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  • Spektralphotometrie, Atomabsorption
  • kinetics
  • Springer  (194)
  • Public Library of Science (PLoS)
  • 1980-1984  (71)
  • 1975-1979  (123)
Collection
Keywords
Publisher
  • Springer  (194)
  • Public Library of Science (PLoS)
Years
Year
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 261 (1983), S. 188-189 
    ISSN: 1435-1536
    Keywords: Polymerization ; kinetics ; redox polymerization ; acrylamide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 2
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    Colloid & polymer science 262 (1984), S. 366-373 
    ISSN: 1435-1536
    Keywords: kinetics ; isothermal crystallization ; polymer ; spherulite ; differential scanning calorimetry
    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 In the DSC technique, isothermal crystallization experiments are usually performed on thin flat specimens, but their interpretation generally uses theories developed for an unbounded volume. In this paper, isothermal crystallization of spherical entities in the volume limited by two parallel infinite planes is considered. Our model, derived from Avrami's theory, gives an analytical expression for the transformed volume fraction as a function of time. It is shown that the influence of thickness becomes important when thickness becomes of the order of or smaller than the average spherulite radius. The main effects of a decreasing thickness are a slower crystallization kinetics and a decrease in the Avrami exponent. These results can be used to interpret experimental data obtained in isothermal polymer crystallization.
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  • 3
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    Colloid & polymer science 261 (1983), S. 621-625 
    ISSN: 1435-1536
    Keywords: Polyamide 6 ; crystallisation ; kinetics ; titania
    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 isothermal and nonisothermal crystallization of polyamide-6 (PA6) containing titania was studied by means of DSC. It was found thatTiO 2 causes an acceleration in the crystallization of polyamide-6 and lowers the value of the Avrami exponent,n. The presence of TiO2 does not affect equilibrium melting pointT m 0 , glass temperatureT g, or surface free energiesσ e andσ of the basal and lateral surfaces.
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  • 4
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    Fire technology 20 (1984), S. 47-63 
    ISSN: 1572-8099
    Keywords: Extinguishment ; fire modeling ; mass loss ; heat release ; char ; reflash ; sprinklers ; radiant flux ; kinetics ; reaction rate ; heat loss ; ash ; latent heat ; spray density ; extinguishing agents
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying
    Notes: Abstract The Ad Hoc Mathematical Fire Modeling Working Group was organized about seven years ago to facilitate voluntary cooperation and coordination in developing mathematical fire modeling capability. The group has a steering committee of representatives of agencies that support fire modeling and related research. These include the National Bureau of Standards' Center for Fire Research, Factory Mutual Research Corp., the Naval Research Laboratory, NASA, and the Federal Aviation Agency. The Group holds plenary meetings when it seems desirable to do so (about once each 1 1/2 years), and workshops on topical subjects. Three workshops were held in 1983. Normally, Group meetings are held before or after other meetings at which a number of interested personnel would likely be present. Minutes are mailed to those who attended and to others (including European and Japanese personnel) who have indicated interest. This workshop was arranged by Ron Alpert of Factory Mutual Research Corp. and held at their facilities at Norwood, MA, in November 1983.
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  • 5
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    Journal of solution chemistry 11 (1982), S. 339-346 
    ISSN: 1572-8927
    Keywords: Carbon dioxide ; hydrolysis ; aqueous solution ; kinetics ; activation volume
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pressure dependence of the dehydration reaction of H2CO3 was measured in acidic aqueous solution for pressures up to 1 kbar using a high-pressure stopped-flow instrument. The corresponding volume of activation was found to be 6.4±0.4 cm3-mol−1 at 25°C and 0.5 ionic strength. Volume equation calculations result in a value of −9.9±1.9cm3-mol−1 for the volume of activation for the hydrolysis of CO2 under the same conditions. For the first time, the reaction mechanism can be interpreted in terms of dissociative and associative modes, respectively. These data are used to construct an overall reaction volume profile.
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  • 6
    ISSN: 1572-8927
    Keywords: Temperature jump ; kinetics ; thermodynamics ; TRIS ; iminodiacetic acid ; magnesium ion ; phenol red
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Equations describing the temperature jump amplitudes associated with a system of two coupled reactions (TRIS-phenol red) as well as the ternary system (Mg2+-iminodiacetic acid-phenol red) are presented. The termodynamic parameters calculated from experimentally measured temperature perturbation amplitudes using a multiparametric curve fitting procedure are found to be in good agreement with those determined from pH- and costant rate thermometric titrations. For phenol red, pK I =7.55, ΔH I =3.45 kcal, and for Mg2+ iminodiacetic acid, log K M =2.84, ΔH M =3.25 kcal, were obtained. It is shown that this method can be used to determine accurate thermodynamic enthalpy changes over a narrow temperature interval of less than 1.0°C from a single experiment requiring about 50 μl of sample solution.
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  • 7
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    Journal of solution chemistry 12 (1983), S. 771-781 
    ISSN: 1572-8927
    Keywords: Ultrasonics ; kinetics ; aqueous solution ; iso-butyl cellosolve
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ultrasonic absorption and velocity measurements in aqueous solution of iso-butyl cellosolve (ethylene glycol iso-butyl ether) as a function of the concentration are reported. The two relaxational absorptions have been attributed to the perturbation of the equilibria expressed by AB⇌A+B and Aα(1/n)An where A is the solute, B is the solvent, AB is the complex and A n is the solute aggregate. The rate constants for each step have been determined. From the concentration dependence of the maximum excess absorption per wave length, the enthalpy change and the volume change for the reaction between the solute and the solvent have been determined for aqueous solutions of butyl cellosolve (ethylene glycol n-butyl ether), iso-butyl cellosolve and propyl cellosolve (ethylene glycol n-propyl ether). The results are consistent with a hydrogen bonding reaction. The effect of the ethers on water structure are considered and it is clear that the fraction of water molecules which can hydrogen bond to the solute decreases with the increasing hydrophobicity of the solute.
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  • 8
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    Journal of solution chemistry 6 (1977), S. 203-216 
    ISSN: 1572-8927
    Keywords: Glucose ; kinetics ; mixed solvent ; kinetic isotope effect ; enthalpy of activation ; entropy of activation ; tetrahydrofuran ; tert-butanol ; mutarotation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The mutarotation rates of glucose in aqueous mixtures of tetrahydrofuran andtert-butanol in the mole fraction (xi) range 0〈xi〈0.2 have been measured at 5° intervals in the range 5–35°C. The kinetic deuterium isotope effects have been determined for the same solvent compositions at 25 and 35°C. A statistical analysis of the Arrhenius plots indicates that the experimental errors, although small, are too large for the establishment of any compensation behavior between ΔH
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  • 9
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    Journal of solution chemistry 5 (1976), S. 163-169 
    ISSN: 1572-8927
    Keywords: Solvent effects ; tetramethylurea ; hydrolysis ; hydrogen bonding ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Tetramethylurea was hydrolyzed in aqueous hydrochloric acid at temperatures of 80, 90, and 100°C. All reactions were carried out in an excess of both tetramethylurea and water, with first-order dependence on acid concentration being observed. As the concentration of water was increased, the rate of hydrolysis decreased until equimolar amounts of water and tetramethylurea were present. Subsequent addition of water had no effect on the observed rate.
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  • 10
    ISSN: 1572-8927
    Keywords: Enthalpies of reaction ; heats of reaction ; kinetics ; ester hydrolysis ; microcalorimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The conditions under which the Picker flow microcalorimeter can be used to measure enthalpies and rates of reactions were investigated. For this purpose, systematic studies were made of the enthalpies of neutralization of HCl, HBr, HNO 3 , acetic, proprionic, and butyric acids with NaOH, enthalpies of hydrolysis of methyl and ethyl acetate with NaOH, and the reaction rates of the ester hydrolysis with NaOH. The general procedure and various sources of error are discussed and it is concluded that enthalpies of slow reactions can be measured to about 1% when the calorimeter is operated in the quasi-isothermal mode and the reaction rates to about 3% when operated in the quasi-adiabatic mode.
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  • 11
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    European journal of clinical pharmacology 21 (1981), S. 215-220 
    ISSN: 1432-1041
    Keywords: phenytoin ; cimetidine ; antipyrine test ; drug interaction ; drug metabolism ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary In a prospective study in nine patients the effects of phenytoin and of cimetidine (1000mg/day) + phenytoin on the antipyrine test and serum phenytoin concentrations were studied. Serum phenytoin increased from the steady state level of 5.7±1.3 mg/l to 9.1±1.4mg/l after three weeks on cimetidine (p〈0.01), and fell to 5.8±1.2 mg/l within two weeks after withdrawal of cimetidine. The protein binding of phenytoin was not changed by cimetidine. After use of phenytoin for 2–4 months, antipyrine clearance increased from 0.67±0.06ml/min/kg to 1.61±0.22 ml/ min/kg, and antipyrine half-live fell from 10.9±1.3h to 4.5±0.6h as compared to the values before phenytoin treatment (p〈0.01). After three weeks combined use of cimetidine and phenytoin, antipyrine clearance was decreased to 1.01±0.07 ml/min/kg and antipyrine half-life was prolonged to 6.1±0.5h, (p〈0.01) compared to the values on phenytoin alone. The distribution volume of antipyrine was not affected by phenytoin nor by cimetidine + phenytoin. The half-life of cimetidine was 2.8±0.3h in the patients on longterm phenytoin treatment. There was a significant positive correlation (p〈0.001) between the increase in serum phenytoin concentration and the prolongation of antipyrine half-life caused by cimetidine. Thus, cimetidine increases serum phenytoin concentration, very probably by inhibiting its metabolism. Care should be taken in the concomitant use of cimetidine and phenytoin, and the dose of phenytoin should be modified according to the clinical symptoms and serum phenytoin concentrations.
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  • 12
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    European journal of clinical pharmacology 22 (1982), S. 225-228 
    ISSN: 1432-1041
    Keywords: pinazepam ; N-desmethyldiazepam ; kinetics ; metabolism ; human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The plasma profile of a single oral dose of pinazepam 10 mg was studied in 6 healthy male volunteers, aged 26 to 31 years. The concentrations of the parent compound and of its metabolite in plasma were measured by gas-chromatography. The peak plasma levels of pinazepam was 36.8±5.1 ng/ml and of N-desmethyldiazepam 150±13.3 ng/ml. The plasma concentration of the metabolite become higher than that of the parent compound shortly after administration, suggesting that pinazepam acts as a prodrug.
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  • 13
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    European journal of clinical pharmacology 22 (1982), S. 545-551 
    ISSN: 1432-1041
    Keywords: oxcarbazepine ; kinetics ; disposition ; metabolites ; renal excretion ; volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Oxcarbazepine (oxcarb) 600 and 900 mg (2360 and 3540 µmol) was taken by 3 volunteers (2 ♀, 1 ♂; 45–67 kg; age 22–34 years) after an overnight fast. Blood, saliva and urine were collected for the next 72 h for assay of oxcarb, 10,11-dihydro-10-hydroxy-carbamazepine (OHcarb), and 10,11-dihydrotrans-10,11-dihydroxy-carbamazepine (diol). Oxcarb reached a maximum level of about 1 µg/ml (3.93 µmol/l) within 1 h and dropped below the detection limit (0.1 µg/ml=0.39 µmol/l) within 3 h. The active metabolite OHcarb appeared in the blood before oxcarb and reached the higher maximum level of 7.4 µg/ml (29 µmol/l) after 7 h. Thereafter serum levels decreased with a t1/2 of about 25 h, and after 40 h with a t1/2 of 9 h, the latter agreeing with the renal excretory t1/2 calculated from the urine data (10 h). The ratio of OHcarb concentration in saliva to that in plasma varied considerably (0.3–1.7; median 1; r〉0.9), whereas that of blood to plasma was 1.25 with only small variation (r〉0.98); OHcarb concentrations in erythrocytes were 50% higher than in plasma. Diol was detected in blood (maximum level 0.5 µg/ml=1.84 µmol/l) in 2 volunteers. 45% of the dose could be recovered in urine (Oxcarb 5%, OH-carb 36%, Diol 4%). Whereas Oxcarb was completely conjugated, only 25% of OHcarb was conjugated and diol was unconjugated.
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  • 14
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    European journal of clinical pharmacology 24 (1983), S. 217-220 
    ISSN: 1432-1041
    Keywords: metoprolol ; pregnancy ; hypertension ; kinetics ; pre-eclampsia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The disposition of oral metoprolol was studied in 5 women during the last trimester of pregnancy and 3 to 5 months after delivery. After a single oral dose of 100 mg the individual peak plasma concentration in the pregnant state was only 20–40% of that after pregnancy. The plasma half-lives of metoprolol were about the same during (average 1.3 h) and after pregnancy (average 1.7 h). By contrast, the area under the plasma concentration versus time curve was much smallerduring (mean 262 nmol/l×h) thanafter (mean 1298 nmol/l×h) pregnancy, resulting in an average apparent oral clearance (Clo) of metoprolol that was 4.4times higher during (362 ml×kg−1 body-weight×min−1) than after pregnancy. The increased Clo in pregnancy is assumed to be due to enhanced hepatic metabolism of the drug. The possible clinical consequence of the difference in the disposition of metoprolol is discussed.
