Reductions by ferrocytochrome c peroxidase: 5. Kinetics of ferricyanide reduction

1995 ◽  
Vol 73 (7) ◽  
pp. 1181-1186 ◽  
Author(s):  
Eddy Cheung ◽  
Ann M. English
Keyword(s):  
Ionic Strength ◽  
Rate Constant ◽  
Heme Proteins ◽  
Amino Acid Content ◽  
Total Charge ◽  
Ferricyanide Reduction ◽  
Cross Reactions ◽  
Ferrocytochrome C ◽  
Strength Formula ◽  
Kinetics Of

The kinetics of reduction of ferricyanide by yeast ferrocytochrome c peroxidase (CPPII) were investigated as a function of ionic strength in phosphate buffers at pH 7.0 and 25 ± 1 °C. The observed bimolecular rate constant (k12) is 8.4 × 104 M−1 s−1 in 0.1 M phosphate. The dependence of the reaction rate on ionic strength indicates a change of −9 on the protein at pH 7.0, which is in good agreement with the total charge of −11 estimated for CCPII from its amino acid content. Substituting k12 at infinite ionic strength [Formula: see text] into the Marcus cross relation yields an electron self-exchange rate constant [Formula: see text] for the FeIII/FeII couple of CCP of 7.2 × 10−5 M−1 s−1. This value is over four orders of magnitude higher than that calculated for the FeIV/FeIII couple of CCP from literature data for cross-reactions with ferrocyanide at pH 7.0. Possible reasons for the large difference in the two CCP [Formula: see text] values are discussed. Literature data also allowed [Formula: see text] values for various other heme proteins to be determined from their cross-reactions with ferricyanide. The calculated rate constants vary by eight orders of magnitude, and the variation of [Formula: see text] with protein structure suggests that the redox reactivity of ferrous heme proteins towards ferricyanide is dependent on the spin state and coordination of iron, as well as on the accessibility of the heme. Keywords: cytochrome c peroxidase, ferricyanide, Marcus cross relation, electron self-exchange.

scholarly journals Kinetic and spectrophotometric studies on the renaturation of deoxyribonucleic acid

1968 ◽  
Vol 109 (4) ◽  
pp. 543-557 ◽  
Author(s):  
K. J. Thrower ◽  
A. R. Peacocke
Keyword(s):  
Ionic Strength ◽  
Rate Constant ◽  
Base Pairs ◽  
Phage Dna ◽  
Dna Strands ◽  
Entropy Of Activation ◽  
T7 Phage ◽  
Kinetics Of ◽  
Rate Controlling Step ◽  
Adenine Thymine

The kinetics of the renaturation of Escherichia coli DNA in 0·4–1·0m-sodium chloride at temperatures from 60° to 90° have been studied. The extent of renaturation was a maximum at 65° to 75° and increased with ionic strength, and the rate constant increased with both ionic strength and temperature. The energy and entropy of activation of renaturation were calculated to be 6–7kcal.mole−1 and −40cal.deg.−1mole−1 respectively. It has been shown that renaturation is a second-order process for 5hr. under most conditions. The results are consistent with a reaction in which the rate-controlling step is the diffusion together of two separated complementary DNA strands and the formation of a nucleus of base pairs between them. The kinetics of the renaturation of T7-phage DNA and Bordetella pertussis DNA have also been studied, and their rates of renaturation related quantitatively to the relative heterogeneity of the DNA samples. By analysis of the spectra of DNA at different stages during renaturation it was shown that initially the renatured DNA was rich in guanine–cytosine base pairs and non-random in base sequence, but that, as equilibrium was approached, the renatured DNA gradually resembled native DNA more closely. The rate constant for the renaturation of guanine–cytosine base pairs was slightly higher than for adenine–thymine base pairs.

