescence enhancement. A number of control experiments have shown that the trp fluorescence kinetics are the result of conformational changes in GLUT1. One shows that nontransportable l-glucose has no kinetic response, in contrast to d-glucose kinetics. Other controls show that d-glucose binding is inhibited by cytochalasin B and by extracellular d-maltose. A typical time course for a transportable sugar, such as d-glucose, consists of a zero-time displacement, too fast for us to measure, followed by three rapid reactions whose exponential time courses have rate constants of0.5–100 sec+−1 at 20°C. It is suggested that the zero-time displacement represents the initial bimolecular ligand/GLUT1 association. Exponential 1 appears to be located at, or near, the external membrane face where it is involved in discriminating among the sugars. Exponential 3 is apparently controlled by events at the cytosolic face. Trp kinetics distinguish the K d of the epimer, d-galactose, from the K dfor d-glucose, with results in agreement with determinations by other methods. Trp kinetics distinguish between the binding of the α- and β-d-glucose anomers. The exponential 1 activation energy of the β-anomer, 13.6 ± 1.4 kcal mol+−1, is less than that of α-d-glucose, 18.4 ± 0.8 kcal mol+−1, and the two Arrhenius lines cross at ≈23.5°C. The temperature dependence of the kinetic response following α-d-glucose binding illustrates the interplay among the exponentials and the increasing dominance of exponential 2 as the temperature increases from 22.3 to 36.6°C. The existence of these interrelations means that previously acceptable approximations in simplified reaction schemes for sugar transport will now have to be justified on a point-to-point basis.
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  • 58
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    The journal of membrane biology 133 (1993), S. 145-160 
    ISSN: 1432-1424
    Keywords: Acetabularia ; K+ channels ; kinetics ; planar lipid bilayers ; voltage dependence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary Plasma membrane from Acetabularia acetabulum was prepared by aqueous-polymer two-phase partitioning and incorporated into planar 1-palmitoyl-2-oleoyl phosphatidylethanolamine bilayers by stirring in the presence of a (cis∶trans) 325∶100 mm KCl gradient. Under these conditions five distinct K+-selective channels were observed which had unitary chord-conductances (determined between 30 mV either side of the reversal potential) and frequencies of incorporation (in parentheses) of 1,600 pS (26%), 485 pS (21%), 259 pS (53%), 140 pS (37%) and 27 pS (37%). Two Cl−-selective channels were also observed, which had unitary chord-conductances of 8 and 48 pS and were present in 21 and 16% of bilayers, respectively. The voltage dependencies of channel open probability (P o ), open-state time constant (τ o) and closed-state time constant (τ c) were determined for the 259, 140 and 27 pS K+ channels. The P o of all three channels increased with increasingly positive membrane potentials. Thus, since these channels were oriented with their extracellular face adjacent to the cis chamber, which was grounded, all would exhibit outward rectification in vivo. Changes in P o were effected by modulation of τ c in all channels, which shortened as membrane potentials became more positive, and also of τ o in the 140 and 27pS channels, which increased as membrane potentials became more positive. Extracellular (cis) KCl concentration (and/or the KCl gradient across the bilayer) affected the P o of all three K+ channels, shifting the P o /membrane potential relationship in the direction of the change in the potassium reversal potential. In all channels this was achieved largely by changes in τ c .
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  • 59
    ISSN: 1573-9171
    Keywords: benzyl bromide, trimethylvinylsilane, addition ; radicals ; metal-complex initiation ; kinetics ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The general kinetics of the addition of benzyl bromide to trimethylvinylsilane in the presence of the Fe(CO)5—DMF system has been studied. The reaction orders with respect to each reagent found in the study correspond to a radical chain mechanism of the process. The metal-complex system takes part only in the initiation stage and only at a strictly defined ratio of the components.
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  • 60
    ISSN: 1573-9171
    Keywords: kinetics ; organomercury nitroxyls ; organothallium nitroxyls ; coordination bond ; hydrazobenzene ; reduction ; rate constant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An increase is found in the reactivity of organomercury and organothallium nitroxyl mono- and biradicals of the imidazoline type in comparison with the analogous compounds without organometallic fragments. This is explained by the formation of coordination bonds N→Hg, N→Tl, and N→O→Hg.