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  • 15
    ISSN: 1432-1041
    Keywords: prizidilol ; antihypertensive effect ; acute and long-term blood pressure control ; plasma renin activity ; acetylator phenotype ; antinuclear antibodies ; side effects ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary After an initial placebo period of four weeks 24 patients with primary hypertension were treated with prizidilol, a hydrazinopyridazine derivative with combined vasodilator and non-selective beta-adrenoceptor blocking actions, for a dose titration period of 14 weeks. Prizidilol 200 to 800 mg was given once daily to achieve a target supine diastolic blood pressure (BP)〈90 mmHg. Supine and standing BP recorded 24–27 h after drug intake decreased from 172±17/106±6 mmHg (mean±SD) and 167±18/111±8 mmHg, respectively, after placebo to 159±16/99±8 and 154±18/101±9 mmHg after active treatment for six weeks (mean dose 447 mg), and to 154±16/97±7 and 148±14/97±7 mmHg after treatment for 14 weeks (mean dose 687 mg/day). A slight reduction in HR was seen after treatment for six weeks and in plasma renin activity and urinary methoxycatecholamine excretion after treatment for 14 weeks. A sustained decrease in BP was observed for 10 h after prizidilol 800 mg (n=9), with a maximum antihypertensive effect (mean reduction in supine BP 33/18 mmHg) 2.5 h after dosing, which coincided with the mean peak plasma concentration. The plasma elimination half-life of the drug was 3.9 h (range 2.0–8.9 h). Changing to a twice daily regimen in 17 patients (mean daily dose 748 mg at six months) did not produce any further reduction in the BP (recorded 12–15 h after dosing) as compared to the once daily regimen at 14 weeks. During treatment for up to 24 months, 16 patients did not achieve satisfactory BP control. Eight of them were withdrawn and eight received additional treatment with bendroflumethiazide (2.5–5 mg/day). In 7 of the latter satisfactory BP control was achieved. Side effects were few. Dizziness and tiredness occurred in four patients 2–5 h after prizidilol 600–800 mg once daily. These symptoms partly subsided when the subjects changed to a twice daily regimen. No ocular side-effects were found. Before treatment 13 out of 24 patients had a low titre of IgM antinuclear antibodies (ANA) and one patient also a low titre of IgG ANA. During treatment the frequency of patients with positive ANA-titres became higher, and after treatment for 12 months (n=17) 15 patients had positive IgM and seven patients positive IgG ANA-titres. However, the titres were low and no patient showed a clinical lupus erythematosus syndrome. There was no relation between acetylator phenotype of the patient and acute or longterm effecton BP, pharmacokinetics of the drug or the development of a raised ANA-titre.
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  • 16
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    European journal of clinical pharmacology 24 (1983), S. 273-276 
    ISSN: 1432-1041
    Keywords: undernourished ; chlorquine ; kinetics ; plasma levels ; red cell uptake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The plasma and whole blood kinetics of chloroquine was studied in 7 normal and 8 undernourished subjects following a single oral dose of 600 mg. The terminal half-lives were similar in both groups. The AUC was also similar in the 2 groups, even though a higher dose per kg body weight was administered to the undernourished. This was probably because of faster clearance in this group. Chloroquine uptake by erythrocytes, its main site of action in malaria, was also comparable in the two groups. The plasma concentration of chloroquine over a period of time was found to be similar in 4 normal and 4 undernourished subjects following administration of 1.5 g of the drug in divided doses. The undernourished appear, therefore, to handle chloroquine in such a way that they do not suffer a greater risk of toxicity than normals.
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  • 17
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    European journal of clinical pharmacology 24 (1983), S. 525-527 
    ISSN: 1432-1041
    Keywords: theophylline ; airway obstruction ; biotransformation ; kinetics ; oral dosage
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Oral theophylline was given to 6 adults with airways obstruction. The initial dose was 125 mg daily and this was increased by 125 mg each week. The final total daily dose reached was determined by side effects and ranged from 500 mg to 1125 mg. At the end of each week and before the next dosage increment steady state, trough plasma theophylline concentrations were measured. For each individual and for the group as a whole there was a highly significant linear correlation between theophylline dose and trough plasma concentration. This indicates that for oral theophylline, in adults, dose-dependent kinetics do not play a significant role and dose may be adjusted without fear of a disproportionate rise in plasma concentration.
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  • 18
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    European journal of clinical pharmacology 27 (1984), S. 491-494 
    ISSN: 1432-1041
    Keywords: amiodarone ; kinetics ; volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary We studied three healthy volunteers after a single i.v. bolus of amiodarone, during 1 month of chronic oral dosing and after the discontinuation of the drug. Blood concentrations of amiodarone declined rapidly in a bi-exponential fashion after i.v. bolus. The terminal half-life ranged from 10 to 17 h; after discontinuation of chronic treatment the terminal half-lives were 8–21 days. The i.v. data, the trough levels during multiple dosing and the washout phase could be simultaneously fitted using a tri-exponential equation. The subjects were carefully monitored for cardiac and thyroid function. One subject had to stop taking amiodarone because of profound bradycardia. A reduction of serum TT3 and FT3 concentrations and an increase of serum rT3 and FT4 was found.
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  • 19
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    European journal of clinical pharmacology 10 (1976), S. 43-48 
    ISSN: 1432-1041
    Keywords: Spironolactone ; acetylsalicylic acid ; fludrocortisone ; kinetics ; pharmacology ; interaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The influence of 600 mg acetylsalicylic acid (ASA) on the renal excretion and clearance of canrenone, the principal unconjugated metabolite of spironolactone, was examined in a double-blind crossover study in six healthy subjects. ASA significantly reduced the urinary excretion, and the fractional excretion, of canrenone between 4 — 6 hours after administration of 50 mg spironolactone. The pharmacological activity of spironolactone, assessed simultaneously by alterations in fludrocortisone-induced urinary electrolyte changes, was slightly but not significantly reduced. The reductions in urinary canrenone excretion correlated with changes in the urinary log 10 Na/K ratio. The results suggest that canrenone may be actively secreted at the proximal renal tubule, and that secretion is blocked by ASA or its conjugates. This is a possible mechanism for the pharmacological interaction between ASA and spironolactone which has been described previously.
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  • 20
    ISSN: 1432-1041
    Keywords: Theophylline ; kinetics ; apnea ; premature newborns ; developmental pharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Aminophylline (theophylline-ethylenediamine) was administered to 27 premature newborns to prevent apneic spells. Of the 22 patients monitored for theophylline concentration, a therapeutic blood level was reached in 19 in 1–2 days, and 3 stayed below it. ‘Toxic’ blood levels (≥20 µg/ml) were reached in 3 cases, one of whom showed signs of toxicity. Theophylline treatment was not efficient in the prevention of apnea when a serious underlying disease was present. Theophylline blood half-life (mean : 27.0 h) and clearance (mean 12.9 ml/h/kg) confirmed the slow elimination pattern of the drug in the premature infant.
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  • 21
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    European journal of clinical pharmacology 17 (1980), S. 285-293 
    ISSN: 1432-1041
    Keywords: tolbutamide ; chlorpropamide ; kinetics ; food ; age ; blood glucose ; plasma insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The influence of food intake (standardized breakfast) on the oral single-dose kinetics and effects of tolbutamide (0.5 g) and chlorpropamide (250 mg) was investigated in young, healthy volunteers. The single-dose kinetics of the two drugs was also studied in elderly healthy subjects. There was great interindividual variation in the elimination rate of both drugs, but food intake influenced neither their AUCs nor their rates of absorption and elimination. The peak concentration of chlorpropamide, but not that of tolbutamide, was reduced by food intake. The peak concentrations of serum tolbutamide were approximately doubled by an increase in dose from 0.5 to 1.0 g, and from 1.0 to 2.0 g. At no time did tolbutamide 0.5 g affect the plasma insulin level, neither in the fasting nor in the non-fasting state. However, this dose did reduce the blood glucose level during fasting and the increase in blood glucose in response to the meal. The latter effect was recorded within 30 min, when the serum level of tolbutamide still was close to zero. Plasma insulin concentrations did increase within 30 min after a higher dose of tolbutamide (1.0 g), when the serum concentration of tolbutamide was about 50 µmol/l. Between 2.5 and 8 h after administration of chlorpropamide 250 mg, serum drug concentrations were lower than those following tolbutamide 0.5 g. The blood glucose response was smaller and occurred later, being significant at 2 h, when the serum concentration of the drug was about 70 µmol/l. There was no significant change in plasma insulin. There was no significant pharmacokinetic difference between young and elderly subjects, except that the peak concentration of tolbutamide was higher in the latter. It appears that both for tolbutamide and chlorpropamide there is great interindividual variation in drug disposition, but food intake does not influence the bioavailability of either drug. The effect of any particular drug concentration seems dependent upon the blood glucose level and hence upon the elapsed time since the last meal. Both drugs can reduce blood glucose without an alteration in the peripheral blood concentration of insulin. This may reflect an extrapancreatic effect of the drugs, but it could also be an expression of increased insulin secretion, which is not detected because of enhanced hepatic degradation of the hormone released into the portal circulation. The observations made in young individuals are also probably relevant for elderly subjects.
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  • 22
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    European journal of clinical pharmacology 21 (1982), S. 403-408 
    ISSN: 1432-1041
    Keywords: glibenclamide ; diabetes ; insulin ; kinetics ; blood glucose ; relationship to meals ; absorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary In an attempt to assess whether intake of glibenclamide before meals would improve its therapeutic capacity, the present investigation compared the effect of glibenclamide 2.5mg t.i.d. given before and together with meals. In addition, these effects were compared with that of glibenclamide given as a single morning dose of 7.5mg. The subjects studied were six Type 2 diabetics not previously exposed to sulphonylurea drugs. Irrespective of dosage and mode of administration, addition of glibenclamide to a standardized breakfast, lunch and dinner enhanced plasma IRI concentrations and reduced blood glucose concentrations as compared to administration of meals without the drug. The different modes of glibenclamide administration did not differ significantly with respect to IRI responses. However, the blood glucose reduction after breakfast was significantly greater when glibenclaimde 2.5mg had been given before the meal than when 2.5 or 7.5mg were given with the meal; a similar, but non-significant tendency was observed after lunch; no consistent difference was seen after dinner. Food intake did not affect glibenclamide kinetics. It appears that administration of glibenclamide 2.5mg before breakfast improved glucose utilization following the breakfast load, due to earlier attainment of an effective concentration of glibenclamide.
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  • 23
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    European journal of clinical pharmacology 22 (1982), S. 309-314 
    ISSN: 1432-1041
    Keywords: acetylsalicylic acid ; salicylic acid ; dipyridamol ; bioavailability ; kinetics ; rapid- and slow-release formulations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Acetylsalicylic acid (ASA) is a strong, irreversible inhibitor of platelet aggregation, but loses this activity following first-pass deacetylation to salicylic acid (SA). In order to compare the bioavailability of unchanged ASA from rapid- and slow-release formulations, the single-dose concentration profiles of ASA and SA were studied in healthy volunteers following intake of two different rapid-release (conventional and effervescent tablets) and three different slow-release (microencapsulated ASA in tablets and in capsules, and enteric-coated tablets) formulations of ASA, and of one slow-release formulation of sodium salicylate. Since anti-platelet therapy with ASA is often combined with dipyridamol, the influence of this drug was also examined. The concentrations of ASA and SA were measured by high-pressure liquid chromatography. While the bioavailability of SA from the 5 ASA formulations was essentially equal and similar to that of the salicylate formulation, the bioavailability and peak concentrations of ASA appeared to be the much greater after rapid-release than after slow-release formulations. Indeed, ASA was only rarely detected in systemic blood following intake of slow-release ASA. Co-administered dipyridamol did not significantly influence the kinetics of ASA or SA. It appears that rapid-release formulations of ASA should be prefered in anti-platelet therapy, either alone or in combination with dipyridamol.
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  • 24
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    European journal of clinical pharmacology 24 (1983), S. 41-47 
    ISSN: 1432-1041
    Keywords: quinidine ; digoxin ; interaction ; kinetics ; absorption ; elimination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary To evaluate the possible effect of quinidine on digoxin bioavailability, the steady state digoxin kinetics was examined with and without concomitant quinidine therapy, in 7 cardiac patients after simultaneous administration of oral digoxin and intravenous [3H]-digoxin. In the presence of quinidine, the absorption rate constant of digoxin (ka) increased from 2.72±1.04 to 3.53±1.34 h−1 (p〈0.05), whereas lag time and peak time decreased from 0.16±0.10 to 0.05±0.04 h (p〈0.05) and from 0.92±0.27 to 0.69±0.19 h (p〈0.02), respectively. Predose plasma digoxin increased from 0.41±0.25 to 0.70±0.31 ng/ml (p〈0.02), while peak plasma digoxin increased from 0.93±0.34 to 1.63±0.46 ng/ml (p〈0.02). The systemic availability of digoxin increased from 68.48±13.35 to 79.09±14.89% (p〈0.05) in the presence of quinidine. Quinidine had no effect on the biotransformation pattern of digoxin, as assessed by thin layer chromatography. Quinidine increases the rate and extent of digoxin absorption, and this interaction contributes significantly to the elevation in plasma digoxin during both its distribution and elimination phases.
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  • 25
    ISSN: 1432-1041
    Keywords: lorcainide ; oral antiarrhythmic therapy ; nor-lorcainide ; first-pass metabolism ; kinetics ; alternative dosage ; regimens
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The feasibility of giving a supplementary starting dose of the antiarrhythmic drug lorcainide, in order to minimalize the impact of the extensive, but saturable first-pass metabolism, was evaluated. Twenty-five adult patients were given 100 mg lorcainide tablets according to one of 3 different dosage schedules: Eight patients took one tablet at 0, 12 and 24h, 8 took 1 tablet at 0, 1, 12 and 24h and 9 took 1 tablet at 0, 2, 12 and 24h. Levels of lorcainide and its metabolite, nor-lorcainide, during treatment were determined by gas-liquid chromatography. The results show that giving a second tablet 1 or 2h after the first may produce faster saturation of the pre-systemic metabolism of lorcainide in the liver.