THE REACTION BETWEEN CYANATE AND HYPOCHLORITE

1956 ◽  
Vol 34 (4) ◽  
pp. 489-501 ◽  
Author(s):  
M. W. Lister
Keyword(s):  
Activation Energy ◽  
Ionic Strength ◽  
Rate Constant ◽  
Hypochlorous Acid ◽  
Effect Of Temperature ◽  
Slow Step ◽  
True Activation Energy ◽  
Rate Of Reaction ◽  
Different Temperatures ◽  
Kinetics Of

The reaction between sodium hypochlorite and potassium cyanate in the presence of sodium hydroxide has been examined. The main products are chloride, and carbonate ions and nitrogen; but, especially if much hypochlorite is present, some nitrate is formed as well. The rate of reaction is proportional to the cyanate and hypochlorite concentrations, but inversely proportional to the hydroxide concentration: the rate constant is 5.45 × 10−4 min.−1 at 65 °C, at an ionic strength of 2.2. The rate constant increases somewhat as the ionic strength rises from 1.7 to 3.5. The effect of temperature makes the apparent activation energy 25 kcal./gm-molecule. The kinetics of the reaction suggest that the slow step is really a reaction of hypochlorous acid and cyanate ions, and possible intermediate products of this reaction are suggested. Allowing for the different extent of hydrolysis of hypochlorite at different temperatures, the true activation energy is found to be 15 kcal./gm-mol., which is consistent with the observed rate of reaction.

Kinetics of oxidation of reduced cytochrome c by aquacopper(II) and chlorocopper(II) complexes in the presence of oxygen

1981 ◽  
Vol 34 (1) ◽  
pp. 99 ◽  
Author(s):  
JK Yandell
Keyword(s):  
Reaction Mechanism ◽  
Ionic Strength ◽  
Cytochrome C ◽  
Rate Constants ◽  
Kinetics Of Oxidation ◽  
Ferrocytochrome C ◽  
Kinetics Of

The rate constants for the oxidation of reduced cytochrome c by aquacopper(II) ion, aquachloro- copper(II) ion and aquadichlorocopper(II) were found to be 5.7�0.3 1. mol-1 s-1, 2.3×102 1. mol-1 s-1 and 5.6xl031. mol-1 s-1 respectively at 25�C, ionic strength 0.1 and pH 4.0. At low ratios of aquacopper(II) ion to ferrocytochrome c, when oxygen is required to completely oxidize the cytochrome, the reaction mechanism was found to be complex. No evidence for the involvement of copper bound to the cytochrome was found.

Studies on Horseradish Peroxidase. VII. A Kinetic Study of the Oxidation of Iodide by Horseradish Peroxidase Compound II

1971 ◽  
Vol 49 (18) ◽  
pp. 3059-3063 ◽  
Author(s):  
R. Roman ◽  
H. B. Dunford ◽  
M. Evett
Keyword(s):  
Ionic Strength ◽  
Horseradish Peroxidase ◽  
Kinetic Study ◽  
Rate Constant ◽  
Ph Dependence ◽  
Order Rate Constant ◽  
Acid Dissociation ◽  
Ph Range ◽  
Compound Ii ◽  
Kinetics Of

The kinetics of the oxidation of iodide ion by horseradish peroxidase compound II have been studied as a function of pH at 25° and ionic strength of 0.11. The logarithm of the second-order rate constant decreases linearly from 2.3 × 105 to 0.1 M−1 s−1 with increasing pH over the pH range 2.7 to 9.0. The pH dependence of the reaction is explained in terms of an acid dissociation outside the pH range of the study.

THE KINETICS OF THE CHELATION OF NICKEL (II) AND 1,10-PHENANTHROLINE

1964 ◽  
Vol 42 (4) ◽  
pp. 934-940 ◽  
Author(s):  
P. F. Barrett ◽  
W. MacF. Smith
Keyword(s):  
Ionic Strength ◽  
Rate Constant ◽  
Order Rate Constant ◽  
Second Order ◽  
Hydrogen Ion ◽  
Kinetic Behavior ◽  
Ion Concentrations ◽  
Order Rate ◽  
Kinetics Of ◽  
Limiting Values

The kinetics of the formation of the bidentate monocomplex of 1,10-phenanthroline and nickel (II) have been examined spectrophotometrically at ionic strength 0.5 over the range of temperatures 8 to 37 °C and over the range of hydrogen ion concentrations 0.01 to 0.30 molar. The kinetic behavior over the range of conditions is consistent with that found at 25 °C by Margerum, Bystroff, and Banks. The limiting values for the second-order rate constant for the reaction at high acidities have been assessed and imply associated values of ΔH≠and ΔS≠ of 9.5 kcal mol−1 and −5.3 e.u. respectively.

scholarly journals The kinetics of oxygen exchange between the sulfite ion and water