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  • 61
    ISSN: 1573-9171
    Keywords: cationic polymerization ; polyisobutylene ; Lewis acids ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Polymerization of isobutylene in hexane at −78 °C under the action of the complex AcBr · 2AlBr3 (Ac-2) affords polyisobutylene having C=O groups at the head and C-Br or C=C groups at the tail of all the molecules. The presence of the latter indicates that there occurs proton elimination from the growing carbocation with the formation of a superacid HBr · 2AlBr3 which is unable to initiate the polymerization repeatedly under given contitions. This makes it possible to consider proton elimination as the reaction of the decay of active centers with the rate constantk d. This value has been calculated from the rate of accumulation of the polymeric molecules having terminal C=C bonds:k d=3.5 · 10−4 s−1. The rate constant of chain growthk g has been determined from polymerization kinetics and from the content of active centers:k g=6.2 L mol−1 s−1.
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  • 62
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    Russian chemical bulletin 42 (1993), S. 1027-1031 
    ISSN: 1573-9171
    Keywords: nitroxyls ; hydrazobenzene ; reduction ; tetranitromethane ; oxidation ; kinetics ; constants ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The values of isotropic HFS constantsa N were obtained for nitroxyl radicals (NR) of the piperidine series in hexane and water. The interrelation between rate constants for NR reduction and oxidation reactions, isotropic HFS constantsa N, inductive constants σ″ of the piperidine substituents, and electrochemical characteristics of NR were found. The dependence of the rate constants for the reduction of NR by hydrazobenzene (HB) and its oxidation by tetranitromethane (TNM) upon the Hammett type inductive constantsσ EPR, obtained using HFS constantsa N as the basis, was analyzed. The solvent effect on the reduction and oxidation reaction rate constants, the kinetic isotopic effect of the reduction reaction for a number of NR-HB systems, and alternative reaction mechanisms are considered.
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  • 63
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    Russian chemical bulletin 42 (1993), S. 1811-1815 
    ISSN: 1573-9171
    Keywords: hydroxylammonium nitrate ; preparation ; thermal decomposition ; kinetics ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of thermal decomposition of melted hydroxylammonium nitrate have been investigated by the rate of heat production in the temperature range 84.8–120.9°C. The decomposition proceeds with autocatalysis and up to 60 % of conversion the rate of the process increases proportionally to the square of the degree of decomposition. The initial rate is proportional to the square of the concentration of HNO3 formed due to dissociation of the salt. The activation energy of this process is 15.3±1.8 kcal/mol. It is suggested that the initial stage the process proceeds via interaction between N2O3 and NH3OH+, whereas the subsequent acceleration is due to oxidation of NH3OH+ by nitrogen oxides formed as well as by nitrous acid.
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  • 64
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    Russian chemical bulletin 42 (1993), S. 457-460 
    ISSN: 1573-9171
    Keywords: kinetics ; mechanism ; 6-tert-butyl-2-methylphenol ; alkylation with methyl acrylate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A kinetic scheme of the reaction between 6-tert-butyl-2-methylphenol and methyl acrylate in the presence of an alkali metal phenoxide has been proposed. The rate constants of the elementary steps describing the catalytic mechanism have been calculated. The reaction gives methyl 3-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionate as the only product (Calkylation). The nature of the metal cation does not affect the reaction mechanism.
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  • 65
    ISSN: 1573-9171
    Keywords: H-complexes ; polyimide ; 3,3′,4,4′-benzophenonetetracarboxylic acid, diethyl ester ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of thermal imidization of the H-complexes derived from the diethyl ester of 3,3′,4,4′-benzophenonetetracarboxylic acid (EBZP) and various diamines have been studied. A comparison of kinetic parameters obtained for the imidization of H-complexes based on ethyl or methyl esters of this acid has disclosed the differences in the behavior of each of the two H-bonds and the contribution of each bond to the mechanism of polyimide formation from the respective H-complexes.
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  • 66
    ISSN: 1573-904X
    Keywords: fosinopril sodium ; magnesium ions ; C–P bond cleavage ; kinetics ; mechanism ; tablet formulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Fosinopril sodium (I), a new angiotensin converting enzyme inhibitor, is a diester prodrug of the active moiety II. We report here a novel transformation of fosinopril into β-ketoamide, III, and a phosphonic acid, IV, mediated through metal ion participation. The interaction of fosinopril with magnesium ions was studied in a solution model system in which methanol was used as the solvent and magnesium acetate as the source of metal ions. Kinetic analysis indicated the degradation to be a bimolecular process, with the rate being first order in both metal ion and fosinopril concentration. The degradation products II, III, and IV effectively retarded the magnesium ion mediated reaction of fosinopril. Based on the results of 31P-NMR, 1H-NMR, Mn(II)-EPR spectroscopy experiments and mass spectrometry, a mechanism is postulated for this transformation. A key reactive intermediate has been characterized that supports the proposed mechanism. The results can account for the observed degradation profile of the fosinopril sodium in a prototype tablet formulation.
