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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    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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  • 2
    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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  • 3
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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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  • 4
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    Adsorption 1 (1995), S. 133-151 
    ISSN: 1572-8757
    Keywords: PSA process ; sensitivity ; equilibria ; kinetics ; heats
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Mathematical models for pressure swing adsorption (PSA) processes essentially require the simultaneous solutions of mass, heat and momentum balance equations for each step of the process using appropriate boundary conditions for the steps. The key model input variables needed for estimating the separation performance of the process are the multicomponent adsorption equilibria, kinetics and heats of adsorption for the system of interest. A very detailed model of an adiabatic Skarstrom PSA cycle for production of high purity methane from a ethylene-methane bulk mixture is developed to study the sensitivity of the process performance to the input variables. The adsorption equilibria are described by the heterogeneous Toth model which accounts for variations of isosteric heats of adsorption of the components with adsorbate loading. A linear driving force model is used to describe the kinetics. The study shows that small errors in the heats of adsorption of the components can severely alter the overall performance of the process (methane recovery and productivity). The adsorptive mass transfer coefficients of the components also must be known fairly accurately in order to obtain precise separation performance.
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  • 5
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    Catalysis letters 31 (1995), S. 431-438 
    ISSN: 1572-879X
    Keywords: partial hydrogenation of benzene ; production of cyclohexene ; kinetics ; reaction mechanism ; ruthenium catalyst
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A method has been developed for direct measurement of reaction rates in a continuously operated slurry (CST-) reactor. In contrast to the usual procedure in a two-liquid-phase system the reactor contains only one liquid phase, an aqueous zinc chloride solution in which a ruthenium lanthanoxide catalyst is suspended. The selectivity of benzene hydrogenation with respect to cyclohexene is higher when the new one-liquid-phase procedure is applied. With decreasing degree of benzene conversion the selectivity with respect to cyclohexene approaches 100%. The conclusion is that cyclohexane is formed only by consecutive hydrogenation of cyclohexene.
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  • 6
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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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  • 7
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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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  • 8
    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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  • 9
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    European journal of clinical pharmacology 21 (1981), S. 149-153 
    ISSN: 1432-1041
    Keywords: cinromide ; epilepsy ; kinetics ; metabolites
    Source: Springer Online Journal Archives 1860-2000
    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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  • 10
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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
    Source: Springer Online Journal Archives 1860-2000
    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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  • 11
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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
    Source: Springer Online Journal Archives 1860-2000
    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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  • 12
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    European journal of clinical pharmacology 27 (1984), S. 367-369 
    ISSN: 1432-1041
    Keywords: flurbiprofen ; syrup ; suppository ; kinetics ; children ; bioavailability
    Source: Springer Online Journal Archives 1860-2000
    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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  • 13
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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
    Source: Springer Online Journal Archives 1860-2000
    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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  • 14
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    Plasma chemistry and plasma processing 1 (1981), S. 233-245 
    ISSN: 1572-8986
    Keywords: Plasma ; kinetics ; polymerization ; propylene
    Source: Springer Online Journal Archives 1860-2000
    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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  • 15
    ISSN: 1573-1421
    Keywords: calcite ; precipitation ; dissolution ; kinetics ; reaction mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Calcite dissolution rates were measured using a free-drift technique at 25°C, 1 atm total pressure, and various $$P_{CO_2 } $$ in deionized water. The data were corrected for gas phase disequilibrium and fitted to a kinetic expression derived by coupling the mechanistic models of Plummeret al. (1987a) and Chouet al. (1989) to the surface complexation model of Van Cappellenet al. (1993). Corrected dissolution and precipitation rate measurements from previous investigations were combined to our data set and fitted to the same expression. The following reactions provide an adequate description of the calcite dissolution and precipitation mechanism in dilute solutions: for which the overall reaction rate is given by where 〉i are the densities of surface complexes (mol/m2),a i are the activities of dissolved species and,k i are the rate constants corresponding to the above reactions. This rate equation satisfies the principle of microscopic reversibility and applies to both dissolution and precipitation reactions over a wide range of $$P_{CO_2 } $$ , pH and saturation states. The rate constants obtained from fitting the data set to Equation (3) are compatible with values reported by Plummeret al. and Chouet al., as well as yielding a very good estimate of the thermodynamic solubility constant of calcite, K 0 sp .