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  • 26
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    European journal of clinical pharmacology 24 (1983), S. 801-806 
    ISSN: 1432-1041
    Keywords: acebutolol ; hydrochlorothiazide ; kinetics ; drug combination ; interaction ; diacetolol ; healthy subjects ; renal clearance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics of acebutolol and hydrochlorothiazide (HCT) alone or in combination were studied in 12 healthy subjects in a cross over study. Acebutolol and diacetolol (the main metabolite) in plasma and urine were determined by HPLC and hydrochlorothiazide by GLC. The main pharmacokinetic parameters of acebutolol did not differ significantly: AUC 4492±272 µg l−1 h given alone versus 4118±354 µg l−1 h with HCT, half-life (7,69±0,32 h vs 8,10±0,72 h) and renal clearance (13,1±0,5 lh−1 vs 13,8±0,9 lh−1), respectively. There was no difference in diacetolol pharmacokinetics. HCT values were not significantly different: AUC 784±48 µg l−1 h given alone and 720±42 µg l−1 h with acebutolol, t1/2 (4,79±0,37 h vs 4,73±0,43 h). The renal clearance was slightly higher when HCT was given with acebutolol (26,2±2,6 vs 20,3±2,11 h−1,p〈0,05). This increase, observed during the first four hours, was probably due to competition between the drugs for binding to red blood cells.
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  • 27
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    European journal of clinical pharmacology 23 (1982), S. 261-266 
    ISSN: 1432-1041
    Keywords: mexiletine ; rifampicin ; kinetics ; enzyme induction ; excretion ; antipyrine clearance ; dosage adjustment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary To study the effects of enzyme induction on its pharmacokinetics, a single oral dose of the new antiarrhythmic agent mexiletine hydrochloride 400 mg was administered to 8 healthy volunteers before and after treatment with rifampicin 300 mg b.i.d. for ten days. The absorption and distribution of mexiletine were not changed after rifampicin, but its elimination half-life fell from 8.5±0.8 h (mean±SE) to 5.0±0.4 h (p〈0.01), and its nonrenal clearance increased from 435±68 ml/min to 711±101 ml/min (p〈0.01). The mean renal clearance of mexiletine did not change, but it showed an exponential correlation with urinary pH. The amount of unchanged mexiletine excreted in urine over two days decreased from 32±7 to 18±3 mg (p〈0.01). The half-life of antipyrine fell from 11.8±0.4 to 5.5±0.3 h and its clearance increased from 40±3 ml to 74±3 ml/min (p〈0.01). There was a significant (p〈0.05) positive linear correlation between both the half-lives and the clearances of antipyrine and mexiletine. The clearances were positively correlated with serum γ-glutamyl transpeptidase. The results suggest that the dosage of mexiletine should be adjusted when enzyme inducing drugs are started or stopped during therapy with it.
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  • 28
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    European journal of clinical pharmacology 23 (1982), S. 87-92 
    ISSN: 1432-1041
    Keywords: phenobarbital ; epilepsy ; kinetics ; bioavailability ; epileptic patients
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The kinetics of phenobarbital (PB) were evaluated in six normal subjects and six epileptic patients treated with phenytoin or carbamazepine. Each normal subject received three single doses of PB: PB-sodium 130 mg i.v. (IV), PB sodium 130 mg i.m. (IM), and PB acid 100 mg orally (PO), in random order at least one month apart. After IV PB distributive half-lives varied from 0.13 to 0.70 h, disposition half-lives were 75 to 126 h, steady state volume of distribution (Vss) was 0.54±0.03 l/kg, and clearance (CL) was 3.8±0.77 ml/h/kg. Absolute bioavailability of IM PB was 101±13%, of PO PB (corrected for dose) 100±11%. Peak serum PB concentrations were achieved from 2 to 8 h after IM administration, and from 0.5 to 4 h after PO administration. Epileptic patients exhibited similar PB kinetics: disposition half-lives were 77 to 128 h, Vss 0.61±0.05 l/kg, and Cl 3.9±0.76 ml/h/kg. Phenobarbital appears to represent an exception among antiepileptic drugs, in that pharmacokinetic data obtained in normals can reasonably be extrapolated to the epileptic population.
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  • 29
    ISSN: 1432-1041
    Keywords: metoprolol ; age ; disposition ; elderly subjects ; kinetics ; metabolism ; alpha-OH-metoprolol
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The absorption and disposition of metoprolol have been evaluated in 10 healthy, non-smoking, elderly individuals (mean age 73.1 years) by simultaneous determination of [3H]-metoprolol and unlabelled metoprolol. The labelled drug was given as an intravenous tracer dose, immediately followed by oral metoprolol 25 mg. The experiment was preceded by administration of metoprolol 25 mg b.i.d. for 3 days. The volume of distribution, elimination half-life and total body clearance were almost the same as previously observed in healthy, young subjects. The mean systemic availability was about 39% in the elderly, which is lower than the mean of 55% observed in a control group of young volunteers who received 50 mg b.i.d. In the elderly, the mean plasma concentration of α-OH-metoprolol was about twice as high as that of the parent drug, whereas the opposite was true of the control group. The results indicate that age-related physiological changes have a negligible effect on the pharmacokinetics of metoprolol.
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  • 30
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    European journal of clinical pharmacology 21 (1981), S. 149-153 
    ISSN: 1432-1041
    Keywords: cinromide ; epilepsy ; kinetics ; metabolites
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Cinromide is an experimental anticonvulsant currently in phase II testing. A single oral dose (900 mg) of cinromide was administered to 8 epileptic subjects on phenytoin therapy. Plasma samples drawn during the next 36 h were analyzed for cinromide and its amide and acid metabolites. The absorption rate of cinromide varied widely between subjects producing maximum cinromide concentrations between 0.5 and 2.5 h after the dose. The median elimination half lives of cinromide and the amide and acid metabolites were 0.73, 1.65, and 4.85 h respectively. The oral clearance of cinromide (median=135 l/h) suggests that it is subject to first pass metabolism. In all subjects the area under the curve (AUC) of acid metabolite (632 to 1777 µM/l) was greater than the AUC of amide metabolite (77 to 185 µM/l) which was greater than the AUC of cinromide (5 to 89 µM/l). Steady-state concentration ratios of metabolite to parent drug predicted from the AUC data were 3.8 for the amide and 35.8 for the acid metabolite. The amide metabolite is known to have anticonvulsant properties and, until the relative contributions of metabolites and parent drug to the efficacy of cinromide are resolved, the monitoring of metabolites as well as parent drug is imperative.
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  • 31
    ISSN: 1432-1041
    Keywords: hyperthyroidism ; propranolol ; methimazole ; metoprolol ; atenolol ; kinetics
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The kinetic profiles of oral methimazole 40mg, propranolol 80mg, metoprolol 100mg and atenolol 100mg were compared in hyperthyroid patients both during the hyper-and euthyroid states. For methimazole, neither the peak concentration (Cmax), the time to reach peak concentration (tmax), the elimination half-life (t1/2) nor the area under the curve (AUC) value was affected by the hyperthyroid state. For propranolol and metoprolol, which undergo extensive presystemic clearance, the AUC values were lower (p〈0.02) when the patients were hyperthyroid than when they had become euthyroid, but the t1/2's were not significantly altered. For atenolol, there were no significant kinetic differences between the hyperthyroid and euthyroid states. The findings are compatible with the assumption that hyperthyroidism does not affect the kinetics of methimazole or atenolol, but that it may enhance presystemic clearance of propranolol and metoprolol.
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  • 32
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    European journal of clinical pharmacology 27 (1984), S. 233-236 
    ISSN: 1432-1041
    Keywords: glibenclamide ; acarbose ; kinetics ; alpha-glucosidase inhibitor ; blood glucose control ; plasma insulin ; Type 2 diabetes
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary A single dose of glibenclamide 5 mg was administered to six Type 2 diabetics, randomly treated for 7 days either with acarbose (3×100 mg daily) or with placebo. The serum concentration of the drug was measured for 10 h. Peak concentrations, times-to-peak concentration, elimination half-lives and the extent of bioavailability of the drug were not significantly modified by acarbose. The combined administration of glibenclamide and acarbose resulted in a modest improvement in the blood glucose profile after breakfast and lunch, together with a significant diminution in plasma insulin. Thus, acarbose appears a useful additional treatment for Type 2 diabetics already receiving sulphonylurea derivatives.
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  • 33
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    European journal of clinical pharmacology 26 (1984), S. 521-530 
    ISSN: 1432-1041
    Keywords: chloroquine ; malaria ; rheumatoid disease ; kinetics ; major metabolite ; optimal dosage ; therapeutic regime ; monodesethylchloroquine ; bidesethylchloroquine
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The kinetics and disposition of chloroquine (CQ) and its metabolite monodesethylchloroquine (CQM) were investigated in 5 healthy volunteers after incremental (150–300–600 mg CQ base) single oral doses of CQ. The analytical method used (HPLC and fluorescence detection) is the most sensitive known method for CQ and CQM. Plasma and whole blood concentrations of CQ, CQM and a third metabolite, bidesethylchloroquine (CQMM), were determined. The kinetics of CQ was found to be unique. The best fit was obtained by a multicompartmental model. The biological half-life appeared to be between 30–60 days; the volume of distribution (Vd) was ∼ 800l/kg, and the clearance ∼ 11/h/kg when calculated from plasma data. The whole blood concentrations were ∼ 8–10 times higher than in plasma, and consequently the Vd and whole blood clearance were ∼ 10 times lower. The kinetics changed as the dose was increased. An indication of capacity-limited steps in CQ disposition was found, as the rate constants decreased even though the clearance remained the same. The intrinsic half-life of CQM was 1/4 of that of CQ, but was prolonged after the highest dose of CQ. The present knowledge of CQ kinetics could provide a basis for revision of current dosage regimens in malaria suppression and rheumatoid disease to ensure efficacious and safe therapy.
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  • 34
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    European journal of clinical pharmacology 27 (1984), S. 367-369 
    ISSN: 1432-1041
    Keywords: flurbiprofen ; syrup ; suppository ; kinetics ; children ; bioavailability
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Eight subjects, aged 6–12 years and weighing 18.8–36.7 kg, received single doses of flurbiprofen 50 or 75 mg (corresponding to 1.4–2.7 mg/kg) as syrup and suppository in a Latin square design. Half-life (2.7–3.2 h), elimination constant (0.22–0.26 h−1), area under the plasma level curve (72.4–77.3 µg·h·ml−1) and time to reach the concentration peak (1–0.75 h) were similar after the syrup and suppository. Flurbiprofen showed equivalent bioavailability after oral and rectal administration and the same pharmacokinetic profile was confirmed in children as observed in adults.
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  • 35
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    European journal of clinical pharmacology 22 (1982), S. 39-45 
    ISSN: 1432-1041
    Keywords: furosemide ; neonates ; kinetics ; placental transfer ; intravenous therapy
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics of furosemide was evaluated in 12 newborns who received the drug transplacentally, and in 21 neonates who received it directly for therapeutic reasons. In the first group, the apparent plasma half-lives ranged from 96 to 6.8 h with a significant inverse relationship (p〈0.01) between the gestational age and the elimination rate. In two cases a clear effect on diuresis was also observed. In the neonates receiving the drug i.v. for therapeutic reasons, the elimination kinetics appeared to follow a two-compartment open model, with a significant difference in the therminal plasma half-life between premature (26.8±12.2 h) and full-term newborns (13.4±8.6 h). In this group no relationship was observed between elimination rate and either gestational or conceptional age. In the case of repeated administration, an increase in plasma clearance and reduction in t1/2 β was noticed.
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  • 36
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    European journal of clinical pharmacology 22 (1982), S. 435-439 
    ISSN: 1432-1041
    Keywords: azlocillin ; kinetics ; biliary excretion ; liver dysfunction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetic of azlocillin was followed in five elderly patients after biliary surgery. Total clearance was 138.6±17.7 ml/min when 2.0 g was given as an i.v. bolus injection. The half-life of the β-phase averaged 110 min. The total clearance and the half-life of azlocillin were influenced by slight impairment of renal function (creatinine clearance 59.4±13.6 ml/min). In patients with normal liver function biliary excretion of the drug amounted to 5.3±2.8% of the dose (n=3) and the kinetics of biliary excretion were linear. In contrast, in two patients with impaired liver function biliary excretion was 0.2% and 0.5% of the dose, and kinetic analysis of biliary excretion rates revealed at least one zero order step in the excretion process. Renal excretion of the drug amounted to 45.0±17.7% of the dose, which means that 50% of the total clearance of azlocillin has to be accounted for by metabolic clearance.
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  • 37
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    European journal of clinical pharmacology 23 (1982), S. 529-533 
    ISSN: 1432-1041
    Keywords: beta-blocker ; bufuralol ; enantiomers ; kinetics ; metabolism ; man
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Single oral doses of (+)-, (−)- and (±)-bufuralol were administered to a healthy volunteer to compare the disposition and metabolism of the individual isomers and the racemate. Plasma levels and area under plasma curve (AUC) of the active isomer, (−)-bufuralol, were higher than those of the (+)-isomer; plasma clearance was correspondingly lower. Intermediate values were found for the racemate. The elimination half-life of (−)-bufuralol was shorter than that of (+)-bufuralol, but similar to the racemate. Both isomers were cleared almost entirely by metabolism. The main metabolic pathway for (−)-bufuralol was aromatic hydroxylation, whereas the principal route for (+)-bufuralol was conjugation. Phenol metabolites in the systemic circulation were present mainly as conjugates. Both isomers also underwent aliphatic hydroxylation. This pathway was more favoured by the (+)-isomer, although plasma levels and AUC of the principal product, 2′-hydroxy-bufuralol, were almost identical for the two forms. Major differences in metabolic fate thus had relatively little effect on the disposition of pharmacologically active metabolites.