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  • 67
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    Journal of pharmacokinetics and pharmacodynamics 21 (1993), S. 299-308 
    ISSN: 1573-8744
    Keywords: saturation ; liposomes ; uptake ; Michaelis-Menten ; kinetics ; AUC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The objective of this study was to examine the AUCdependency of saturable hepatic clearance (CL h )of liposomes and to postulate a mathematical model to describe the characteristics. The AUCdependency of saturable CL h was examined under intravenous rapid administration at various doses. The CL h increased with increasing blood concentration but decreased with the increase of AUCat each dose. In addition, the relationship between AUCand CL h was consistent with that observed in previously reported infusion studies. These experimental data confirm the AUCdependency of saturable CL h of liposomes. A mathematical model was developed for this AUCdependency. The decrease of CL h was described by the uptake amount (X)as follows: CL h =CL m (1−X/X m ),where CL m and X m represent the maximum uptake clearance and the maximum uptake amount, respectively. The rate equation for uptake was analytically solved as CL h =X/AUC=X m AUC(1-exp(CL m /X m AUC)).Uptake clearance can be described by CL m , X m ,and AUC,and so uptake clearance is constant if AUCis constant. These experimental analyses and theoretical considerations show the validity of the AUC-dependent saturable CL h of liposomes.
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  • 68
    ISSN: 1573-904X
    Keywords: solution ; protein stability ; factor VIII ; formulation ; kinetics ; DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To investigate the influence of various nonreducing disaccharides and sugar alcohols on the inactivation kinetics of recombinant factor VIII SQ (r-VIII SQ) in aqueous solution not containing albumin as a stabiliser. Methods. The stability of r-VIII SQ was followed using measurement of activity (VIII: C) and HPLC gel filtration at different temperatures. The thermal stability was investigated using differential scanning calorimetry (DSC). Results. The decline in VIII:C followed pseudo-first order kinetics. However, the Arrhenius plot was not linear for formulations without carbohydrate, demonstrating a distinct, reproducible curvature. The reaction rate at 5°C was faster than expected from the Arrhenius kinetics. The energy of activation (Ea) for formulations without added carbohydrates, derived from the linear part of the Arrhenius plot, varied between 77 and 86 kJ/mole in the temperature range 20−37°C. The addition of 600 mg/ml sucrose increased the Ea to 104 kJ/mole. DSC measurements showed thatTm′ was 64.2 ± 0.2°C for r-VIII SQ without stabiliser. This value increased linearly with increasing concentrations of carbohydrate. This stabilising effect is most probably explained by the theory of preferential hydration. Conclusions. The inactivation kinetics of r-VIII SQ in aqueous solution without addition of carbohydrates followed pseudo-first order kinetics but the Arrhenius plot was nonlinear. Sucrose and sorbitol both had highly stabilising effects on r-VIII SQ at concentrations above 300 mg/ml. The preparation containing 600 mg/ml sucrose was stable for at least 12 months at 5°C and 6 months at 25°C.
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  • 69
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    Colloid & polymer science 275 (1997), S. 303-306 
    ISSN: 1435-1536
    Keywords: Key words Vesicle ; self-assembly ; hydrotrope ; stopped-flow ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  The kinetics of vesicle formation from a hydrotrope (sodium xylenesulfonate) solution of a surfactant (Laureth 4) is studied by the use of a stopped-flow apparatus combined with a dynamic light scattering device to determine vesicle size in the system. The hydrotrope system studied presents a system with a high surfactant solubilization combined with vesicle formation simply by dilution with water. The kinetic results show a single exponential decay time. The kinetic analysis indicates that the vesicles are formed from a molecular solution which resulted from the shear in the stopped-flow device and grow by monomeric association.
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  • 70
    ISSN: 1435-1536
    Keywords: Key words 3-aminopropyltriethoxy silane ; silica gel ; interaction ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  Three silica gel sample systems, modified with 3-amino-propyltriethoxy silane (APTS), were prepared by sequentially sampling the reaction mixture at various time intervals. The concentrations of 3-aminopropylsilyl groups (APS) bound on the silica surface were determined by elemental analysis. For the same sample systems, 29Si NMR intensities of an (–O)4Si species belonging only to the silica gel particles and corrected by a cross-polarization correction factor were also measured. Both the APS-concentrations and the correc-ted 29Si NMR intensities depended upon reaction time, reflecting the rate of the APTS–silica gel reaction. Kinetic analysis of these data was made by use of the Gauss–Newton method, and the overall reaction was found to consist of three reaction processes (an initial fast reaction, a slower second reaction and a much slower third reaction). In particular, the conversion of (–O)3SiOH to (–O)4Si is predominant in the second reaction process and the pore size of a silica gel particle affects the reaction mechanism.