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  • 16
    ISSN: 1573-4919
    Keywords: acetylcholinesterase ; optimization ; kinetics ; venom ; turnover number
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Acetylcholinesterase (AChE) was investigated inWalterinnesia aegyptia venom and characterized with respect to its kinetic properties. It was found that 4.0 ug of crude venom protein and an incubation time of 4.0 min were suitable conditions for linearity of AChE activity at 25°C. The optimum strength of the sodium phosphate buffer was 0.05 M, and the optimum pH was 7.75. The optimum temperature was 30°C. The activation energy and the heat of activation were observed to be 6510 and 5922 cal/mole. The AChE was specific for acetylthiocholine but it did not hydrolyse butyrylthiocholine. The optimum substrate concentration was 3.0 mM but at higher substrate concentrations, the AChE activity declined. The ASCh concentration ranges for different orders of the reactions were determined and kinetic parameters (Km, Vmax, kcat, and ksp) were established at each order of the reaction.
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  • 17
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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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  • 18
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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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  • 19
    ISSN: 1573-4927
    Keywords: alcohol dehydrogenase ; inbred mouse strains ; enzyme structure ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    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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  • 20
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    Journal of sol gel science and technology 4 (1995), S. 117-133 
    ISSN: 1573-4846
    Keywords: kinetics ; precursor chemistry ; silica ; permeability ; microstructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The molecular-scale species distributions and intermediate-scale structure of silicate sols influence the microstructures of the corresponding thin films prepared by dip-coating. Using multi-step hydrolysis procedures, we find that, depending on the sequence and timing of the successive steps, the species distributions (determined by 29Si NMR) and intermediate scale structure (determined by SAXS) can change remarkably for sols prepared with the same nominal composition. During film formation, these kinetic effects cause differences in the efficiency of packing of the silicate species, leading to thin film structures with different porosities.
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  • 21
    ISSN: 1573-4943
    Keywords: Hydrolase ; site-directed mutagenesis ; kinetics ; cyclohexane ; butanoic acid esters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract To reveal the functional role of Glu87 and Trp89 in the lid ofHumicola lanuginosa lipase, site-directed mutagenesis at Glu87 and Trp89 was carried out. The catalytic performance of wild-type and mutated lipases was studied in transesterification reactions in cyclohexane at a controlled water activity. Two different acyl donors were used in the investigation: tributyrin, a natural substrate for a lipase, and vinyl butyrate, an activated ester suitable for fast and efficient lipase-catalyzed transformations in preparative organic synthesis. As acyl acceptor 1-heptanol was used. The Glu87Ala mutation decreased theV max,app value with tributyrin and vinyl butyrate by a factor of 1.5 and 2, respectively. TheK m,app for tributyrin was not affected by the Glu87Ala mutation, but theK m,app for vinyl butyrate increased twofold compared to the wild-type lipase. Changing Trp89 into a Phe residue afforded an enzyme with a 2.7- and 2-fold decreasedV max,app with the substrates tributyrin and vinyl butyrate, respectively, compared to the wild-type lipase. No significant effects on theK m,app values for tributyrin or vinyl butyrate were seen as a result of the Trp89Phe mutation. However, the introduction of a Glu residue at position 89 in the lid increased theK m,app for tributyrin and vinyl butyrate by a factor of 〉5 and 2, respectively. The Trp89Glu mutated lipase could not be saturated with tributyrin within the experimental conditions (0–680 mM) studied here. With vinyl butyrate as a substrate theV max,app was only 6% of that obtained with wild-type enzyme.
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  • 22
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    The protein journal 14 (1995), S. 695-701 
    ISSN: 1573-4943
    Keywords: Aminoacylase ; metal ion ; reactivation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetic theory of the substrate reaction during irreversible change of enzyme activity previously described by Tsou (Tsou (1988),Adv. Enzymol. Relat. Areas Mol. Biol.61, 381–436] has been applied to a study of the kinetics of the course of reactivation during reconstitution of apo-aminoacylase using Mn2+ or Zn2+. The kinetic parameters for Mn2+-and Zn2+-reconstituted enzymes and the microscopic rate constants for reactivation during reconstitution were determined. The kinetic analysis suggests the presence of a second Mn2+ binding site in Mn2+-reconstituted aminoacylase.