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  • 38
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    European journal of clinical pharmacology 24 (1983), S. 243-246 
    ISSN: 1432-1041
    Keywords: tolbutamide ; valproate ; intoxication ; activated charcoal ; inhibition of absorption ; sulphonylureas ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The claim that activated charcoal should be ineffective or even contraindicated in intoxication due to tolbutamide is based only on limited in vitro studies. To test the claim, the effect of activated charcoal 50 g on the absorption of tolbutamide and, as a reference, of sodium valproate, was studied in 6 healthy volunteers. Each volunteer swallowed tolbutamide 500 mg and sodium valproate 300 mg with 50 ml water 1 h after a light breakfast, and within 5 min they took in randomized order either a suspension of activated charcoal or water. The absorption of tolbutamide, calculated as the peak concentration and the area under the serum drug concentration-time curve during 0–48 h, was reduced by 90% by charcoal (p〈0.001). The absorption of valproate in these conditions was reduced on average by 65% (p〈0.01). In each subject charcoal had a greater effect on the absorption of tolbutamide than of valproate. According to these findings and preliminary in vitro studies on other sulphonylureas high doses of activated charcoal can be recommended for the preventing the absorption of sulphonylureas in acute intoxications. The poor aqueous solubility of these substances at the gastric pH probably delays their gastrointestinal absorption, so that they may be adsorbed on to charcoal even given several hours later.
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  • 39
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    European journal of clinical pharmacology 22 (1982), S. 27-32 
    ISSN: 1432-1041
    Keywords: sulfonylureas ; diabetes ; chlorpropamide ; glipizide ; C-peptide ; insulin ; blood glucose ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The influence of sulfonylurea on the secretion, disposal and effect of insulin was studied in 9 Type 2 diabetics during 3 one-month courses of treatment with a) chlorpropamide (t1/2〉24 h) once daily, b) glipizide (t1/2=2–4 h) once daily, and c) glipizide in divided doses. Food intake by each patient was identical during each period. Blood concentrations of immunoreactive insulin (IRI) and C-peptide (radioimmunoassays), and of glucose (enzymatic assay), chlorpropamide (gas chromatography) and glipizide (high-pressure liquid chromatography) were determined before and after breakfast and lunch on the 4th day of each examination period. All comparisons were intraindividual. Despite the lunch-time dose of glipizide given during the divided dose treatment, once-daily administration of this drug led to higher drug concentrations not only after breakfast but also for the first few hours after lunch. Divided dosage, on the other hand, led to higher concentrations later. In contrast to once-daily dosage, continuous exposure to glipizide was found in most patients. Chlorpropamide gave the most continuous sulfonylurea exposure. The blood glucose levels were inversely related to the concurrent sulfonylurea concentrations; glucose levels after breakfast and lunch were lowest during once-daily glipizide, whereas the fasting level was lowest during chlorpropamide treatment. The IRI response to breakfast was 60%–70% higher during once-daily glipizide than during the other two treatments, but the C-peptide responses to breakfast were almost identical. Thus, the greater after-breakfast availability of peripheral insulin appeared to be due to an effect of glipizide on the extrapancreatic disposal of the hormone.
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  • 40
    ISSN: 1432-1041
    Keywords: digoxin ; verapamil ; digoxin-verapamil interaction ; kinetics ; plasma level ; renal clearance ; extra-renal clearance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Single-dose investigations in healthy subjects have demonstrated substantial impairment of renal and extrarenal clearance of digoxin during coadministration of verapamil. A longitudinal study has been performed to assess the changes in digoxin disposition during long-term verapamil therapy. After one week of verapamil 240 mg/d mean plasma digoxin had risen from 0.21±0.01 ng/ml (SE) to 0.34±0.01 ng/ml (p〈0.01), and renal digoxin clearance had fallen from 197.57±17.37 ml/min to 128.20±10.33 ml/min (p〈0.001). These changes gradually subsided, and after six weeks, renal digoxin clearance had normalized and plasma digoxin had declined to 0.27±0.02 ng/ml (NS). The 24-h urinary recovery of digoxin increased from 46.46±3.23% before to 69.78±3.69% (p〈0.001) after six weeks of verapamil co-administration, and this elevation persisted throughout the study. The verapamil-induced suppression of renal digoxin elimination disappears over a few weeks of drug exposure, whereas the inhibition of the extrarenal clearance of digoxin seems to persist.
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  • 41
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    Plasma chemistry and plasma processing 1 (1981), S. 19-35 
    ISSN: 1572-8986
    Keywords: Decomposition of NH3 ; kinetics ; optical spectroscopy ; gas chromatography
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The plasma decomposition of NH3 has been studied as a function of the residence time, power input, and pressure. The process follows apparently zero-order kinetics, which can be interpreted on the basis of a kinetic mechanism involving as initial step the rupture of an N-H bond from vibro-rotationally excited modecules. Simultaneous spectroscopic observations of the emission light due to electronically excited NH2, NH, H, and N2 have been used to confirm the suggested mechanism and to show that NH2 and NH are successive intermediate species and that the final step of the decomposition process is the bimolecular recombination NH+NH→N2+H2.
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  • 42
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    Plasma chemistry and plasma processing 1 (1981), S. 233-245 
    ISSN: 1572-8986
    Keywords: Plasma ; kinetics ; polymerization ; propylene
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Flowing microwave plasma of propylene and propylene with argon was studied by mass spectrometry. Plasma composition was investigated as a function of external parameters such as pressure, argon/propylene ratio, and microwave-induced power. It was found that the propylene broke down to C2H2 and CH4, or reacted further with propylene. Two main products, leading to the determination of three main chain reactions for the polymerization of propylene by ion-molecule interactions, were observed, namely, C2H2 and CH4. These were the propylene, acetylene, and ethylene chain reactions. It was also found that the propylene disappeared in a pseudo-first-order reaction. Consequently an overall rate constant for the polymerization was determined (50 sec−1 at 1 torr pressure for propylene plasma). This constant is found to be linearly dependent upon the propylene percent concentration, and nonlinearly dependent upon plasma pressure.
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  • 43
    ISSN: 1573-4889
    Keywords: tantalum alloy ; oxygen ; dissolution ; kinetics ; oxides
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxygen was added to T-111 (Ta-8W-2Hf, wt.%) at 820 and 990°C at an oxygen pressure of about 3×10−4 Torr (4×10−2N/m2). The technique employed permitted predetermined and reproducible doping of T-111 up to 3.0 at% oxygen. Based on the temperature dependence of the doping reaction, it is concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the latter oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and of other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high-temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990°C. The vaporization of WO3 has no apparent affect on the doping reaction.
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  • 44
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    Oxidation of metals 11 (1977), S. 127-132 
    ISSN: 1573-4889
    Keywords: Duplex oxides ; copper oxidation ; kinetics ; oxygen partitioning
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The theory for the growth of a double oxide layer proposed by Yurek, Hirth, and Rapp, has been applied to copper using experimental rate-constant data obtained by Valensi. Calculated thicknesses of the layers agree very well with experimentally measured values.
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  • 45
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    Oxidation of metals 9 (1975), S. 459-472 
    ISSN: 1573-4889
    Keywords: Cr ; oxidation ; kinetics ; Cr2O3 grain size ; short-circuit diffusion ; surface ; preparation ; Fe-Cr
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Cr was oxidized in 1 aim O2 at 980, 1090, and 1200°C. ElectropolishedCr and some orientations of etched Cr oxidize rapidly and develop compressive stress in the growing Cr2O3; other orientations oxidize slowly, apparently free of stress. SEM examination of fracture sections shows that the thick oxide is polycrystalline whereas the thin oxide on etched Cr is monocrystalline. It is deduced that the monocrystalline oxide grows by lattice diffusion of cations outward, and the polycrystalline layer by the two-way transport of cation diffusion outward and anion diffusion inward along oxide grain boundaries. The consequent formation of oxide within the body of the polycrystalline layer generates compressive stress and leads to wrinkling by plastic deformation. The activation energy for oxidation of Cr by cation lattice transport is 58 kcal/mole. Polycrystalline Cr2O3 forms on Fe-26Cr alloy, whether electropolished or etched; oxidation is accordingly rapid and accompanied by compressive stress.
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  • 46
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    Biochemical genetics 19 (1981), S. 881-893 
    ISSN: 1573-4927
    Keywords: chicken kidney ; ornithine transcarbamylase ; Cochin Bantam ; White Leghorn ; genetics ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Comparisons were made of the renal ornithine transcarbamylase (OTC) activities within different groups of chickens including Japanese native breeds. OTC activities varied markedly within these groups. The Cochin Bantam breed and White Leghorn B line had an especially high activity, about 400 units/g of kidney, in contrast to two Japanese native breeds, Japanese Game (white variety) and Banshuu Gashiwa, and the California Gray breed, which showed a very low activity, the values being almost undetectable. In crossing experiments using the California Gray breed as a tester strain, Cochin Bantam OTC represents a simple autosomal incompletely dominant trait similar to the White Leghorn B line OTC. Kinetic studies using partially purified OTC preparations from the White Leghorn B line and Cochin Bantam breed revealed that both enzymes were identical for a variety of enzymic characteristics. In light of these results, the physiological significance of chick kidney OTC is discussed.
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    Oxidation of metals 10 (1976), S. 85-95 
    ISSN: 1573-4889
    Keywords: boron carbide ; oxidation ; kinetics ; chromatography method
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Thermogravimetry and gas-adsorption chromatography were used to study the kinetics of formation of solid and gaseous products during the hightemperature oxidation of compact boron carbide in oxygen at 740 Torr. Oxidation resistance was observed at temperatures up to 1200°C. The main oxidation products were B2O3 and CO2. Oxidation was paralinear; the carbon consumption exceeded the consumption of boron as compared to the ratio of these elements in the compound B4C. This difference resulted in carbon depletion of the carbide layer in the substrate near the scale〉.
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  • 48
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    Oxidation of metals 10 (1976), S. 361-376 
    ISSN: 1573-4889
    Keywords: metals ; scale structure ; epitaxy ; kinetics ; diffusion
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract An explanation of the deviation from the parabolic law is the treatment which considers both shortcircuit and lattice diffusion in the oxide scale. In this study we examine how the oxidation kinetics are influenced by changing the structure of the scale of copper oxide in order to confirm the role of short-circuit diffusion in determining the oxidation rate. In addition we explain the oxidation kinetics of copper and nickel by using a model of the scale structure which includes recrystallization and grain growth. Results are as follows: (1) The nucleation and growth behavior of oxide have a direct effect on the structure and in turn the oxidation kinetics due to short-circuit diffusion. (2) A modified treatment is valid in the region where volume diffusion and short-circuit diffusion play an important role in which it is necessary to consider the scale structure such as the grain size distribution and the boundary width. (3) When recrystallization takes place it is necessary to consider the model of a two-layered scale structure which is different in properties and morphology. (4) In this region the rate curves are S-shaped when oxide recrystallization takes place and exhibit a transition from a parabolic to an nth-power relationship (n〉2) when grain growth takes place.
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    Oxidation of metals 11 (1977), S. 225-239 
    ISSN: 1573-4889
    Keywords: tantalum ; oxidation ; 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 tantalum in oxygen-nitrogen and oxygen-inert gas mixtures at925°C has been studied. The oxygen pressure was close to 0.5 atm in all experiments, and partial pressures of the second component of from 0 to 180 Torr were employed. Spherical specimens were used to provide quantitatively significant kinetic data. A model has been proposed which suggests that the oxygen pressure at the reaction interface close to the metal surface is lower than the external pressure because of the finite permeability of the porous outer oxide layer, and that the inert gas effectively reduces the permeability. The model gives good quantitative agreement with the experimental results.
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    Oxidation of metals 11 (1977), S. 365-381 
    ISSN: 1573-4889
    Keywords: cobalt oxidation ; kinetics ; parabolic rate constant
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Precise values of parabolic rate constants of cobalt oxidation have been determined over a wide range of temperature (950–1300°C) and oxygen pressure (6.58× 10−4−0.658 atm). The dependence of the calculated values of parabolic rate constants k″p on oxygen pressure and temperature can be described by the following empirical equation: $$k''_p = const. \cdot {\text{p}}_{O_2 }^{{\text{1/n}}} \cdot exp ( - {\text{E}}_{\text{k}} /RT)$$ The exponent 1/n decreases with an increase in temperature from 1/3.40 at 950°C to 1/3.96 at 1300°C, whereas the activation energy Ek decreases with an increase in the oxygen pressure from 41.7 to 38.1 kcal/mole.
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    Oxidation of metals 13 (1979), S. 77-88 
    ISSN: 1573-4889
    Keywords: BaTiO3 ; kinetics ; solid state
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The solid-state reaction between barium carbonate and rutile powders to form barium metatitanate BaTiO3 was studied by thermogravimetric analysis, X rays, and microscopy. Phase-stability domains were drawn in a temperature— $${\text{p}}_{CO_2 } $$ , diagram. The dependence of the reaction kinetics on $${\text{p}}_{CO_2 } $$ , $${\text{p}}_{O_2 } $$ or $${\text{p}}_{N_2 } $$ is discussed. In particular, the rate continuously decreases when $${\text{p}}_{CO_2 } $$ , or $${\text{p}}_{N_2 } $$ increases, but it reaches a maximum as a function of $${\text{p}}_{O_2 } $$ .