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  • 71
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    Photosynthesis research 37 (1993), S. 1-17 
    ISSN: 1573-5079
    Keywords: bacterial photosynthesis ; kinetics ; proton binding ; reaction center ; stoichiometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A proton electrochemical potential across the membranes of photosynthetic purple bacteria is established by a light-driven proton pump mechanism: the absorbed light in the reaction center initiates electron transfer which is coupled to the vectorial displacement of protons from the cytoplasm to the periplasm. The stoichiometry and kinetics of proton binding and release can be tracked directly by electric (glass electrodes), spectrophotometric (pH indicator dyes) and conductimetric techniques. The primary step in the formation of the transmembrane chemiosmotic potential is the uptake of two protons by the doubly reduced secondary quinone in the reaction center and the subsequent exchange of hydroquinol for quinone from the membrane quinone-pool. However, the proton binding associated with singly reduced promary and/or secondary quinones of the reaction center is substoichiometric, pH-dependent and its rate is electrostatically enhanced but not diffusion limited. Molecular details of protonation are discussed based on the crystallographic structure of the reaction center of purple bacteriaRb. sphaeroides andRps. viridis, structure-based molecular (electrostatic) calculations and mutagenesis directed at protonatable amino acids supposed to be involved in proton conduction pathways.
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  • 72
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    Plant and soil 154 (1993), S. 67-72 
    ISSN: 1573-5036
    Keywords: ammonium uptake ; cereals ; kinetics ; legumes ; 15N ; nitrate uptake ; translocation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Influx isotherms were obtained for nitrate and ammonium from three legumes, Cajanus cajan (L.) Millsp., Cicer arietinum L. and Arachis hypogaea L. and three cereals, Sorghum bicolor (L.) Moench., Pennisetum glaucum L. and Zea mays L. The transition in influx isotherms for both nitrogen sources was found to be within the concentration range (0.05–2.5 mM) tested. There were significant differences in Km and Vmax for ammonium between legumes and cereals. The difference in the kinetic properties for nitrate uptake between the two groups of plants only became apparent at the higher concentration tested. Legumes translocated absorbed nitrate and ammonium to shoots more rapidly than cereals. Results show that there are significant differences in uptake and translocation of ammonium and nitrate between legumes and cereals.
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  • 73
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    Hydrobiologia 260-261 (1993), S. 557-561 
    ISSN: 1573-5117
    Keywords: alginate lyase ; specificity ; kinetics ; product inhibition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A purified preparation of the extracellular alginate lyase has been used to study kinetics and specificity towards purified, homopolymeric fragments of alginate. The enzyme preparation from Bacillus circulans 1351 degraded both block types, although with different efficiency, and thus appears to be nonspecific. Addition of calcium ions markedly enhanced the reaction rate for the polymannuronate block but had little or no effect on the reaction with polyguluronate. Michaelis-Menten kinetics are not obeyed in the absence of calcium ions and only for the polymannuronate in the presence of calcium The study of progress curves in response to variation in substrate and enzyme concentrations strongly suggests that the abalone lyase is subject to a reversible product inhibition.
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  • 74
    ISSN: 1573-5044
    Keywords: alfalfa (Medicago falcata) ; direct somatic embryogenesis ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A method for direct somatic embryogenesis in alfalfa (Medicago falcata) is described. The time course in the development phase has been followed for fresh weight, cell density, pH, sugar uptake and embryo number and type. The method of disrupting the explant material has also been shown to influence subsequent embryo formation.