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  • 23
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    The journal of membrane biology 79 (1984), S. 41-51 
    ISSN: 1432-1424
    Keywords: glucose ; brush borders ; sodium cotransport ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    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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  • 24
    ISSN: 1573-9171
    Keywords: electrochemistry ; metal complexes ; dichlorocyclopropane ; kinetics ; reduction
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Electrochemical reduction of the complexes Rh(CO)ClL2 [L = (EtO)2PCN (1), Ph2PCN (2)] and Rh2(CO)4L [L = P(CN)3 (3), $$Ph\begin{array}{*{20}c} P \\ | \\ {CN} \\ \end{array} ---\begin{array}{*{20}c} P \\ | \\ {CN} \\ \end{array} Ph$$ (4)] and their catalytic properties in electrochemical reduction of 2-carbomethoxy-2-methyl-1,1-dichloro-cyclopropane were studied. The catalytic electroreduction of a substrate at the reduction potentials of the central ion was developed for complexes2–4. This process is accelerated substantially for complexes2 and3 in the presence of anthracene.
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  • 25
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    Russian chemical bulletin 44 (1995), S. 1907-1913 
    ISSN: 1573-9171
    Keywords: photochemical transformations ; 1-arylcyanomethyl-9 ; 10-anthraquinones ; nucleophilic addition ; oxidation ; kinetics ; quantum-chemical calculations
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Photochemical transformations of 1-arylcyanomethyl-9,10-anthraquinones were studied. It was established that under irradiation, the hydrogen atom of the substituted methyl group is transferred to aperi-quinoid oxygen atom to form the corresponding 9-hydroxy1, 10-anthraquinone-1-arylcyanomethides. Dark transformations of photoinduced quinonemethides result from three competing parallel processes: intramolecular transfer of the hydrogen atom, a reaction with a solvent (alcohol), and oxidation by dissolved oxygen. The kinetics of these reactions were studied.
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  • 26
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    Russian chemical bulletin 44 (1995), S. 847-850 
    ISSN: 1573-9171
    Keywords: fluoroamines, thermal decomposition ; nitrocompounds ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the thermal decomposition of bis(2,2-dinitropropyl)-N-fluoroamine are studied in the liquid phase. The reaction is autocatalytic in a melt. In dilute solution, the reaction rate is described by the first-order law. It is tens of times faster in polar sulfolan than in weakly polar dimethyl phthalate. A mechanism of the decomposition involving the formation of a cyclic transition state at the first, limiting stage of the process is suggested.
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  • 27
    ISSN: 1573-9171
    Keywords: solvomercuration ; mechanism of reaction ; mercury acetate ; salt effect ; alkenes ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the addition of Hg(OAc)2 to strained and unstrained alkenes was studied in MeOH solution in the presence of NaOAc. Based on salt effects, the HgOAc ion was shown to be the actual reagent in the reaction of the unstrained alkenes, whereas Hg(OAc)2 was the reagent in the case of the strained alkenes. The mechanisms of the solvomercuration of alkenes of various structures were proposed.
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  • 28
    ISSN: 1573-9171
    Keywords: photocatalyst ; adsorption ; surfactant ; kinetics ; colloid ; cadmium sulfide
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Photoreduction of Methyl Orange dye (MOr) by sodium sulfide was studied under steady-state photolysis (λ = 365 nm). The reaction was sensitized by the CdS colloid with the characteristic ∼5-nm particle size. The quantum yield of the reaction is independent of the light intensity when the latter is less than 5 mW cm−2. The form of the dependence of the initial quantum yield of the reaction on [MOr] coincides qualitatively with the adsorption isotherm of the dye on the CdS surface. The reaction kinetics under steady-state irradiation were analyzed. The kinetics in solution as a whole are shown to be adequate to those on a single colloidal particle. On the basis of the experimental data, two types of surfaces of the colloidal particles are suggested (“open” and “covered” with macromolecules of a colloid stabilizer), which significantly differ in the rate at which they establish an adsorption-desorption equilibrium with the solution.