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  • 52
    ISSN: 1573-4889
    Keywords: Cu-Si alloys ; oxidation ; kinetics ; silica
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of Cu-Si alloys (containing up to 4.75 wt. % Si) in $${\text{p}}_{O_2 } $$ =0.01 atm from 800 to 1000°C has been investigated using thermogravimetry and other techniques. A 0.04% Si alloy followed a parabolic oxidation law with a rate similar to that of pure Cu. As the Si concentration increased the rate decreased and became irregular owing to SiO2 particles or flakes at the alloy-scale interface. It is considered that sintering of SiO2 particles and rupture of the sinter because of contraction during sintering are responsible for the irregular kinetics. A SiO2 layer forms directly on the 4.75% Si alloy which oxidizes uniformly. The SiO2 was always amorphous. In pure CO2 a similar pattern of amorphous SiO2 particles, flakes, and layers occurs.
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  • 53
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    Oxidation of metals 13 (1979), S. 283-298 
    ISSN: 1573-4889
    Keywords: oxidation ; surface alloys ; Fe-Cr alloys ; iron ; kinetics
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of several surface and bulk Fe-Cr alloys and iron at 300°C and 4×10−6 Torr oxygen was studied. The surface alloys were fabricated by implantation of 25 keV Cr ions into the outermost 300Å of polycrystalline iron samples. The oxide thickness as a function of oxygen exposure was obtained using proton-excited X-ray analysis, and composition profiles of oxide films were obtained using Auger electron spectroscopy and ion sputtering. The addition of Cr to Fe by surface and bulk alloying caused the oxidation rate to decrease and changed the oxidation kinetics from parabolic (for Fe) to logarithmic (for Cr concentrations ≥4.7at.%). Interpretation of the data in terms of simple oxidation theories indicates that the Cr additions may reduce the oxidation rate by altering the electronic properties of the metal-oxide interface.
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    Oxidation of metals 13 (1979), S. 255-272 
    ISSN: 1573-4889
    Keywords: oxidation ; Fe-C ; graphite deposition ; nonadherent oxide ; kinetics
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of Fe-C alloys containing 0.5 and 1.0% C was studied in 1 atm O2 at 700° C. The oxidation rate is considerably slower than for pure Fe. The oxide scale formed is detached, multilayered, and overoxidized, containing little or no FeO. A thin film of graphite was identified at the metal-oxide interface by electron diffraction. It is proposed that the slow oxidation and abnormal scale are caused by a residue of graphite left at the metal surface from the oxidation of Fe3C. This inhibition of the oxidation of Fe by carbon at 700°C is in contrast to the stimulation observed at 500°C.
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    Oxidation of metals 13 (1979), S. 301-309 
    ISSN: 1573-4889
    Keywords: NiO ; Electrical conductivity ; gas-solid equilibria ; kinetics ; equivalent circuit
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In a previous work it has been stated that the NiO electrical conductivity changes connected to the oxygen pressure changes may be considered as a transitory phenomenon. A mixed kinetics case controlled by the formation of surface cation vacancies and their diffusion in the bulk is proposed to explain the reaction process. By means of an equivalent electrical circuit in good agreement with the kinetics model it was possible to reproduce the experimental phenomenon.
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    Oxidation of metals 13 (1979), S. 481-504 
    ISSN: 1573-4889
    Keywords: kinetics ; sulfidation ; Fe-Cr-Al alloys
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The influence of aluminium on the kinetics and mechanism of high-temperature sulfidation of Fe-Cr alloys containing 20 at.% chromium has been investigated. It has been found that the addition of aluminum greatly improves the scaling resistance of Fe-Cr alloys against attack by sulfur vapors at high temperatures.
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    Oxidation of metals 17 (1982), S. 359-369 
    ISSN: 1573-4889
    Keywords: Oxidation ; microhardness ; oxide thickness ; kinetics ; oxygen partition
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxidation kinetics of Ti-1 wt. % Si and Ti-5 wt. % Si alloys in either pure oxygen or air under a pressure of 0.93 bar and in the temperature range of 1171–1473 K are reported. For the exposure period investigated (up to 12 h) both alloys oxidized slower than pure Ti. The amount of oxygen dissolved in the Ti-1 wt. % Si alloy has been calculated. X-ray diffraction analyses indicate that the oxide scale is mainly TiO 2 ,except for the Ti-5 wt. % Si alloy oxidized at 1473 K where some evidence of SiO 2 was obtained. Hardness profiles were taken across the Ti-1 wt. % Si alloy matrix.
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    Oxidation of metals 20 (1983), S. 37-65 
    ISSN: 1573-4889
    Keywords: Alloy oxidation ; cobalt-chromium-tungsten ; scale formation ; kinetics
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxidation rates in air at 1000–1250°C are reported for a series of Co-Cr-W alloys with 34–40 wt. % Cr and up to 10 wt. % W. Alloys with larger W contents exhibited slower oxidation rates and their parabolic rate constants agreed well with those for binary and ternary, Cr2O3 protected, Ni-base and Co-base alloys in the Co-Cr and Ni-Cr-W systems. The resulting scales were characterized by optical and scanning electron metallography, and electron microprobe analysis. The favorable effect of W additions to a Cr2O3-forming Co-Cr base alloy was the opposite of that reported for Ni-Cr-W alloys. The resupply of Cr to a Cr-depleted matrix beneath a protective CrO3 scale is achieved by the dissolution (denuding) of Cr-rich second phases in the Co-Cr-W alloys. Thus, the internal oxidation of Cr beneath the Cr2O3 scale is avoided for high W alloys. No catastrophic failure by liquid phase formation was observed for high-W alloys oxidized 20 hr at 1250°C.
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  • 59
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    Oxidation of metals 9 (1975), S. 357-365 
    ISSN: 1573-4889
    Keywords: kinetics ; zirconia ; defect structure ; ionic conductivity ; yttria dopant
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A Zr-0.5 Y alloy was found to oxidize about 6 times faster than pure zirconium over the temperature range of 400 to 565°C. The activation energies were nearly identical (∼32 kcal/mole). The activation energies correspond to grain boundary diffusion of oxygen through the scale. The higher oxidation rate of the alloy was attributed to a higher anion vacancy concentration and the assumption that diffusion sites in the lattice and boundaries were in local equilibrium. Measurements on yttria-doped zirconia showed that ionic conductivity was increased markedly by yttrium and extended over a wide range of oxygen pressure. The defect structure of the doped oxide was changed to one of oxygen vacancies, even at the high end of the oxygen pressure range, 10−8 to 0.2 atm, over which pure ziconia contains oxygen interstitials. The doped oxide was found to be extrinsic over the entire range of oxygen pressure and, although ionic conductivity predominated, electronic conductivity was still appreciable. The electronic conductivity, however, was still sufficiently high so that electron transport was not rate-controlling in the predominantly ionic-conducting scale.
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    Molecular and cellular biochemistry 64 (1984), S. 45-50 
    ISSN: 1573-4919
    Keywords: cardiac muscle ; kinetics ; pyruvate kinase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Summary The mechanism of activation by inorganic phosphate and ATP of cardiac muscle pyruvate kinase was studied with the aid of steady-state kinetics. The enzyme was purified to homogeneity to a final specific activity of 400 units/ mg (phosphate buffer, pH 7.6, 25 °C). At pH 7.6 the enzyme displays Michaelis-Menten kinetics with respect to both its substrates, phosphoenolpyruvate and ADP. Substrate kinetic constants are: app.Km(phosphoenolpyruvate) −0.04 mM, app.Km(ADP) =0.22 mM. Under the conditions used in the standard assay the specific activity is greatly enhanced by inorganic phosphate (50 mM) or ATP (2.5 mM). Each of these modifiers, acting separately, increases the Vmax without seriously affecting Michaelis constants and Hill coefficients. In the presence of both Pi and ATP, only a decrease in Vmax was observed. The kinetics of activation by inorganic phosphate of pyruvate kinase was examined. Studying the effect of varying concentrations of Pi on the initial rate we obtained a hyperbolic saturation curve with the app. Km(Pi) = 20 mM and Vmax = 167 units/ mg. The evidence is presented that inorganic phosphate is a substrate for a side reaction catalyzed by cardiac pyruvate kinase. It is shown that in the presence of pyruvate, inorganic phosphate and ATP in the assay system, Pi is incorporated into acid-labile products of this reaction, inorganic pyrophosphate being one of them. These findings indicate the existence of an alternative reaction catalyzed by pyruvate kinase by which energy may be stored in the form of inorganic pyrophosphate.
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    Oxidation of metals 10 (1976), S. 97-103 
    ISSN: 1573-4889
    Keywords: silicon carbide ; oxidation ; molecular oxygen ; glow-discharge oxygen plasma ; 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 kinetics and structure of the oxide scales formed on high-density SiC were studied in molecular oxygen at 740 Torr and in a glow-discharge oxygen plasma at 0.1 Torr at temperatures of 1000, 1100, and 1200°C. The monatomic oxygen formed by the glow discharge markedly increased the reaction rate and the vaporization of some of the oxidation products. The marked differences in kinetics suggest that the rate-controlling step during oxidation in molecular oxygen is the dissociation of adsorbed diatomic oxygen to the monatomic species. Films formed in molecular oxygen were mostly amorphous SiO2 with small inclusions of SiC and graphite, whereas films formed in dissociated oxygen were primarily amorphous SiO2 containing SiO, S2O3, and the coesite form of SiO2.
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    Oxidation of metals 12 (1978), S. 215-225 
    ISSN: 1573-4889
    Keywords: oxidation ; Fe-Ni alloys ; kinetics ; scale morphology ; EPMA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of an Fe—19.34 wt. % Ni alloy in dry CO2 has been studied at 700—1000°C using thermogravimetry, metallography, and EPMA. Weight gains for oxygen consumption followed a linear-parabolic-linear sequence at all temperatures. During the initial linear stage the scale consisted mainly of magnetite and the activation energy of 133±25 kJ · mole−1 is considered to be due to dissociation of CO2 into CO and adsorbed oxygen on the outer magnetite surface. During the parabolic oxidation stage a continuous Ni-rich layer containing ∼ 70% Ni forms a barrier to the diffusion which has an activation energy of 192±79 kJ · mole−1. The breakdown of the barrier layer causes a return to linear kinetics with an activation energy of 138±42 kJ · mole−1 for dissociation of CO2 on the outer surface. During the final linear stage there is pronounced general and intergranular subscale formation. Detailed information is presented of the Ni redistribution and concentrations during oxidation and its correlation with the kinetics and morphology.
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    Oxidation of metals 14 (1980), S. 85-108 
    ISSN: 1573-4889
    Keywords: alloy oxidation ; nickel-chromium-tungsten ; scale formation ; kinetics
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior in air at 1000–1250°C of four Ni-Cr-W alloys containing sufficient chromium content (∼22 at. % Cr) for protective Cr2O3 formation in a binary Ni-Cr alloy is reported. Generally for alloys high in W (10 and 16 at.% W), the rejection of tungsten into the alloy beneath the scale introduced a steep Cr concentration gradient and slower Cr diffusion such that continuous precipitation of Cr2O3 internal oxides prevented the formation of a Cr2O3 protective scale. The alloy most dilute in W (1.6 at. % W) formed a protective scale at short times with little outer NiO scale, but scale fractures led to internal oxidation and rapid nonprotective kinetics. After an initially rapid oxidation increment to form NiO, the 3 at.% Walloy formed a protective Cr2O3 scale with about the same steady-state parabolic kinetics as a binary Ni-30Cr alloy. The effect of ternary Wadditions on the development of Cr2O3 scales on Ni-Cr-W alloys is considered as a ternary analog to Wagner's description of the oxidation of Cu-Pt or Cu-Pd alloys.
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  • 64
    ISSN: 1573-4889
    Keywords: titanium ; oxidation ; oxide scale ; solid state diffusion ; 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 titanium was studied over the temperature range of 600 to 800°C in a pure oxygen atmosphere. A parabolic kinetics period is made up of a succession of short parts whose weight gain is nearly constant and whose beginning is characterized by an alteration of the oxidation rate. The kinetics curve is closely correlated with the morphology of the oxide scale which contains several layers separated by short cracks. These cracks decrease the diffusional flows of oxygen and titanium and alter the oxidation rate. A parabolic-linear kinetics transition is attributed to the formation of a continuous crack between the oxide scale and the matrix. The oxide scale then forms a porous barrier of constant thickness which induces a linear rate law due to the steady-state oxygen diffusion. Titanium cannot diffuse across the continuous crack. During the linear kinetics period several layers of constant thickness, separated by a continuous crack, spread out.
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    Oxidation of metals 15 (1981), S. 437-445 
    ISSN: 1573-4889
    Keywords: chromium nitriding ; kinetics ; parabolic rate constant ; diffusivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Parabolic rate constants of the reaction of chromium with nitrogen gas under oxygen-free conditions have been determined over a range of temperature (1000–1250°C) and nitrogen pressure (0.265–101.33 kPa). The growth rate of the subnitride was measured by a thermogravimetric technique using a single specimen. Wagner's oxidation theory is used to calculate the self-diffusivity and intrinsic diffusivity of nitrogen in the subnitride from a theoretical analysis of the parabolic rate constant. The calculated diffusivities varied with the composition of the subnitride, having minimum values at intermediate compositions of the nonstoichiometric chromium nitride “Cr2N.”
