KINETIC STUDIES OF PROTEIN–DYE AND ANTIBODY–HAPTEN INTERACTIONS WITH THE TEMPERATURE-JUMP METHOD

1962 ◽  
Vol 40 (9) ◽  
pp. 1786-1797 ◽  
Author(s):  
A. Froese ◽  
A. H. Sehon ◽  
M. Eigen
Keyword(s):  
Relaxation Time ◽  
Bovine Serum Albumin ◽  
Rate Constants ◽  
Temperature Jump ◽  
Relaxation Times ◽  
Kinetic Studies ◽  
Single Relaxation Time ◽  
Effects Of Temperature ◽  
Arsonic Acid ◽  
Kinetics Of

The kinetics of protein–dye and antibody–hapten reactions were studied with the temperature-jump method. The systems used consisted of (i) bovine serum albumin (BSA) and the dye 1-naphthol-4-[4-(4′-azobenzene azo)phenyl arsonic acid], referred to as N—R′, (ii) BSA and the dye 1-naphthol-2-sulphonic acid-4-[4-(4′-azobenzene azo)phenyl arsonic acid], referred to as NS—R′, and (iii) rabbit antibodies to phenyl arsonic acid [Ab] and the hapten N—R′.Each of the systems exhibited a single relaxation time. From the analysis of the concentration dependence of the relaxation times, it was concluded that each system could be represented by the reactions[Formula: see text]where P refers to BSA or Ab, and D to N—R′ or NS—R′. The following rate constants were calculated for the three systems at 25 °C:[Formula: see text]The effects of temperature and pH on the rate constants of the system BSA – N—R′ are discussed.

The Self-Decay Characteristics of Chlorine Dioxide in Water

2012 ◽  
Vol 610-613 ◽  
pp. 296-299
Author(s):  
Xin Jie Li ◽  
Dan Nan Jiang ◽  
Yue Jun Zhang
Keyword(s):  
Rate Constants ◽  
Tap Water ◽  
Pure Water ◽  
Decay Behaviour ◽  
Increase With Increase ◽  
Higher Temperature ◽  
Effects Of Temperature ◽  
Lower Temperature ◽  
Kinetics Of ◽  
Temperature Water

In order to learn the ClO2 decay behaviour in tap water, the kinetics of ClO2 decay in pure water was studied. Under the conditions of tap water treatment and keeping away from light, the effects of temperature and pH on ClO2 degradation were investigated. The results show that the ClO2 decay reaction in pure water is the first-order with respect to ClO2, the decay rate constants increase with increase in temperature or pH. At pH=6.87, the rate constants are 0.012h-1(15°C), 0.017h-1(25°C), 0.023h-1(35°C), and 0.029h-1(45°C), respectively. At 25°C, the rate constants are 0.0083h-1(pH=4.5), 0.0111h-1(pH=5.5), 0.0143h-1(pH=6.5), 0.0222h-1(pH=7.5), and 0.0351h-1(pH=8.5), respectively. The experimental data prove that ClO2 is more stable in acidic or lower temperature water than in neutral, alkalescent, or higher temperature water.

scholarly journals STUDY OF CARBON DIOXIDE ADSORPTION ON CHROMIUM OXIDE AND GALLIUM OXIDE CATALYSTS ON BASIS OF NON-LINEAR RELAXATION TIMES

2018 ◽  
Vol 61 (2) ◽  
pp. 46 ◽  
Author(s):  
Nikolay I. Kol'tsov
Keyword(s):  
Carbon Dioxide ◽  
Relaxation Time ◽  
Chromium Oxide ◽  
Rate Constants ◽  
Gallium Oxide ◽  
Relaxation Times ◽  
Oxide Catalysts ◽  
Linear Relaxation ◽  
Adsorption And Desorption ◽  
Non Linear