1970 ◽  
Vol 48 (13) ◽  
pp. 2035-2041 ◽  
Author(s):  
R. H. Betts ◽  
R. H. Voss
Keyword(s):  
Aqueous Solution ◽  
Ionic Strength ◽  
Rate Constant ◽  
Rate Constants ◽  
Time Rate ◽  
A Value ◽  
First Time ◽  
Kinetics Of ◽  
Sulfite Ion ◽  
Gross Rate

Oxygen of mass 18 was used as a stable tracer to measure the rate of exchange between the sulfite ion and water as a function of pH and total sulfite concentration. A value for the rate constant of hydration of SO2 in aqueous solution was determined. The gross rate constants k1 and k−1 for the overall reaction[Formula: see text]at 24.7 °C and ionic strength = 0.9 were evaluated from exchange results to be [Formula: see text]Also, for the first time, rate constants for the pyrosulfite equilibrium[Formula: see text]Were obtained[Formula: see text]at 24.7 °C and ionic strength = 0.9

Kinetics of the anation reaction of nickel(II) and 1,10-phenanthroline in methanol–water mixtures

1969 ◽  
Vol 47 (20) ◽  
pp. 3773-3778 ◽  
Author(s):  
M. L. Sanduja ◽  
W. MacF. Smith
Keyword(s):  
Ionic Strength ◽  
Rate Constant ◽  
Rate Constants ◽  
Solvent Composition ◽  
Solvent Mixtures ◽  
Methanol Content ◽  
Dependent Rate ◽  
Kinetics Of Formation ◽  
Kinetics Of ◽  
Anation Reaction

The kinetics of formation of the monophenanthroline complex of nickel(II) has been studied spectrophotometrically in water–methanol mixtures of 0 to 97 weight % of methanol, at ionic strength 0.050, at varying acidities at 25 °C. Values for the rate constants for the acid independent and acid dependent reactions together with values for the equilibrium acid ionization quotient of phenanthrolium ion over the range of solvent mixtures have been determined. The values of the acid independent rate constant show little dependence on solvent compositions up to 76% methanol, then decrease and show no correlation with trends in the ionization quotient of phenanthrolium ion. The acid dependent rate constant shows only a modest dependence on solvent composition over most of the range of solvent compositions except in the range of highest methanol content where it is not significantly different from zero.

The effect of binding ions on the oxidation of horse heart ferrocytochrome c

1979 ◽  
Vol 57 (5) ◽  
pp. 372-377 ◽  
Author(s):  
B. F. Peterman ◽  
R. A. Morton
Keyword(s):  
Ionic Strength ◽  
Rate Constant ◽  
Binding Sites ◽  
Oxidation Rate ◽  
Specific Binding ◽  
Electron Transfer Reaction ◽  
Oxidation Rate Constant ◽  
Binding Model ◽  
Ferrocytochrome C ◽  
Cacodylate Buffer

The effect of various specific binding ions on the rate of oxidation by potassium ferricyanide of electrodialyzed horse heart ferroeytochrome c was studied. The ionic strength was kept constant using Tris–cacodylate buffer, pH 7.0. Either the Tris or cacodylate ion was replaced by the binding ion studied. At an ionic strength of 0.194 M (24 °C), replacing cacodylate by chloride decreased the bimolecular oxidation rate constant from about 13.3 × 106 (Tris–cacodylate) to about 8.8 × 106 M−1 s−1 (Tris–chloride). Comparable decreases were found when cacodylate was replaced by phosphate or when Tris was replaced by potassium. When picrate replaced cacodylate (ionic strength 0.0485 M) a larger decrease was found, from about 5.2 × 107 to about 0.8 × 107 M−1 s−1. Data at intermediate ion concentrations were consistent with a simple cooperative binding model. The calculated association constants for chloride, potassium, and phosphate were in the range of 2–20 M−1, while for picrate it was 500 M−1. The data were consistent with one bound ion per ferroeytochrome c molecule, except for picrate, for which two binding sites were suggested. The results were interpreted by the hypothesis that the picrate ion binds near the solvent-exposed heme edge. The electron transfer reaction of ferricyanide was also presumed to take place through this region. The other ions probably bind at some distance from the heme edge and were suggested to exert their effect by perturbing the proteins' solvent shell. Consistent with this was the effect of replacing H2O by D2O which decreased the oxidation rate constant by about 50%.

scholarly journals Catalytic Effect of 1,4-Dioxane on the Kinetics of the Oxidation of Iodide by Dicyanobis(bipyridine)iron(III) in Water