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    Oxidation of metals 16 (1981), S. 175-191 
    ISSN: 1573-4889
    Keywords: Sulfidation ; Fe-Cr alloy ; 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 scaling of an Fe-20Cr alloy has been studied in H2-H2O-H2S mixtures between 973 and 1223 K. According to a simplified phase diagram, Cr2O3 and FeS should be the thermodynamically stable compounds in the gas mixtures chosen. The reaction followed a mixed rate law between linear and parabolic, indicating that the reaction rate at the scale-gas interface was comparable with the diffusion rate in the scale. At a constant H2/H2S ratio the scaling rate initially decreased slightly with increasing water-vapor pressure. A further increase of the water-vapor pressure resulted in localized sulfide formation, while the other parts of the surface were covered with a Cr2O3 film. Only Cr2O3 formed above a critical water-vapor content. Three zones could be distinguished when a sulfide scale is formed. The outer zone consisted of practically pure FeS; the intermediate zone was a solid solution of (Fe,Cr)S, partially decomposed to FeCr2S4 and metal during cooling; and the inner zone contained small Cr2O3 inclusions in an (Fe,Cr)S matrix.
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    Oxidation of metals 21 (1984), S. 21-37 
    ISSN: 1573-4889
    Keywords: internal oxidation ; kinetics ; alloy ; silver ; precipitation ; coalescence ; ageing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The internal oxidation mechanism in silver alloys was studied by residual resistivity, gravimetric, and calorimetric measurements, and by transmission electron microscopy. If the flux, of oxygen atoms is very large with respect to the oxide formation, the mechanism of internal oxidation includes two stages. The first one is the fixation of oxygen in the form of oxidized elementary species, including only one solute atom. These species are stable and keep a certain mobility. The second one is the coalescence process of these elementary species with the formation of the first clusters. When the flux of oxygen atoms is slowed down, the oxide formation mechanisms are more complicated. The initially formed species can include more than one solute atom because of their diffusion. The two stages are not separate.
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    Oxidation of metals 21 (1984), S. 103-118 
    ISSN: 1573-4889
    Keywords: duplex steels ; sulfidation ; kinetics ; transport processes
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Two austeno-ferritic stainless steels were sulfidized at temperatures of 783, 873, and 963 K under sulfur pressures in the range 4×10−12 to 3×10−5 atm. In all cases a triplex scale developed, consisting of an outermost layer of (Fe, Cr)1−xS, an intermediate layer of FeCr2S4, and an innermost layer of porous (Cr, Fe)1−xS containing particles of Mo2S3. Parabolic kinetics were observed except at the lowest temperature where one of the steels reacted according to irregular kinetics. The Mo2S3 particles in the innermost layer acted as inert markers, imaging the former positions of the steels' ferrite phase in which Mo is enriched. The lamellar microstructure of the steel was thus reproduced in the innermost sulfide layer. The positions of the Mo2S3 particles together with the porosity of the inner layer are taken to imply inward sulfur transport through this layer and outward metal transport through all three layers.
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    Oxidation of metals 9 (1975), S. 99-116 
    ISSN: 1573-4889
    Keywords: oxidation ; kinetics ; ilmenite ; rutile ; pseudobrookite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of ilmenite (FeTiO3) in air and dry oxygen was investigated over the temperature interval 600 to 970°C. Dense platelets of ilmenite crystals as well as powder samples of ilmenite were oxidized. The weight data were recorded employing a thermobalance. The oxidation kinetics of ilmenite platelets were parabolic except for the initial stages during which logarithmic kinetics were observed. For powder samples the logarithmic rate law was followed primarily. The logarithmic rate law was attributed to free penetration of oxygen through cracks and short-circuit paths. The activation energies associated with the logarithmic rate law were nearly one-half of those obtained from parabolic oxidation. The growth morphology of the products of oxidation of ilmenite was observed with a scanning electron microscope. The effect of growth morphology on the kinetics is discussed, and a probable reaction mechanism is suggested for the oxidation of ilmenite.
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  • 70
    ISSN: 1573-4889
    Keywords: kinetics ; cobalt and nickel oxidation ; parabolic rate constant
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A new fast method is proposed for the determination of parabolic rate constants of metal oxidation as a function of pressure and temperature. The method consists of determining rate constants by oxidation of a single metal sample in a continuous manner, periodically changing the oxidant pressure or temperature. This method eliminates a number of errors inherent in the classical method which involves the use of a new metal specimen in each experiment and it further shortens the time of evaluating the functions k p '' = f (p, T). The method is particularly suitable for the determination of rate constants of slow processes. To verify the proposed method measurements of the kinetics of oxidation of cobalt and nickel at different oxygen pressures over the temperature range 1000–1300° C were carried out.
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  • 71
    ISSN: 1573-4889
    Keywords: kinetics ; oxidation ; microcalorimetry ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
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    Notes: Abstract In the kinetic theories of Bodenstein or Semenov the expression for the rate of a chemical reaction with several elementary stages can be expressed by different physical parameters. If two experimental methods are used, one method of necessity being microcalorimetry to measure the thermal flux produced by the reaction, it is possible to distinguish a pure kinetics case from a mixed one. The two-method technique has been verified by a study of the oxidation of niobium.
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  • 72
    ISSN: 1573-4889
    Keywords: titanium ; nitridation ; kinetics ; diffusion ; scaling
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The nitridation behavior of titanium has been examined in an atmosphere of nitrogen over the temperature range 900–1000° C. In addition to determining the reaction kinetics, microhardness and metallographic studies have been carried out on the nitrided substrates and nitride scales. Overall parabolic kinetics were exhibited, while a linear scaling reaction (associated principally with Ti2N formation) was observed. Extensive dissolution of nitrogen in the substrate was evident from the microhardness studies, and at 950 and 1000° C the growth of the nitrogen-stabilized αTi phase layer followed a parabolic law. Consideration of all the observed processes and derived data suggested that diffusion of nitrogen in the metal substrate was probably the rate-controlling mechanism.
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    Oxidation of metals 11 (1977), S. 263-276 
    ISSN: 1573-4889
    Keywords: nickel ; sulfidation ; kinetics ; mechanism
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The reaction between pure nickel and H2S-H2 mixtures containing 1–65% H2S has been studied over the temperature range 450–600°C. The sulfidation of nickel in the temperature range 560–600°C has been found to follow a linear rate law at low concentrations of H2S and a parabolic rate law at higher concentrations (10% and 65% H2S); X-ray examination of the scale formed on the metal showed it to be almost entirely β-Ni3S2. On the basis of the kinetics and marker studies it can be concluded that the sulfide scale on nickel is formed by the outward transport of the metal and the inward transport of sulfur. In the temperature range 450–500°C the sulfidation of nickel follows a parabolic rate law. In mixtures containing 10% H2S the scale formed contains voids, the occurrence of which is connected with formation of Ni7S6. It has also been shown that the rate of transport through the Ni3S2 layer has an essential influence on the formation of a continuous layer of Ni7S6. Marker studies have shown that both nickel and sulfur appear to be mobile in β′-Ni3S2.
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  • 74
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    Oxidation of metals 12 (1978), S. 67-82 
    ISSN: 1573-4889
    Keywords: oxidation ; Fe-C ; kinetics ; oxide grain size ; grain-boundary diffusion
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Fe-C alloys containing 0.1, 0.5, and 1.0% C were oxidized in 1 atm O2 at 500°C. Two specimen preparations were used: annealed followed by slow cooling to form coarse pearlite plus proeutectoid ferrite or cementite; and cold-worked by abrading after annealing. The cold-worked alloys oxidize more rapidly. Annealed pearlite oxidizes faster than annealed ferrite. The differences in oxidation rate are caused by differences in the Fe3O4 grain size, that is, by the number of oxide grain boundaries available to act as easy diffusion paths for the outward diffusion of Fe through the Fe3O4. The oxidation rate constant is 10 times larger for fine-grained poly crystalline oxide than for oxide in which the Fe3O4 is monocrystalline.
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  • 75
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    Oxidation of metals 13 (1979), S. 437-456 
    ISSN: 1573-4889
    Keywords: Fe-Cr ; oxidation ; kinetics ; oxide morphology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Ferritic polycrystalline Fe-24 wt.% Cr was oxidized in pure oxygen at 190 ≤ T≤490° C and pressures in the range 5.3×10−2–13.3 Pa for periods of up to 5 hr. The reaction proceeded in three stages. An initial period of accelerating rate was accompanied by oxide island nucleation and growth. Following island coalescence the rate was approximately logarithmic at low temperatures and somewhat slower than parabolic at high temperatures. Rate control during this period was thought to be due to mass transport through the oxide grain boundaries left by the island impingement process. During these first two stages the oxide formed was γ-M2O3 with possibly some spinel. The final stage of reaction involved the appearance of α-M2O3 on the outer oxide surface and a substantial slowing of the oxidation rate due to the low diffusivity in this phase.
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  • 76
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    Oxidation of metals 13 (1979), S. 89-104 
    ISSN: 1573-4889
    Keywords: BaTiO3 ; kinetics ; solid state ; mechanisms
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The authors propose a mechanism for the solid-solid reaction BaCO3+ TiO2→BaTiO3+CO2. This mechanism is based on the real structure of the present semiconductors. The reactions at different interfaces and the diffusing species are identified. The reaction rates are calculated and the dependence of the reaction rate upon O2, N2, and CO2 gas pressure is interpreted and discussed.
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  • 77
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    Oxidation of metals 13 (1979), S. 119-158 
    ISSN: 1573-4889
    Keywords: nickel-chromium alloys ; oxidation ; high temperature ; kinetics ; mechanisms
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of binary Ni-Cr alloys containing 44 and 50 wt. % Cr has been studied over a range of oxygen partial pressures at temperatures between 800 and 1100°C. The effects of cold work, surface preparation, and distribution of the Cr-rich second phase have been studied. The oxidation behavior is complex and cannot be described by a single model. The oxide grows by short-circuit diffusion as well as bulk transport through Cr 2 O 3 scales. The scale-growth mechanism includes extensive metal-oxide separation requiring Cr vapor transport to the scale, compressive stresses within the oxide which result in scale bulging and cracking, and the formation of a second oxide layer which results in voids being incorporated into the scale. Any factor which reduces the oxide grain size, such as cold work, finer distribution of the Cr-rich α phase or reduced oxygen pressure, results in an increased oxidation rate of binary alloys because of an increased number of grain-boundary short-circuit diffusion paths.
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  • 78
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    Oxidation of metals 14 (1980), S. 147-165 
    ISSN: 1573-4889
    Keywords: oxidation in air or oxygen ; kinetics ; oxide identification ; oxygen diffusion
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation kinetics of Ti-4.32 wt.% Nb (2.27 at.%) alloy in either air or oxygen under 1 bar pressure have been investigated in the temperature range of 1255–1471 K. For oxidation in oxygen the kinetics follow consecutively decreasing parabolic rate laws. The kinetics become nonparabolic after prolonged oxidation in air. X-ray data reveal the presence of TiO2 (rutile) as the main oxide. The presence of Ti2O, δ-TiN, and ɛ-TiN is found on the metal surface after oxidation in air. Microhardness and electron microprobe measurements are used to determine Ti, Nb, O, and N profiles across the oxidized alloy. The oxygen diffusion coefficient in the alloy can be expressed byD=65.6 exp(−234.3/RT) with the activation energy in kilojoules per mole. The oxidation behavior of the alloy is explained.
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  • 79
    ISSN: 1573-4889
    Keywords: oxidation ; titanium ; Ti-Ni alloy ; Ti-Cu alloy ; kinetics ; oxide scale ; solid-state diffusion
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    Notes: Abstract The kinetics and morphologic oxidation properties of titanium, Ti-1.5Ni and Ti-2.5Cu were compared. Titanium and Ti-1.5Ni have a similar behavior, concerning the kinetics and the oxide micro structure. Copper additions decrease the oxidation rate of titanium. The oxide scales formed on Ti-Cu are thinner and less cracked than those obtained on Ti or Ti-1.5Ni. Copper is found in the oxide scale of Ti-Cu, whereas nickel is not found in the oxide scale of Ti-Ni. The oxidation of titanium and its alloys is controlled chiefly by diffusional phenomena in the oxide scale. Thus the alterations of the oxide scale structure and the slower oxidation rate of Ti-2.5Cu can be attributed to the copper which diffuses towards the gas-oxide interface.
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  • 80
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    Oxidation of metals 16 (1981), S. 107-131 
    ISSN: 1573-4889
    Keywords: Oxidation ; iron ; kinetics ; sulfur ; surface analysis
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The growth of thin (0–200 Å) oxide films on iron at 200 and 300 °C has been studied as a function of time and oxygen partial pressure using proton-induced X-ray emission (PIXE) and Auger electron spectroscopy (AES). Oxidation was found to be initially retarded by sulfur which had segregated onto the iron surfaces during preoxidation annealing, but only if the iron surface contained the maximum or near-maximum sulfur coverage (ca. one-half monolayer). During and immediately following the oxygen-sulfur interaction, oxide buildup appeared to be limited by a surface reaction (adsorption, ionization, or dissociation). For most of the oxidation period, pressure-dependent logarithmic oxide growth was observed at 200°C, and pressure-independent parabolic oxide growth at 300°C. Interpretation of the data indicated that oxide growth at 200°C may be limited by quantum mechanical tunneling of electronic species through the previously formed oxide film, and oxide growth at 300°C may be limited by ionic diffusion through the previously formed oxide film. Comparison of AES and PIXE data indicated that the oxide films formed at 200°C were uniform in thickness over the surface of the metal, whereas films formed at 300°C had relatively thin areas where sulfur had remained.