Recently the analysis of transient regimes of chemical reactions is paid much attention. This is due to the fact that the time-dependent relaxation modes prior to achieving steady states contain important information about the features of the reactions. During unsteady mode the changes in reactant concentrations and rate of the reaction in time are observed. These changes are due to their own relaxation processes, depending on the structure of the reaction mechanism. A complete study of the reaction mechanism involves the study of the relaxation characteristics both near and away from the stationary state. Linear relaxation time describes the local transient modes near the steady state and it is calculated as the time decrease deviations of reactant concentrations from steady-state values in the e-times. Non-linear relaxation time describes the overall behavior reactions and it can be evaluated through the reaction time from the initial state to a stationary. Depending on the structural features of reactions ratio to determine the non-linear relaxation time through of reactions parameters (rate constants stages and reactant concentrations) differ significantly. The establishment of such ratio for a particular reaction allows getting more information to identify the mechanism and the constituent rate constants of its stages. The mechanism of any catalytic reaction involves stages adsorption of one or more of the starting materials on the catalyst surface. As a rule these stages are initial remaining stages of chemical transformation of reactants adsorbed forms follow them. Therefore, it is necessary to have the data on these stages and rate constants of adsorption of reagents on the catalyst surface. Earlier by author the method for estimating the values of the rate constants of adsorption and desorption by linear relaxation times was described. This method was used for determine of mechanism and kinetic parameters of process of adsorption of carbon dioxide on the chromium oxide and gallium oxide catalysts. In this article the method for estimating the values of the rate constants of adsorption and desorption by non-linear relaxation times for this process is described. The previously found CO2 dissociative adsorption mechanism was proved by the obtained results. The intervals of values changes of the rate constants of adsorption and desorption of carbon dioxide on the gallium oxide and chromium oxide catalysts were defined.Forcitation:Kol’tsov N.I. Study of carbon dioxide adsorption on chromium oxide and gallium oxide catalysts on basis of non-linear relaxation times. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 2. P. 46-52

Kinetics of the Ozonation of Tetrabromobisphenol-A in Wastewater

2011 ◽  
Vol 383-390 ◽  
pp. 2945-2950 ◽  
Author(s):  
Jie Zhang ◽  
Shi Long He ◽  
Mei Feng Hou ◽  
Li Ping Wang ◽  
Li Jiang Tian
Keyword(s):  
Rate Constants ◽  
Apparent Rate Constant ◽  
Reaction Rate ◽  
Batch Reactor ◽  
Kinetic Studies ◽  
Tetrabromobisphenol A ◽  
First Order ◽  
Reaction Rate Constants ◽  
Pseudo First Order ◽  
Kinetics Of

The kinetics of TBBPA degradation by ozonation in semi-batch reactor was studied. The reaction rate constants of TBBPA with O3 and •OH were measured by means of direct ozone attack and competition kinetics, and the values of which were 6.10 l/(mol•s), 4.8×109 l/(mol•s), respectively. Results of kinetic studies showed that TBBPA degradation by ozonation under the different conditions tested followed the pseudo-first-order. The values of apparent rate constant of TBBPA degradation increased with the increase of ozone dosage and pH, but decreased with the increase of initial TBBPA concentration.

KINETIC STUDIES OF METHYL-BIS-β-CHLOROETHYLAMINE: III. THE KINETICS OF THE DIMERIZATION IN METHANOL

1948 ◽  
Vol 26b (2) ◽  
pp. 175-180 ◽  
Author(s):  
C. A. Winkler ◽  
A. W. Hay ◽  
A. L. Thompson
Keyword(s):  
Rate Constants ◽  
Initial Rate ◽  
Kinetic Studies ◽  
First Order ◽  
Rate Expression ◽  
Principal Reaction ◽  
Kinetics Of ◽  
Rate Controlling Step

The principal reaction of methyl-bis-β-chloroethylamine in methanol is dimerization, which results in one chlorine from each molecule becoming ionic, but this is accompanied by slight alcoholysis. The rate-controlling step is believed to be the first order formation of an ethylenimonium ion which reacts rapidly with one of its kind to form dimer. The rate expression as calculated from initial rate constants is k (initial) = 4.0 × 1013e−19600/RThr.−1.

The dielectric behaviour of dipolar mixtures I: chlorobenzene–nitrobenzene mixtures

1986 ◽  
Vol 64 (11) ◽  
pp. 1534-1536 ◽  
Author(s):  
F. F. Hanna ◽  
K. N. Abdel-Nour ◽  
A. M. Ghoneim
Keyword(s):  
Relaxation Time ◽  
Thermodynamic Parameters ◽  
Relaxation Times ◽  
Dielectric Behaviour ◽  
Dilute Solutions ◽  
Single Relaxation Time ◽  
Microwave Region ◽  
Dielectric Absorption

The dielectric absorption of dilute solutions of nitrobenzene, chlorobenzene, and their mixtures in cyclohexane and Decalin® have been measured in the microwave region at three temperatures between 20 and 40 °C. The relaxation times and thermodynamic parameters are determined. A single relaxation time is found for the mixtures, and the results are discussed.