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  • 29
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    Russian chemical bulletin 44 (1995), S. 840-843 
    ISSN: 1573-9171
    Keywords: isopentenols, reaction scheme ; Prins reaction ; acid catalysis ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The reactions occurring in an equilibrium mixture of 3-methyl-1-buten-3-ol and 3-methyl-2-buten-1-ol in 24–49 % aqueous solutions of H2SO4 yield isoprene, 3-methyl-3-buten-1-ol, isobutylene, formaldehyde, 3-methylbutane-1,3-diol. Isobutylene is rapidly hydrated to give 2-methylpropan-2-ol. The presence of formaldehyde in the reaction mixture indicates that the transformations involve the reverse Prins reaction. On the basis of experimental and literature data, two most probable reaction schemes were suggested.
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  • 30
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    Russian chemical bulletin 44 (1995), S. 989-991 
    ISSN: 1573-9171
    Keywords: sorption ; kinetics ; mechanism ; polymer ; dibenzo-18-crown-6 ; RbCl ; equilibrium constant ; diffusion coefficients
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics and mechanism of the sorption of rubidium chloride from ethanol by granulated polymer containing immobilized dibenzo-18-crown-6 are studied. The sorption of RbCl is controlled by internal diffusion accompanied by complex formation in the polymer. The equilibrium constants of the sorption and diffusion coefficients of the electrolyte in the sorbent are calculated.
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  • 31
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    Journal of pharmacokinetics and pharmacodynamics 9 (1981), S. 181-190 
    ISSN: 1573-8744
    Keywords: drug displacement ; interaction ; kinetics ; simple model
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A simple model simulating the kinetics of drug displacement kinetics is investigated. It is demonstrated that for highly bound, lowly cleared drugs, displacement interactions are transitory. Consequently, the kinetics of the interaction have to be considered as well as the in vitrointeraction. It is possible to have a significant in vitrodisplacement interaction with no in vivocounterpart. Methods of moderating drug displacement by adjusting the rate and the timing of administration of the displacing agent are discussed.
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  • 32
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    Pharmaceutical research 12 (1995), S. 599-604 
    ISSN: 1573-904X
    Keywords: famotidine ; degradation ; isothermal ; nonisothermal ; kinetics ; stability
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of hydrolysis of famotidine in aqueous solution was studied by isothermal and nonisothermal method over the pH range of 1.71 to 10.0. Nonisothermal kinetics was studied with the purpose of determining its use in the establishment of the expiration date of pharmaceutical preparations, particularly drugs in solutions and for assessment of stability characteristics of pharmaceutical formulations during the development stage. A comparison of isothermal (55, 70 and 85°C) and nonisothermal kinetics was performed. Aqueous solutions of famotidine were buffered at pH 1.71, 2.24, 2.66, 4.0, 8.5, 9.0 and 10.0 were used. In the nonisothermal studies, the temperature rate of the reaction was continuously varied throughout the experiment. The energies of activation were found to be in close agreement for isothermal and nonisothermal studies, indicating that nonisothermal studies may save considerable amount of time in the early stages of drug development and stability testing. Logk-pH profiles were constructed for 55, 70 and 85°C from the first-order rate constants obtained from isothermal studies at pH values ranging from 1.71 to 10.00. The pH-rate profile indicated that famotidine undergoes specific acid catalysis in the acidic region and general base catalysis in the alkaline region. Hydrolysis in the acidic and alkaline media resulted in the formation of four and five degradation products, respectively. A possible degradation pathway for the acidic and alkaline hydrolysis was discussed.
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  • 33
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    Journal of pharmacokinetics and pharmacodynamics 5 (1977), S. 183-192 
    ISSN: 1573-8744
    Keywords: propranolol ; kinetics ; volunteers ; bioavailability ; threshold dose
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The pharmacokinetics of propranolol in blood was studied in healthy volunteers, following intravenous administration of 0.1 mg/kg and increasing oral doses of 10,20, and 40 mg, using a specific and sensitive gas Chromatographie method. The systemic availability of orally administered propranolol varied from 9% to 38% between subjects, but it was constant within each subject. A linear relationship was found between the area under the blood concentration-time curve and the oral dose. At variance with literature data, we could not observe a threshold dose.