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    Oxidation of metals 17 (1982), S. 43-54 
    ISSN: 1573-4889
    Keywords: Coatings ; oxidation ; titanium silicide ; kinetics
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Coatings of Ti 5Si3 on titanium have been prepared by means of decomposition of silane SiH4 on heated titanium ribbons. Oxidation of the coated titanium specimens was much slower than that of the noncoated ones. Gravimetric and morphological experiments allowed to propose a mechanism describing the oxidation process.
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  • 82
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    Oxidation of metals 22 (1984), S. 45-57 
    ISSN: 1573-4889
    Keywords: Ni-Cr-Mo alloys ; sulfidation ; scale structures ; kinetics
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The effect of molybdenum additions 5, 10, 15, and 20 wt. %, on the sulfidation behavior of Ni-20Cr, and the effect of chromium additions, 5, 10, 15, and 20 wt.%, on the sulfidation of Ni-20Mo were studied in pure sulfur vapor at 700°C. In general, the alloys followed a linear or near-linear rate law, the sulfidation rate of Ni-20Mo being slightly less than that of Ni-20Cr. The alloys having the lowest ternary addition, e.g., Ni-Cr-5Mo and Ni-20Mo-5Cr. exhibited the most rapid reaction rates. The highest alloying additions of 20 wt.% had no appreciable benefit on reaction rates. Scale structures were complex but generally consisted of several layers. The outer layer was always NiS1.03, although both binaries formed Ni3S2 within the NiS1.03. An inner layer of Cr3S4 existed in which there was considerable dissolved molybdenum. A thin, intermediate layer of Cr2S3 generally formed between the Cr3S4 and the outer nickel sulfide. An innermost layer of MoS2 formed on all alloys containing more than 10 wt. % Mo, and a second phase of Mo2S3 formed within the MoS2 on Ni-20Mo. Although the scales changed with alloy composition, no significant changes in reaction rate were observed. Notable differences in both scale structure and reaction kinetics between this study and previous studies were apparent. The differences and possible reaction mechanisms are discussed.
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  • 83
    ISSN: 1573-4927
    Keywords: alcohol dehydrogenase ; inbred mouse strains ; enzyme structure ; kinetics
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Alcohol dehydrogenase activity in mouse liver homogenate-supernatants is 1.7 times greater in the C57BL/10 strain than in the BALB/c strain, regardless of whether activity is expressed in units per gram liver, total liver, or milligram DNA. The K m values for ethanol and NAD+, approximately 0.4 and 0.03mm, respectively, of enzyme purified from both strains are similar. Moreover, the K i for NADH, 1 µm, the pH optimum for ethanol oxidation, 10.5, and the V max for ethanol oxidation, 160 min−1, for ADH from the C57BL/10 and BALB/c strains are similar. Therefore, the difference in ADH activity in the two strains cannot be due to differences in the catalytic properties of the enzyme. The electrophoretic and isoelectric focusing patterns and two-dimensional tryptic peptide maps of the purified enzyme from both strains are identical. Thus the amino acid sequences of enzyme from C57BL/10 and BALB/c mice must also be identical or very similar. The difference in ADH activity in the two strains is most likely the result of genetic differences in the content of ADH protein in liver.
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    The journal of membrane biology 69 (1982), S. 35-40 
    ISSN: 1432-1424
    Keywords: axon ; hydrostatic pressure ; K currents ; kinetics ; activation volume
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary The effect of pressure upon the delayed, K, voltage-clamp currents of giant axons from the squidLoligo vulgaris was studied in axons treated with 300nm TTX to block the early, Na, currents. The effect of TTX remained unaltered by pressure. The major change produced by pressures up to 62 MPa is a slowing down of the rising phase of the K currents by a time scaling factor which depends on pressure according to an apparent activation volume, ΔV∓, of 31 cm3/mole at 15°C; ΔV∓ increased to about 42 cm3/mole at 5°C. Pressure slightly increased the magnitude, but did not produce any obvious major change in the voltage dependence, of the steady-state K conductance estimated from the current jump at the end of step depolarizations of small amplitude (to membrane potentials,E, ≦20 mV) and relatively short duration. At higher depolarizations, pressure produced a more substantial increase of the late membrane conductance, associated with an apparent enhancement of a slow component of the K conductance which could not be described within the framework of the Hodgkin-Huxley (HH)n 4 kinetic scheme. The apparent ΔV∓ values that characterize the pressure dependence of the early component of the K conductance are very close to those that describe the effect of pressure on Na activation kinetics, and it is conceivable that they are related to activation volumes involved in the isomerization of the normal K channels. The enhancement of the slow component of membrane conductance by pressure implies either a large increase in the conductance of the ionic channels that are responsible for it or a strong relative hastening of their turn-on kinetics.
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    The journal of membrane biology 69 (1982), S. 23-34 
    ISSN: 1432-1424
    Keywords: axon ; hydrostatic pressure ; Na currents ; kinetics ; temperature ; activation volume
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary The effects of hydrostatic pressures up to 62 MPa upon the voltage-clamp currents of intact squid giant axons were measured using mineral oil as the pressure transmitting medium. The membrane resistance and capacitance were not appreciably affected over the whole range of pressures explored. The predominant effect of pressure is to slow the overall kinetics of the voltage-clamp currents. Both the early (Na) currents and the delayed (K) ones were slowed down by approximately the same time scale factor, which was in the range of 2 to 3 when pressure was increased from atmospheric to 62 MPa. Finer details of the effects, most evident at moderate depolarizations, are: the apparent initial delay in the turn-on of Na currents is increased by pressureless than is the phase of steepest time variation, and the later decay is slowedmore than is the rising phase. The initial time course of the currents at high pressures can be made to overlap with that at normal pressure by a constant time compression factor, Θm, together with a small, voltage-dependent delay. In a given axon, Θm was fairly independent of voltage, and it increased exponentially with pressure according to an apparent activation volume, ΔV∓, ranging between 32 and 40 cm3/mole. ΔV∓ tended to decrease with increasing temperature. Contrary to what is observed for moderate or large depolarizations, the kinetics of Na inactivation produced by conditioning prepulses of −50 or −60 mV was little affected over the whole range of pressures explored. Inferences about the pressure dependence of the steady-state Na activation were made from the comparison of the plots of early peak currents,I p, versus membrane potential,E. The Na reversal potential,E Na, and the slope of the plots nearE Na did not change significantly with pressure, but the peak Na conductancevs. E relationship was shifted by about +9 mV upon increasing pressure to 62 MPa. Steady-state Na inactivation,h ∞, was slightly affected by pressure. At 62 MPa the midpoint potential of theh ∞ (E) curve,E h, was shifted negatively by about 4 mV, while the slope atE h decreased by about 38%. Under the tentative assumption that pressure directly affects the gating of Na channels, the Na activation data follows a simple Hodgkin-Huxley scheme if the opening of anm gate involves an activation volume of about 58 Å3 and a net volume increase of about 26 Å3. However, a self-consistent description of the totality of the effects of pressure on Na inactivation cannot be obtained within a similar simple context.
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    The journal of membrane biology 74 (1983), S. 85-94 
    ISSN: 1432-1424
    Keywords: sodium ; lithium ; chloride ; pH ; transport ; kinetics ; ion permeability
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary Na+, Li+, K+, Rb+, Br−, Cl− and SO 4 2− transport were studied in brush border membrane vesicles isolated from rabbit jejunum., Li+ uptakes were measured by flameless atomic absorption spectroscopy, and all others were measured using isotopic flux and liquid scintillation counting. All uptakes were performed with a rapid filtration procedure. A method is presented for separating various components of ion uptake: 1) passive diffusion, 2) mediated transport and 3) binding. It was concluded that a Na+/H+ exchange mechanism exists in the jejunal brush border. The exchanger was inhibited with 300 μm amiloride or harmaline. The kinetic parameters for sodium transport by this mechanism depend on the pH of the intravesicular solution. The application of a pH gradient (pHin=5.5, pHout=7.5) causes an increase inJ max (50 to 125 pmol/mg protein·sec) with no change inK t (≈4.5mm). Competition experiments show that other monovalent cations, e.g. Li+ and NH 4 + , share the Na+/H+ exchanger. This was confirmed with direct measurements of Li+ uptakes. Saturable uptake mechanisms were also observed for K+, Rb+ and SO 4 2− , but not for Br−. TheJ max for K+ and Rb+ are similar to theJ max for Na+, suggesting that they may share a transporter. The SO 4 2− system appears to be a Na+/SO 4 2− cotransport system. There does not appear to be either a Cl−/OH− transport mechanism of the type observed in ileum or a specific Na+/Cl− symporter.
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    The journal of membrane biology 74 (1983), S. 175-182 
    ISSN: 1432-1424
    Keywords: kinetics ; transport inhibition ; noncompetitive ; competitive ; inhibition mechanism ; carrier model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary A new analysis of the conventional carrier model shows that noncompetitive inhibitors can give rise to either competitive, noncompetitive or uncompetitive kinetics; the true mechanism and also the relative affinity of the inhibitor on each surface of the membrane can be decided from the patterns of inhibition observed in different transport experiments. The priciples governing the kinetics of inhibition apply to both reversible and irreversible inhibitors, for in either case the substrate may increase or decrease inhibition or be without effect. Ambiguity arises if the noncompetitive inhibitor acts on only one side of the membrane and if the substrate, in the course of being transported, alters the steady-state distribution of the carrier between inner and outer forms. In facilitated transport systems only equilibrium exchange should give rise to noncompetitive kinetics, whatever the location of the inhibitor. In active systems even the interpretation of exchange in the final steadystate is complicated if the energy-coupling mechanism produces a large displacement in the distribution of the free carrier or the substrate complex: the inhibition could be competitive or uncompetitive, depending on the location of the inhibitor. The actual mechanism is revealed in the uncoupled system.
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    The journal of membrane biology 79 (1984), S. 41-51 
    ISSN: 1432-1424
    Keywords: glucose ; brush borders ; sodium cotransport ; kinetics
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary Brush border membrane vesicles (BBMV) purified from steer jejunum were used to study the kinetics of sodiumd-glucose cotransport under voltage clamped, zero-trans conditions. When the initial rate of glucose transport (J gluc) was measured over a wide range of glucose concentrations ([S]=0.01–20mm), curvature of the Woolf-Augustinsson-Hofstee plots was seen, compatible with a diffusional and one major, high capacity (maximal transport rateJ max=5.8–8.8 nmol/mg·min) saturable system. Further studies indicated that changes incis [Na] altered theK t , but not theJ max, suggesting the presence of a rapid-equilibrium, ordered bireactant system with sodium adding first.Trans sodium inhibitedJ gluc hyperbolically. KCl-valinomycin diffusion potentials, inner membrane face positive, loweredJ gluc, while potentials of the opposite polarity raiseJ gluc. At low glucose concentrations ([S]〈0.05mm), a second, minor, high affinity transport system was indicated. Further evidence for this second saturable system was provided by sodium activation curves, which were hyperbolic when [S]=0.5mm, but were sigmoidal when [S]=.0.01mm. Simultaneous fluxes of22Na and [3H]glucose at 1mm glucose and 30mm NaCl yielded a cotransport-dependent flux ratio of 2∶1 sodium/glucose, suggestive of 1∶1 (Na/glucose) high capacity, low affinity system and a ∼3∶1 (Na/glucose) high affinity, low capacity system. Kinetic experiments with rabbit jejunal brush borders revealed two major Na-dependent saturable systems. Extravesicular (cis) Na changed theK t , but not theJ max of the major system.
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    The journal of membrane biology 76 (1983), S. 289-297 
    ISSN: 1432-1424
    Keywords: neuron ; internal perfusion ; Mn current ; kinetics ; Ca blocker
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary Characteristics of currents carried by Mn2+ and other divalent cations were studied in the isolated identified neuron in the circumesophageal ganglia ofHelix aspersa using a suction pipette technique which allows internal perfusion of the cell body and voltage clamp. Increases in [Mn2+] 0 induced not only saturation of the peak ofI Mn but also shifts theI–V relationships along the voltage axis to the more positive potentials. Internal perfusion with F−, which blocks Ca channels, depressedI Mn. Diltiazem, an organic Ca blocker, inhibitedI Mn over the entire range of theI–V relation without shifting the threshold and peak voltage of theI–V relation. Co2+, Ni2+, Cd2+ and La3+ also suppressedI Mn. Relative maximum peak currents of the divalent cations wereI Ba=I Sr〉I Ca〉I Mn=I Zn. Time constants for activation (τ m ) and inactivation (τ h ) of these cations were voltage dependent, and both time constants were greater in the sequence ofI Mn=I Zn〉I Ba=I Sr〉I Ca over the whole voltage range.