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  • 75
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    Journal of bioenergetics and biomembranes 25 (1993), S. 525-535 
    ISSN: 1573-6881
    Keywords: Mitochondria ; transport ; carrier proteins ; reconstitution ; kinetics ; liposomes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Physics
    Notes: Abstract Eight mitochondrial carrier proteins were solubilized and purified in the authors' laboratories using variations of a general procedure based on hydroxyapatite and Celite chromatography. The molecular mass of all the carriers ranges between 28 and 34 kDa on SDS-PAGE. The purified carrier proteins were reconstituted into liposomes mainly by using a method of detergent removal by hydrophobic chromatography on polystyrene beads. The various carriers were identified in the reconstituted state by their kinetic properties. A complete set of basic kinetic data including substrate specificity, affinity, interaction with inhibitors, and activation energy was obtained. These data closely resemble those of intact mitochondria, as far as they are available from the intact organelle. Mainly on the basis of kinetic data, the asymmetric orientation of most of the reconstituted carrier proteins were established. Several of their functional properties are significantly affected by the type of phospholipids used for reconstitution. All carriers which have been investigated in proteoliposomes function according to a simultaneous (sequential) mechanism of transport; i.e., a ternary complex, made up of two substrates and the carrier protein, is involved in the catalytic cycle. The only exception was the carnitine carrier, where a ping-pong mechanism of transport was found. By reaction of particular cysteine residues with mercurial reagents, several carriers could be reversibly converted to a functional state different from the various physiological transport modes. This “unphysiological” transport mode is characterized by a combination of channel-type and carrier-type properties.
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  • 76
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    Journal of inclusion phenomena and macrocyclic chemistry 28 (1997), S. 95-103 
    ISSN: 1573-1111
    Keywords: Inclusion complex ; β-cyclodextrin ; thermal analysis ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The stability of the β-CD cinnamic aldehyde inclusion complex wasinvestigated by TG and DSC. The weight loss takes place in three stages:dehydration occurs at 50–120 °C; the dissociationof β-CD⋅C9H8O occurs at 200–260 °C;and the decomposition of β-CD begins at 280 °C. Thekinetics of the dissociation of cinnamic aldehyde from the β-CD cavitywere studied by means of thermogravimetry both at constant temperatureand linear increasing temperature. The results show that the dissociationof β-CD⋅C9H8O is dominated by a one-dimensional diffusionprocess. The activation energy, E, is 160 kJ⋅mol-1. Thepre-exponential factor A is 5.8 × 1014 min-1.
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  • 77
    ISSN: 1573-1561
    Keywords: Nitrosomonas europaea ; nitrification ; inhibition ; kinetics ; monoterpenes ; Sequoia sempervirens ; conifers ; nitrogen cycling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Inhibition by allelochemicals, including monoterpenes, has been suggested as a factor in the extremely low nitrification rates observed in coastal redwood forests. Similarities between the molecular structure of known nitrification inhibitors and some conifer monoterpenes have been suggested as one reason for the inhibition of autotrophic nitrifiers by conifer monoterpenes. The effect of monolerpenes on nitrification rate and growth of Nitrosomonas europaea was examined in whole-cell pure culture experiments using the five most abundant monoterpenes in coastal redwood needles. These are (in order of decreasing concentration in the needles) limonene, α-pinenc, sabinene, myrcene, and γ-terpinene. Four of the five compounds significantly inhibited growth of N. europaea in batch culture experiments. Short-term kinetic studies of the two most inhibitory monoterpenes, limonene and α-pinene, were performed on whole cells to evaluate the mode of interaction between these chemicals and nitrification rates. Inhibition constants (K i) of limonene (38 μM) and α-pinene (95 μM) were determined. Lineweaver-Burk plots of nitrification in the presence of monoterpenes appear to fit a noncompetitive inhibition model; however, the mechanisms of inhibition may be more complex.
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  • 78
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    Antonie van Leeuwenhoek 63 (1993), S. 225-235 
    ISSN: 1572-9699
    Keywords: kinetics ; transport ; collision frequency ; growth
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Traditional concepts of nutrient uptake and growth kinetics as linked by cell yield are presented. Phenomena affecting the kinetics are examined along with a discussion of those which lead to ambiguity. Concepts of flux control are presented to help understand the distribution of material along metabolic pathways. Specific affinity is described to relate nutrient accumulation rates to transporter density. It is shown to be a primary kinetic constant and the best available index of nutrient collection ability. As an aid to understanding, specific affinity is reexpressed in terms of membrane permeability. Formulations of nutrient transport rate as a function of cellular composition, particularly transporter and enzyme content and known as janusian kinetics, are described as an improvement to specific affinity theory. Procedures for quantified unidirectional fluxes are reviewed to identify the difference between gross and net transport rates of substrate. Collision frequency theory is used to show that in addition to total biomass, cell size and transporter density should also be included in rate equations describing microbial growth. Theory diversity suggests that one reason for microbial metabolic is that the likelihood of additional collisions of substrate molecules with a cell surface, after an initial collision, requires only a sparse distribution of transporter sites for maximal rate, leaving room for additional transporters able to collect other substrate types.