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  • 34
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    Journal of pharmacokinetics and pharmacodynamics 6 (1978), S. 389-397 
    ISSN: 1573-8744
    Keywords: probenecid ; methotrexate ; cerebrospinal fluid ; kinetics ; interaction ; dogs ; choroid plexus ; intrathecal
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Probenecid is known to inhibit the renal excretion of methotrexate (MTX) and the transport of organic anions by the choroid plexus of the brain. The effect of probenecid on the CSF clearance of MTX given by the intrathecal route was examined in anesthetized dogs. Plasma and CSF MTX levels were measured following intrathecal injection of 0.4 mg/kg MTX, with and without pretreatment with probenecid. In the absence of probenecid, the peak plasma MTX concentration of 3.18×10−7±1.09×10−7 M (mean±SD) was reached 5 hr after intrathecal injection. With probenecid pretreatment, the mean peak plasma MTX concentration was lower (2.09×10−7+-0.98×10−7 M) and plasma disappearance was prolonged. A biexponential decay of CSF MTX levels was observed over the duration of sampling. The half-life of the second exponential phase was 21 hr without probenecid pretreatment and was longer after probenecid pretreatment. These results provide strong evidence that probenecid inhibits transfer of MTX from CSF to plasma following intrathecal injection.
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  • 35
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    Journal of pharmacokinetics and pharmacodynamics 7 (1979), S. 557-578 
    ISSN: 1573-8744
    Keywords: kinetics ; enzyme induction ; drug interaction
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Equations were derived to describe the time course of drug levels during auto- and heteroinduction under a variety of input conditions. These equations were based on a pharmacokinetic theory of induction which assumes that metabolic clearance increases exponentially to a maximum value and that the rate of this increase is governed by the degradation rate constant of the induced enzyme (k′). Closed form solutions could be obtained only for intravenous single-dose (case I) and multiple-dose (case IV) administration. For each of the other cases, constant-rate intravenous infusion (case III), oral single-dose administration (case II), and multiple-dose administration (case V), an exact solution (not closed form) and an approximation (closed form) were derived. Two sets of equations were derived for each of the five cases to take into consideration the possibility of a latency term (λ).Plots of drug amount X(or concentration C) vs. time (t) were constructed. In case I, a log Xvs. tplot was convex, the slope increasing with time. In case II, Xincreased,reached a peak, and decayed as in case I. In case III (λ 〉 5In 2V/Q) Creached a preinduction steady state before decreasing to a lower (induced) steady state. When λ=0, Creached a maximum before decreasing to the same induced steady state. The behavior of Cvs. tfor cases IV and V was similar to that for case III. Determination of parameters was attempted in case III. Nonlinear least-square fitting of generated data with 3–9% error yielded reasonable estimates of k′.
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  • 36
    ISSN: 1573-904X
    Keywords: oligodeoxynucleotides ; nuclease degradation ; plasma stability ; kinetics ; in vitrometabolism ; thrombin inhibitor
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To determine the degradation rates and pathways of GS-522, a potent oligodeoxynucleotide (GGTTGGTGTGGTTGG) inhibitor of thrombin, in serum and plasma. Methods. A stability-indicating, anion-exchange HPLC method was developed and used to determine concentrations of GS-522 and metabolites. Results. In monkey plasma at 2 µM or below, the degradation of GS-522 can be fit to a first-order exponential with a kp obs ~ 0.01 min−1. At 3 µM and above the degradation process deviates from a monoexponential decay profile. An initial fast degradation process is followed by a slower phase with an observed rate constant equal to that observed at 2 µM and below. In monkey serum, the KMand Vmaxare 8.4 µM and 0.87 µM min−1, respectively. Conclusions. The kinetics are consistent with an equilibrium binding of GS-522 to prothrombin in plasma (Kd = 50 nM) which saturates at GS-522 concentrations 〉2 µM. Compared to a scrambled sequence (GGTGGTGGTTGTGGT), with no defined tertiary structure, GS-522 is 4-fold more stable in serum. The metabolic profile in plasma is consistent with a 3′-exonuclease catalyzed hydrolysis of GS-522.
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  • 37
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    Colloid & polymer science 273 (1995), S. 524-532 
    ISSN: 1435-1536
    Keywords: Blends ; tetramethyl polycarbonate ; polystyrene ; LCST ; phase separation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A new method for the detection of phase separation and its kinetics through real-time measurements is presented using the dielectric technique. The kinetics of phase separation were determined for a blend of tetramethyl bisphenol-A polycarbonate TMPC and polystyrene PS at different temperatures. The temperature dependence of the rate constant of phase separation was determined. The activation energy of phase separation process is found to be equal to 46 kcal/mole. In addition, it was possible to determine the variation in the composition of the TMPC-rich phase with time. The results obtained were compared with the literature data and were found to be in good agreement.