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  • 90
    ISSN: 1432-1424
    Keywords: ion transport ; carriers ; lipid bilayers ; kinetics ; nonactin ; methylation ; macrotetralides
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary The effects of methylation on the rate constants of carrier-mediated ion transport have been studied on monooleindecane bilayers with K+, Rb+, NH 4 + , and TI+ ions, using the series of homologue carriers, nonactin, monactin, dinactin, trinactin, and tetranactin, each member of the series differing from the previous one by only one methyl group. Measurements of the amplitude and time constant of the current relaxation after a voltage jump over a large domain of voltage and permeant ion concentration, together with a computer curve-fitting procedure, have allowed us, without the help of steady-state current-voltage data, to deduce and compare the values of the various rate constants for ion transport: formation (k Ri) and dissociation (k Di) of the ion-carrier complex at the interface, translocation across the membrane interior of the carrier (k s) and the complex (k is). With the additional information from steady-state low-voltage conductance measurements, we have obtained the value of the aqueous phase-membrane and torus-membrane partition coefficient of the carrier ({ie191-1} and {ie191-2}). From nonactin to tetranactin with the NH 4 + ion,k is, and {ie191-3} are found to increase by factors of 5 and 3, respectively,k Di and {ie191-4} to decrease respectively by factors 8 and 2, whilek Ri andk s are practically invariant. Nearly identical results are found for K+, Rb+, and Tl+ ions.k Ri,k s andk is are quite invariant from one ion to the other except for Tl+ wherek Ri is about five times larger. On the other hand,k Di depends strongly on the ion, indicating that dissociation is the determining step of the ionic selectivity of a given carrier. The systematic variations in the values of the rate constants with increasing methylation are interpreted in terms of modifications of energy barriers induced by the carrier increasing size. Within this framework, we have been able to establish and verify a fundamental relationship between the variations ofk is andk Di with methylation.
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    Fresenius' Zeitschrift für analytische Chemie 279 (1976), S. 100-101 
    ISSN: 1618-2650
    Keywords: Best. von Spurenelementen, Mangan, Kobalt in Serum ; Spektralphotometrie, Atomabsorption
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    Topics: Chemistry and Pharmacology
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    Fresenius' Zeitschrift für analytische Chemie 279 (1976), S. 205-205 
    ISSN: 1618-2650
    Keywords: Best. von Schwermetallen in Wasser, Biolog. Material ; Spektralphotometrie, Atomabsorption ; verbesserter Gas-stop
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    Topics: Chemistry and Pharmacology
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    Fresenius' Zeitschrift für analytische Chemie 278 (1976), S. 121-124 
    ISSN: 1618-2650
    Keywords: Best. von Titan ; Spektralphotometrie, Atomabsorption ; Einfluß von Wertigkeit, Säuren, Liganden
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Der Einfluß der Wertigkeit des Titans, von Mineralsäuren und von verschiedenen organischer Komplexliganden auf die Ti-Absorption in N2O-Acetylen-Flammen wurde ausführlich untersucht. Die thermischen Prozesse in den trockenen Aerosolpartikeln scheinen für die Atomisierung wichtiger zu sein, als die Komplexbildungsgleichgewichte in der Lösung. In Gegenwart von Chromotropsäure ist die Titanbestimmung mit AAS empfindlicher und selektiver als bei der bisherigen Ausführung.
    Notes: Abstract The atomic absorption method for the determination of titanium in N2O-acetylene flames is studied from the point of view of the valence state of titanium, the effect of mineral acids and various organic complexing ligands in solution. It seems evident that the thermal procedures within the dry aerosol particle are rather more deciding for the atomisation processes than the complexation equilibria in solution. In the presence of chromotropic acid the sensitivity and selectivity of the method are increased in comparison with the usual procedure in pure solutions.
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    Fresenius' Zeitschrift für analytische Chemie 291 (1978), S. 213-216 
    ISSN: 1618-2650
    Keywords: Best. von Blei in Boden, Sedimenten ; Spektralphotometrie, Atomabsorption ; Flamme, Reextraktion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung In Vorversuchen wurde gezeigt, da\ beim Aufbewahren der organischen APDC/MIBK-Extrakte starke Bleiverluste auftraten. Daher war es notwendig, das Blei mit SalpetersÄure in die wÄ\erige Phase zu reextrahieren. Wiederfindungsversuche bestÄtigten, da\ Extraktion und Reextraktion quantitativ verlaufen. Das Blei wird dabei um den Faktor fünf angereichert. Es werden mittlere Standardabweichungen für vier Konzentrationsbereiche angegeben. Als Nachweisgrenze wurde eine Konzentration von 0,16 mg Pb/l gefunden, die durch die Anreicherung auf ca. 0,03 mg Pb/l gesenkt wird. Arbeitsvorschriften für das Verfahren sind angegeben.
    Notes: Summary Preliminary investigations have shown, that considerable losses of lead occur during storage of the organic APDC/MIBK-extracts. Therefore, it was necessary to reextract lead into the aqueous phase by nitric acid. Investigations of recoveries confirmed, that extraction and reextraction of lead were quantitative. In this way the concentration of lead is increased by a factor of five. Mean standard deviations for four concentration ranges are given. A detection limit of 0.16 mg of Pb/l is obtained, which is lowered by the preceding enrichment to about 0.03 mg of Pb/l. Details of the procedure are given.
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    Fresenius' Zeitschrift für analytische Chemie 294 (1979), S. 345-351 
    ISSN: 1618-2650
    Keywords: Best. von Wismut, Cadmium, Thallium in Gesteinen ; Spektralphotometrie, Atomabsorption ; fraktionierte Destillation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Summary The analysis of bismuth, cadmium and thallium in rock samples can be performed by flameless atomic absorption spectrometry, after separation and preconcentration by a volatilization technique. This method has the major advantage that small amounts of substance can be used with a minimum consumption of chemicals, so that sources of contamination are reduced. The detection limit for Bi and Tl is about 1 ppb and for Cd about 0.1 ppb in the rock. Depending on the content in the rock samples, the relative standard deviation is between 2 and 30%. Several attempts have been made to determine the yields of Bi, Cd and Tl from synthetic and natural samples.
    Notes: Zusammenfassung Die Bestimmung von Wismut, Cadmium und Thallium in Gesteinen kann mit der flammenlosen Atomabsorptions-Spektroskopie nach verdampfungsanalytischer Abtrennung erfolgen. Die Verdampfungsnalyse hat den Vorteil, daß bei geringem Reagentienverbrauch kleine Mengen analysiert werden können. Die Gefahr der Einschleppung von Verunreinigungen wird erheblich vermindert. Die Nachweisgrenze bezogen auf die Probe beträgt für Wismut und Thallium ca. 1 ppb und für Cadmium ca. 0.1 ppb. In Abhängigkeit von der Konzentration liegt die relative Standardabweichung zwischen 2 und 30 %. An synthetischen und natürlichen Proben sind die Ausbeuten an diesen Elementen bestimmt worden.
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    Fresenius' Zeitschrift für analytische Chemie 295 (1979), S. 355-361 
    ISSN: 1618-2650
    Keywords: Best. von Blei in Geolog. Material, Biolog. Material ; Spektralphotometrie, Atomabsorption ; Graphitrohrküvette
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Summary Serious systematic errors inherent in the determination of lead in geological and biological samples by flameless atomic-absorption spectrometry are demonstrated. The reduced absorption of lead is due to partial interaction with alkaline, alkaline-earth and iron chlorides during the atomization stage. Incomplete dissociation of the volatile monochloride of lead in the gaseous phase reduces the absorption signal. An addition of 20% hydrogen to nitrogen (purge gas) diminishes signal suppression by removing the chlorine in form of volatile HCl. The detection limit is about 0.6 ppm in rocks and about 0.3 ppm in plant materials. Depending on the content in the samples the relative standard deviation is between 1 and 12%. The accuracy of the method was tested on 39 international standard reference samples.
    Notes: Zusammenfassung Schwerwiegende systematische Fehler bei der Bestimmung von Blei in geologischen und biologischen Materialien mit der Graphitrohrküvette werden aufgezeigt. Die Reaktion von Blei mit Alkali-, Erdalkali- und Eisenchloriden während der Atomisierungsphase führt zur Bildung von Bleimonochlorid, das nur unvollständig dissoziiert und eine Signalunterdrückung zur Folge hat. Ein Zusatz von 20% Wasserstoff zu Stickstoff als Spülgas vermindert die Signalunterdrückung, indem überschüssiges Chlor als Chlorwasserstoff entfernt wird. Die Nachweisgrenze liegt bei ca. 0,6 ppm für Gesteine und bei ca. 0,3 ppm für Pflanzenmaterialien. Je nach der Konzentration beträgt die relative Standardabweichung 1–12%. Die Genauigkeit der Methode wurde an 39 internationalen Standardreferenzproben überprüft.
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  • 97
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    Fresenius' Zeitschrift für analytische Chemie 293 (1978), S. 141-144 
    ISSN: 1618-2650
    Keywords: Best. von Quecksilber in Zähnen, Knochen ; Spektralphotometrie, Atomabsorption ; HNO3/HF-Aufschluß, Kaltdampfverfahren
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird ein Verfahren zur Bestimmung von Quecksilber in Zahnwurzeln und Kieferknochen beschrieben. Die homogenisierten Proben werden in Teflonbomben unter Druck mit einem Gemisch von HNO3/HF aufgeschlossen. Die Quecksilberbestimmung erfolgt mit einem Atomabsorptionsspektrophotometer nach dem Kaltdampfverfahren. Unter Einsatz von 200 mg Probe können Quecksilbergehalte bis zu 0,1 μg/g bestimmt werden. Die relativen Standardabweichungen liegen im Arbeitsbereich von 10–100 ng Quecksilber zwischen 2,7 und 5,6 %. Es wurden Quecksilbergehalte von 〈0,1–187 μg/g in den Proben gefunden.
    Notes: Summary The homogenized samples are decomposed with a mixture of HNO3/HF in teflon vessels under pressure. The determination of mercury is carried out with an atomic absorption spectrophotometer by means of the cold-vapour technique. The limit of detection is 0.1 μg/g for a 200 mg sample. A relative standard deviation of 2.7–5.6% is achieved in the working range of 10–100 ng mercury. Mercury contents of 〈0.1–187 μg/g were found in the samples.
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    Fresenius' Zeitschrift für analytische Chemie 294 (1979), S. 402-404 
    ISSN: 1618-2650
    Keywords: Best. von Antimon in Biolog. Material ; Spektralphotometrie, Atomabsorption ; Nanospuren
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Eine selektive Bestimmung von Antimon durch Atomabsorptionsspektrometrie ist durch elektrothermale Atomisierung von Antimonwasserstoff in einem Argonspülgasstrom möglich. Das Verfahren erfordert eine hohe und reproduzierbare Geschwindigkeit der Reduktion des Antimons zu Antimonwasserstoff in der wäßrigen Probelösung. Geeignete Bedingungen für diese Reduktion erreicht man, wenn man in der Lösung zunächst einen Komplex von Antimon(III) mit Äthylendiamintetraessigsäure bildet; dieser Komplex reagiert mit Natriumborhydrid in der geforderten Weise zu Antimonwasserstoff. Bei der Mineralisierung des organischen Materials ist auf genaue Temperaturführung zu achten.
    Notes: Summary High selectivity in measuring antimony by atomic absorption spectrometry is obtained by electrothermal atomisation of stibine in a stream of argon purging gas. This procedure requires a fast and reproducible reduction to stibine of the total antimony present in an aequeous solution. Optimum conditions for this reduction are reached by first transforming all antimony in the solution to an EDTA-chelate of antimony(III) which then reacts uniformly with sodium boron hydride to give stibine. Close temperature control is essential in decomposition of biological samples.
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    Fresenius' Zeitschrift für analytische Chemie 294 (1979), S. 416-416 
    ISSN: 1618-2650
    Keywords: Best. von Blei in Benzin ; Spektralphotometrie, Atomabsorption ; emulgierte Proben
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
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  • 100
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    Fresenius' Zeitschrift für analytische Chemie 295 (1979), S. 110-115 
    ISSN: 1618-2650
    Keywords: Best. von Cadmium in Boden, Sedimenten ; Spektralphotometrie, Atomabsorption ; Zr-beschichtete Graphitrohre
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird ein Verfahren beschrieben, das es gestattet, nach einer Anreicherung von Cadmium durch Extraktion mit APDC/MIBK und anschließender Reextraktion mit Salpetersäure, die stark salpetersaueren Reextrakte direkt in Zirkonium-beschichteten Graphitrohren bei Verwenden der flammenlosen Atomabsorption zu vermessen. Diese Rohre zeigten eine gute Lebensdauer (150–300 Analysen). Durch eine Behandlung der Rohre mit einer Fe3+-Lösung konnten Beeinflussungen der Cadmiumsignale durch Begleitstoffe verhindert werden. Cadmium wird bei der Extraktion und Reextraktion um den Faktor fünf angereichert. Bei hohen Cadmiumgehalten in den Proben kann die Analyse bei gleicher Probenvorbereitung mit Hilfe der Flammenatomabsorption durchgeführt werden. Die Arbeitsbedingungen für die flammenlose, sowie für die Flammen-Atomabsorption werden angegeben. Als Nachweisgrenzen bei Verwenden der flammenlosen Atomabsorption wurden im Mittel 0,53 μg Cd/l, für die Flammenatomabsorption 19,4μg Cd/l gefunden, die durch die Anreicherung auf ca. 0,1, bzw. 4 μg Cd/l gesenkt werden.
    Notes: Summary Cadmium is enriched by an extraction with APDC/MIBK and subsequent reextraction with nitric acid. A procedure is described for analyzing these solutions directly by means of flameless atomic absorption, inspite of the high concentration of nitric acid in a zirconium coated graphite tube. These tubes, proved to be very resistant (150–300 analyses). After treatment of the tubes with a Fe3+-solution no interference by accompanying anions and cations could be observed. By the extraction and reextraction procedure described cadmium is enriched by a factor of five. Samples of higher cadmium concentrations were analyzed by means of flame atomic absorption after the same sample preparation. Working conditions for flameless and flame atomic absorption are given. Detection limits have been calculated as 0.53 μg Cd/l in the case of flameless, 19.4 μg Cd/l in the case of flame atomic absorption. These values are further decreased by the above enrichment procedure to 0.1 and 4 μg Cd/l, respectively.
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