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  • 79
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    Antonie van Leeuwenhoek 63 (1993), S. 353-373 
    ISSN: 1572-9699
    Keywords: aeration ; bioreactor ; growth ; inhibition ; kinetics ; metabolism ; microorganism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The optimization of fermentation processes depends to a large extent on the modelling of microbial activity under complex environmental conditions where aeration is an important limiting and control factor. Simple relationships are used to establish the sensitivity of cultures to oxygen stress. Specific limitation coefficients which can be determined in laboratory reactors allow a projection to industrial operation and the definition of appropriate aeration and agitation profiles. Optimum control can be assured on the basis of directly measurable process parameters. This is shown for the case of ethanol production usingS. cerevisiae at high cell dry weight concentrations.
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  • 80
    ISSN: 1572-9729
    Keywords: cometabolism ; cosubstrate ; 4-chlorophenol ; inhibition ; kinetics ; modeling ; monooxygenase ; phenol ; substrate interactions
    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 on the simultaneous utilization of phenol (primary substrate) and 4-chlorophenol (cometabolic secondary substrate) demonstrated two critical substrate interactions. First, the cometabolic degradation of 4-chlorophenol was proportional to the rate of phenol oxidation, which provided the electrons for the initial monooxygenase reaction. Second, 4-chlorophenol inhibited the oxidation of the primary substrate, phenol. Modeling analyses of the degradation of phenol alone and of phenol and 4-chlorophenol together showed that the proportionality between phenol and 4-chlorophenol degradation rates averaged 0.1 mg 4-CP/mg phenol, which corresponds to 0.5% of the electrons generated by phenol oxidation being used as a cosubstrate for the monooxygenase reaction of 4-chlorophenol. In addition, modeling analyses suggest that 4-chlorophenol was a noncompetitive inhibitor of phenol oxidation for high phenol concentrations, but a competitive inhibitor for low phenol concentrations.
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  • 81
    ISSN: 1573-5079
    Keywords: hydrogen peroxide ; hydroxylamine ; kinetics ; manganese ; oxygen release ; photosynthesis ; Photosystem II
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Flash-induced amperometric signals were measured with a Joliot-type O2 rate electrode in spinach Photosystem II (PS II) membrane fragments exposed to very low concentrations of added hydroxylamine or hydrogen peroxide. In both cases ‘anomalous O2 signals’ were observed on the first two flashes, and oscillating four-flash patterns were observed on subsequent flashes. The anomalous signals were eliminated in the presence of catalase but not EDTA. The rise times of the O2-release kinetics associated with the anomalous signals were slow (ca. 20 ms with NH2OH and ca. 120 ms with H2O2) compared to the kinetics of O2 release on subsequent flashes and in control membranes (3–6 ms). It is proposed that when the intact PS II O2-evolving complex is perturbed with small concentrations of added reductant, H2O2 can gain access and bind to the complex. Bound H2O2 can then reduce lower S states in some centers leading to anomalous O2 signals on the first two flashes. A model is presented to explain both types of anomalous O2 production. Oxygen observed on the third and subsequent flashes is due to the normal photosynthetic O2-evolution process arising from the S3-state. Anomalous O2 production could be a protective mechanism in PS II centers subjected to stress conditions.
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  • 82
    ISSN: 1573-5079
    Keywords: activation ; deactivation ; induction ; irradiance ; kinetics ; photosynthesis ; phytoplankton ; Rubisco
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The activity of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) was examined in three marine microalgae: the chlorophyte t Dunaliella tertiolecta and the chromophytes t Pavlova lutheri and t Thalassiosira pseudonana. The three species differed in the sensitivity of Rubisco activity in crude extracts to magnesium ion concentration, the presence of protease inhibitors, the duration of the incubation on activity, and the potential for full activation of Rubisco with 20 mM magnesium chloride and 20 mM bicarbonate t in vitro. t D. tertiolecta had responses that were similar to those described in vascular plants: regulation of initial activity on a gradient of irradiances; maximum initial activities that were 80– 90% of light-saturated photosynthesis; total activities that exceeded light-saturated photosynthesis by 30–100%; and deactivation of Rubisco in darkness. Both initial and total activity declined in darkness and increased on a return to growth irradiance. First-order time constants were about 9 min for deactivation and 3 min for reactivation of initial activity. The decline in total activity after a transition into darkness could not be reversed t in vitro but could be reversed by exposing t D. tertiolecta to light, a characteristic of regulation by CA1P. The responses of t T. pseudonana were qualitatively similar, except that recovery of initial activity was low and could only account for 30–40% of light-saturated photosynthesis. Rubisco from t T. pseudonana exposed to low irradiance could be activated t in vitro but at growth irradiance and higher, total activity was lower than initial activity. The time constants for deactivation and reactivation of initial activity after reciprocal switches between growth irradiance and darkness were 12–18 min and 3 min in t T. pseudonana. t P. lutheri showed no regulation of Rubisco activity in response to changes in irradiance or light-dark transitions. This may have been an artifact of the conditions chosen to measure activity.