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  • 38
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    Journal of bioenergetics and biomembranes 16 (1984), S. 391-406 
    ISSN: 1573-6881
    Keywords: OS-ATPase ; temperature effect ; kinetics ; lipid role ; membrane enzyme ; protein-lipid interaction (bovine mitochondria)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Physics
    Notes: Abstract The temperature dependence of the oligomycin-sensitive ATPase (complex V) kinetic parameters has been investigated in enzyme preparations of different phospholipid composition. In submitochondrial particles, isolated complex V, and complex V reconstituted in dimirystoyl lecithin vesicles, the Arrhenius plots show discontinuities in the range 18–28°C, while no discontinuity is detected with dioleoyl lecithin recombinant. Van't Hoff plots ofK m also show breaks in the same temperature interval, with the exception of the dioleoylenzyme vesicles, whereK m is unchanged. Thermodynamic analysis of the ATPase reaction shows that DMPC-complex V has rather larger values of activation enthalpy and activation entropy below the transition temperature (24°C) than those of the other preparations, while all enzyme preparations show similar free energies of activation (14.3–18.5 kcal/mol). The results indicate that temperature and lipid composition influence to a different extent both kinetic and thermodynamic parameters of ATP hydrolysis catalyzed by the mitochondrial ATPase.
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  • 39
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    Journal of bioenergetics and biomembranes 27 (1995), S. 331-340 
    ISSN: 1573-6881
    Keywords: Cytochromeb 5 ; cytochromec ; electron transfer ; kinetics ; ruthenium
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    Topics: Biology , Chemistry and Pharmacology , Physics
    Notes: Abstract The reaction of cytochromeb 5 with cytochromec has become a very prominent system for investigating fundamental questions regarding interprotein electron transfer. One of the first computer modeling studies of electron transfer and protein/protein interaction was reported using this system. Subsequently, numerous studies focused on the experimental determination of the features which control protein/protein interactions. Kinetic measurements of the intracomplex electron transfer reaction have only appeared in the last 10 years. The current review will provide a summary of the kinetic measurements and a critical assessment of the interpretation of these experiments.
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  • 40
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    Journal of bioenergetics and biomembranes 27 (1995), S. 583-596 
    ISSN: 1573-6881
    Keywords: Oxygen limitation ; p 50 ; critical oxygen pressure ; respirometry ; polarographic oxygen sensor ; human endothelial cells ; rat liver mitochondria ; intracellular $$p_{O_2 } $$ ; oxygen gradients ; kinetics ; nonequilibrium thermodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Physics
    Notes: Abstract Control and regulation of mitochondrial and cellular respiration by oxygen is discussed with three aims: (1) A review of intracellular oxygen levels and gradients, particularly in heart, emphasizes the dominance of extracellular oxygen gradients. Intracellular oxygen pressure, $$p_{O_2 } $$ , is low, typically one to two orders of magnitude below incubation conditions used routinely for the study of respiratory control in isolated mitochondria. The $$p_{O_2 } $$ range of respiratory control by oxygen overlaps with cellular oxygen profiles, indicating the significance of $$p_{O_2 } $$ in actual metabolic regulation. (2) A methodologically detailed discussion of high-resolution respirometry is necessary for the controversial topic of respiratory control by oxygen, since the risk of methodological artefact is closely connected with far-reaching theoretical implications. Instrumental and analytical errors may mask effects of energetic state and partially explain the divergent views on the regulatory role of intracellular $$p_{O_2 } $$ . Oxygen pressure for half-maximum respiration,p 50, in isolated mitochondria at state 4 was 0.025 kPa (0.2 Torr; 0.3 ΜM O2), whereasp 50 in endothelial cells was 0.06–0.08 kPa (0.5 Torr). (3) A model derived from the thermodynamics of irreversible processes was developed which quantitatively accounts for near-hyperbolic flux/ $$p_{O_2 } $$ relations in isolated mitochondria. The apparentp 50 is a function of redox potential and protonmotive force. The protonmotive force collapses after uncoupling and consequently causes a decrease inp 50. Whereas it is becoming accepted that flux control is shared by several enzymes, insufficient attention is paid to the notion of complementary kinetic and thermodynamic flux control mechanisms.