Catalysts ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 840
Author(s):  
Rozina Khattak ◽  
Muhammad Sufaid Khan ◽  
Zahoor Iqbal ◽  
Rizwan Ullah ◽  
Abbas Khan ◽  
...  
Keyword(s):  
Ionic Strength ◽  
Rate Constant ◽  
Carrier Transport ◽  
Dye Sensitized Solar Cells ◽  
Catalytic Efficiency ◽  
Spectrophotometric Analysis ◽  
Binary Solvent ◽  
Experimental Conditions ◽  
Reaction Media ◽  
Kinetics Of

Dye-sensitized solar cells (DSSCs) are a technically and financially viable alternative to today’s photovoltaic systems using p-n junctions. The two functions are isolated here, which are unlike traditional systems where the semiconductor is thought to perform both light absorption and charge carrier transport. This article discusses the potential use of dicyanobis(bipyridine)iron(III) to oxidize iodide as a sensitizer in DSSCs. However, it is critical to understand the kinetics of this essential process in order to understand the mechanism of electron transport. The oxidation of iodide by dicyanobis(bipyridine)iron(III) in three reaction media was studied: water, 10% v/v 1,4-dioxane-water, and 20% v/v 1,4-dioxane-water. The reaction was carried out in a regular laboratory setting, with no special sensitive conditions or the use of expensive materials, making it a cost-effective and practical method. Dicyanobis(bipyridine)iron(III) oxidized iodide in selected media at 0.06 M ionic strength and constant temperature. The reaction was subjected to a spectrophotometric analysis. The data were acquired by measuring the rise in visible absorbance as a function of time after the formation of dicyanobis(bipyridine)iron(II). The reaction proceeded with an overall fractional (0.5), first order, and third order in water, 10% media, and 20% media, respectively. The presence of dicyanobis(bipyridine)iron(III) in either of the reaction media had no effect on the rate. The effect of protons (H+) on the rate constant indicated resistance in water and catalysis in dioxane-water media containing 10–20% dioxane. When the ionic strength was raised, there was no change in the rate constant in water, but there was a deceleration in both binary solvent media. In an aqueous medium, the thermodynamic parameters of activation were computed as Ea 46.23 kJ mol−1, 24.62 M s−1, ΔH# 43.76 kJ mol−1, ΔS# −226.5 J mol−1 K−1, and ΔG# 111.26 kJ mol−1 (25 °C). By increasing the rate of the reaction to its maximum, this study discovered the binary solvent media with the highest catalytic efficiency, i.e., 20% v/v 1,4-dioxane-water, which may increase the efficiency of DSSCs without using any expensive material or unusual experimental conditions.

scholarly journals Determination of the Effects of Medium Composition on the Monochloramine Disinfection Kinetics of Nitrosomonas europaea by the Propidium Monoazide Quantitative PCR and Live/Dead BacLight Methods

2010 ◽  
Vol 76 (24) ◽  
pp. 8277-8280 ◽  
Author(s):  
David G. Wahman ◽  
Karen A. Schrantz ◽  
Jonathan G. Pressman
Keyword(s):  
Ionic Strength ◽  
Quantitative Pcr ◽  
Rate Constant ◽  
Nitrosomonas Europaea ◽  
Medium Composition ◽  
Phosphate Concentration ◽  
Propidium Monoazide ◽  
Standard Medium ◽  
Kinetics Of

ABSTRACT Various medium compositions (phosphate, 1 to 50 mM; ionic strength, 2.8 to 150 meq/liter) significantly affected Nitrosomonas europaea monochloramine disinfection kinetics, as determined by the Live/Dead BacLight (LD) and propidium monoazide quantitative PCR (PMA-qPCR) methods (lag coefficient, 37 to 490 [LD] and 91 to 490 [PMA-qPCR] mg·min/liter; Chick-Watson rate constant, 4.0 × 10−3 to 9.3 × 10−3 [LD] and 1.6 × 10−3 to 9.6 × 10−3 [PMA-qPCR] liter/mg·min). Two competing effects may account for the variation in disinfection kinetic parameters: (i) increasing kinetics (disinfection rate constant [k] increased, lag coefficient [b] decreased) with increasing phosphate concentration and (ii) decreasing kinetics (k decreased, b increased) with increasing ionic strength. The results support development of a standard medium for evaluating disinfection kinetics in drinking water.

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