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  • 83
    ISSN: 1573-6822
    Keywords: diabetes ; rat ; cell culture ; antidepressant ; kinetics ; biotransformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Biotransformation of amitriptyline (AMI) was studied at different intervals in freshly isolated hepatocytes from healthy or streptozocin-induced diabetic rats in order to investigate the influence of the diabetic state. Levels of free and conjugated AMI, demethylated and hydroxylated metabolites, were assessed by HPLC analysis. In hepatocytes isolated from diabetic rats, AMI was less completely metabolized and the demethylation reaction became more important than in non-diabetic rat hepatocytes. Although the proportions of hydroxylated metabolites decreased in diabetic rats, it always remained predominant. Furthermore, glucuronidation of metabolites was greater, especially for (Z)-10-hydroxynortriptyline in diabetic animals.
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  • 84
    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,U ts 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 (GARB) 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. TheU ts 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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  • 85
    ISSN: 1573-0778
    Keywords: hypoxia ; recombinant protein ; animal cells ; erythropoietin ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Expression of specific genes is a strategy of animal cells for adaptation to oxygen deficiency and the mechanism underlying the hypoxic activation of gene expression may be useful for efficient production of recombinant proteins by animal cells, because oxygen is a limiting factor in animal cell cultures. We prepared an animal cell line harboring the plasmid in which expression of a reporter gene, β-galactosidase, is controlled by an enhancer responsible for the hypoxic activation of gene transcription. The purpose of this paper is to understand this hypoxic production of recombinant proteins quantitatively by a mathematical model originally developed based on the following hypotheses; 1 lacZ (the reporter gene) is transcribed after HIF-1 protein complex is bound to the hypoxic enhancer, 2. β-galactosidase synthesis rate is limited at the transcription of lacZ, 3. HIF-1 is an inactive form under a normal oxygen concentration, 4. Oxygen works as a repressor in the synthesis of HIF-1 protein, 5. Both β-galactosidase and HIF-1 are decomposed according to the first order reaction. The effects of hypoxic duration as well as oxygen concentration on the β-galactosidase production were successfully predicated by the model.
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  • 86
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    Reaction kinetics and catalysis letters 62 (1997), S. 179-183 
    ISSN: 1588-2837
    Keywords: Dioxiranes ; kinetics ; thermolysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Dimethyldioxirane decomposition in oxygen atmosphere follows a first-order kinetic law. Decomposition rate constant (k, s−1) in acetone in the temperature range from 30 to 50°C has been determined as lgk=(7.1±0.9)−(16.0±1.4)/θ, θ=2.303RT kcal/mol.
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  • 87
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    Reaction kinetics and catalysis letters 62 (1997), S. 339-346 
    ISSN: 1588-2837
    Keywords: Alkylation ; hydrotalcite ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Vapor phase alkylation of phenol with methanol was carried out over catalysts derived from a series of hydrotalcite (HT)-like compounds of the form M(II)Al-HT; where M(II)=Mg, Mn, Co, Ni, Cu and Zn with M(II)/Al atomic ratios of2–5. The kinetic parameters such as rate constant (k), apparent activation energy (Ea) and Arrhenius frequency factor (Ao) for the disappearance of phenol were evaluated employing a power law equation assuming pseudo-first order kinetics. The kinetic parameters were found to be in good agreement with phenol conversion. The existence of the compensation effect between Ea and ln Ao was tested.
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  • 88
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    Reaction kinetics and catalysis letters 62 (1997), S. 353-358 
    ISSN: 1588-2837
    Keywords: Ce(IV) oxidation ; arylthioacetic acid ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of ruthenium(III)-catalyzed oxidation of several arylthioacetic acids by Ce(IV) have been studied. The proposed mechanism involves the formation of a 1∶1 complex between Ru(III) and arylthioacetic acid, which then reacts with Ce(IV).