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  • 41
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    Journal of bioenergetics and biomembranes 27 (1995), S. 387-396 
    ISSN: 1573-6881
    Keywords: Plant mitochondria ; alternative oxidase ; kinetics ; regulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Physics
    Notes: Abstract The kinetic modelling of the respiratory network in plant mitochondria is discussed, with emphasis on the importance of the choice of boundary conditions, and of modelling of both quinol-oxidising and quinone-reducing pathways. This allows quantitative understanding of the interplay between the different pathways, and of the functioning of the plant respiratory network in terms of the kinetic properties of its component parts. The effects of activation of especially succinate dehydrogenase and the cyanide-insensitive alternative oxidase are discussed. Phenomena, such as respiratory control ratios depending on the substrate, shortcomings of the Bahr and Bonner model for electron distribution between the oxidases and reversed respiratory control, are explained. The relation to metabolic control analysis of the respiratory network is discussed in terms of top-down analysis.
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  • 42
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    Colloid & polymer science 273 (1995), S. 1028-1032 
    ISSN: 1435-1536
    Keywords: Hydrolyzed polyacrylamide ; hematite ; adsorption ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The adsorption measurements of hydrolyzed polyacrylamide (HPAM) onto hematite suspension are carried out to study the dynamics of the polymer adsorption onto the suspension particles and to investigate the mode of the polymer adsorption. The polymer is found to show much affinity for the adsorption because of the opposite charges possessed by the polymeric flocculant and the suspension particles. Various adsorption parameters such as adsorption coefficient, the rate constants for the adsorption and desorption, are evaluated with the help of a recently proposed kinetic scheme. It is found that the extent of adsorption and the adsorption rate are adequately affected by increasing the pH of the suspension while, unexpectedly, the adsorption is found to show only a marginal increase on addition of Na2SO4. Both the amount of the adsorbed polymer and the adsorption rate are also found to increase with the degree of hydrolysis of the polyelectrolyte.
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  • 43
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    Aquatic geochemistry 1 (1995), S. 399-426 
    ISSN: 1573-1421
    Keywords: manganese reduction ; manganese oxidation ; organic matter oxidation ; kinetics ; bacteria ; alkalinity ; lake chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The redox processes regulating transport of Mn in the water column of a eutrophic, dimictic lake (Lake Norrviken, Sweden) are interpreted based on a one-dimensional diffusion-reaction model for Mn(II). It is found that rates and rate constants for oxidation and reduction vary greatly with depth and also with time during the season of stratification. Calculated rates show that Mn(II) oxidation and reduction generally occur in narrow depth intervals (25–50 cm). This is in good agreement with measured profiles of particulate Mn (MnO x ). Maximum oxidation rate constants (assuming first order kinetics) at each date are in the first half of the season 〈1 d−1, but then increases to a rather constant value of about 25 d−1. These high rate constants are indicative of microbiological involvement in the Mn(II) oxidation. This is further evidenced by SEM-EDS analysis showing Mn enriched particles morphologically similar toMetallogenium. Reductive dissolution of Mn oxides occurs mainly in the zone just below the zone of maximum oxidation rate. The release of Mn(II) is accompanied by production of alkalinity and ΣCO2. The relation between production rates of Mn(II) and alkalinity indicates that Mn oxides act as terminal electron acceptors in the bacterially mediated oxidation of organic matter. However, the ΔMn2+/ΔΣCO2 ratio is significantly lower than what is expected from this process. It is suggested that the Mn reduction is coupled to fermentation. Close coexistence of Mn reduction and oxidation at high rates, such as found in the water column of this lake, facilitates rapid and continuous regeneration of reducible Mn oxides. This gives rise to a quantitatively important mechanism of organic matter oxidation in the water column.
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  • 44
    ISSN: 1573-9171
    Keywords: azidomercuration ; alkenes ; cycloalkenes ; strained double bond ; kinetics ; reaction mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of azidomercuration of alkenes, cycioalkenes, and their derivatives with a Hg(OAc)2-NaN3 system (1 ∶ 1, 1 ∶ 2, and 1 ∶ 3) was studied. Based on the data on the product structure and kinetic results, it was concluded that HgOAcN3 and Hg(N3)2 play the role of azidomercuration reagents. The reactions with alkenes having a strained double bond occur by a concerted scheme. With nonstrained alkenes, a multistep mechanism is realized, its first reversible step involving the formation of a mercurinium intermediate with an ion pair structure.
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