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  • 89
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    Reaction kinetics and catalysis letters 62 (1997), S. 299-304 
    ISSN: 1588-2837
    Keywords: carbon ; kinetics ; surface state
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The formation of carbonaceous deposits on Pt(110) surface due to ethylene decomposition in the temperature range of 770–970 K has been studied. Both kinetic and XPS data show that chemisorbed carbon (with no C−C bonds, but only C−Pt bonds) forms at T=770–870 K, the saturation coverage θs being about 1 ML. At higher temperatures, θs increases by a factor of 1.5, indicating the formation of more densely packed carbon species (DPC) due to C−C bonding. A kinetic model has been proposed to describe the process of carbon conversion.
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  • 90
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    Reaction kinetics and catalysis letters 62 (1997), S. 347-352 
    ISSN: 1588-2837
    Keywords: catalyst ; kinetics ; Fe−Mo/SiO2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The loss rate of molybdenum in Fe−Mo/SiO2 catalyst has been measured. When the catalyst is composed of a Fe2(MoO4)3 crystalline phase and monolayer dispersed MoO3, the loss rate of MoO3 varies with the content of MoO3 in the catalyst. If a MoO3 crystalline phase arises in the catalyst, the loss rate will be accelerated.
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  • 91
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    Reaction kinetics and catalysis letters 62 (1997), S. 83-88 
    ISSN: 1588-2837
    Keywords: Photocatalysis ; photooxidation ; CO ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The paper reports quantum efficiency dependence of the steady state gas phase photocatalytic oxidation of CO over dispersed anatase on CO and CO2 concentrations, temperature and UV light intensity. A tentative mechanism of the process is proposed.
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  • 92
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    World journal of microbiology and biotechnology 9 (1993), S. 357-360 
    ISSN: 1573-0972
    Keywords: Candida utilis ; inhibition ; kinetics ; regulation ; sugar ; transport ; xylose ; yeast
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Low-affinity (K m=67.6±3.2 mM) and high-affinity (K m=1.9±1.2 mM) D-xylose transport occur in Candida utilis grown, respectively, on D-glucose or D-xylose. Starvation of glucose-grown cells decreases the K m value (10.5±2.6 mm). The high-affinity system appearing during starvation required protein synthesis and it was inactivated when cells were exposed to glucose, by a process independent of protein synthesis. High-affinity transport was accompanied by transient alkalinization of yeast suspensions, indicating that it is a proton symport, whereas low-affinity transport was not. Both systems, however, were inhibited by metabolic inhibitors and by replacing H2O in the transport assay with D2O, indicating that both may be proton symports. Glucose and acetic acid also inhibited both high-and low-affinity xylose transport.
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  • 93
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    World journal of microbiology and biotechnology 9 (1993), S. 479-482 
    ISSN: 1573-0972
    Keywords: Benzyl viologen ; dichloromethane ; inhibitor ; kinetics ; nitrous oxide ; nitrous oxide reductase ; tetrachloromethane ; trichloromethane ; Wolinella succinogenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Nitrous oxide reductase from Wolinella succinogenes was tested for benzyl viologen cation (BV+)-chlorinated methane oxidoreductase activity, using di-, tri- and tetra-chloromethanes, and for the inhibition of BV+-N2O oxidoreductase activity by these chloromethanes. No BV+-chlorinated methane oxidoreductase activity was detected. Any such activity, if it exists, must be less than 0.1% of the BV+-N2O oxidoreductase activity of the enzyme. Inhibition of the BV+-N2O oxidoreductase activity by dichloromethane was detected and was apparently reversible and non-competitive, as is the case with the small metal-ligand type inhibitors of the enzyme (e.g. acettlene, azide, cyanide and carbon monoxide). Trichloromethane was a weaker inhibitor and inhibition was not detected with tetrachloromethane.
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  • 94
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    Journal of elasticity 46 (1997), S. 53-90 
    ISSN: 1573-2681
    Keywords: phase transitions ; kinetics ; traveling waves
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The theory of thermoelastic materials undergoing solid-solid phase transformations requires constitutive information that governs the evolution of a phase boundary. This is known as a kinetic relation which relates a driving traction to the speed of propagation of a phase boundary. The kinetic relation is prescribed in the theory from the onset. Here, though, a special kinetic relation is derived from an augmented theory that includes viscous, strain gradient and heat conduction effects. Based on a special class of solutions, namely travelling waves, the kinetic relation is inherited from the augmented theory as the viscosity, strain gradient and heat conductivity are removed by a suitable limit process.
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