Dynamics of the Bis-Tris and High Spin-Low Spin Equilibria of 2-(2′-Pyridyl)imidazoleiron(II) Complexes in Dimethyl Sulfoxide Solutions

1988 ◽  
Vol 41 (9) ◽  
pp. 1315 ◽  
Author(s):  
JK Beattie ◽  
KJ Mcmahon
Keyword(s):  
Relaxation Time ◽  
Dimethyl Sulfoxide ◽  
Equilibrium Constant ◽  
Rate Constants ◽  
Temperature Jump ◽  
Free Ligand ◽  
Relaxation Curve ◽  
Dissociation Equilibrium ◽  
Laser Temperature Jump ◽  
Equilibrium Transition

Ultrasonic and temperature-jump relaxation kinetics have been used to observe, respectively, the spin equilibrium and tris-bis ligand dissociation equilibrium of the 2-(2′-pyridyl) imidazoleiron (II) complexes in dimethyl sulfoxide solutions. In the ultrasonic experiments a single relaxation curve describes the excess sound absorption with a relaxation time of 73�3 ns. This was identified as perturbation of the singlet-quintet spin equilibrium by comparison with previous laser temperature-jump measurements in other solvents and by the temperature dependence of the relaxation amplitude. The equilibrium constant for the singlet-quintet transition was determined by the Evans n.m.r . method to be 0.48 at 298 K. From the relaxation time and the equilibrium constant the rate constants for the spin-equilibrium transition can be calculated to be k15 of 4.5×106 s-1 and k51 of 9.4×106s-1. In the temperature-jump experiments a millisecond relaxation time was observed. The dependence of the relaxation time on the concentration of the free ligand is of the form kobs = a + b[L]. From the ratio b/a an equilibrium constant for the perturbed process can be calculated. An independent measure of this equilibrium constant was obtained from spectrophotometric measurements. The rate constants for the formation and dissociation of the tris complex are calculated to be 2.8 × 104 dm3 mol-1 s-1 and 2.1 × 102 s-1, respectively, at 298 K.

scholarly journals Nitrogenase of Klebsiella pneumoniae. Kinetic studies on the Fe protein involving reduction by sodium dithionite, the binding of MgADP and a conformation change that alters the reactivity of the 4Fe-4S centre

1987 ◽  
Vol 246 (2) ◽  
pp. 455-465 ◽  
Author(s):  
G A Ashby ◽  
R N F Thorneley
Keyword(s):  
Klebsiella Pneumoniae ◽  
Rate Constants ◽  
Protein Conformation ◽  
Kinetic Studies ◽  
Sodium Dithionite ◽  
Conformation Change ◽  
Fe Protein ◽  
Redox Active ◽  
Dithionite Ion ◽  
Kinetics Of

The kinetics of reduction of indigocarmine-dye-oxidized Fe protein of nitrogenase from Klebsiella pneumoniae (Kp2ox) by sodium dithionite in the presence and absence of MgADP were studied by stopped-flow spectrophotometry at 23 degrees C and at pH 7.4. Highly co-operative binding of 2MgADP (composite K greater than 4 × 10(10) M-2) to Kp2ox induced a rapid conformation change which caused the redox-active 4Fe-4S centre to be reduced by SO2-.(formed by the predissociation of dithionite ion) with k = 3 × 10(6) M-1.s-1. This rate constant is at least 30 times lower than that for the reduction of free Kp2ox (k greater than 10(8) M-1.s-1). Two mechanisms have been considered and limits obtained for the rate constants for MgADP binding/dissociation and a protein conformation change. Both mechanisms give rate constants (e.g. MgADP binding 3 × 10(5) less than k less than 3 × 10(6) M-1.s-1 and protein conformation change 6 × 10(2) less than k less than 6 × 10(3) s-1) that are similar to those reported for creatine kinase (EC 2.7.3.2). The kinetics also show that in the catalytic cycle of nitrogenase with sodium dithionite as reductant replacement of 2MgADP by 2MgATP occurs on reduced and not oxidized Kp2. Although the Kp2ox was reduced stoichiometrically by SO2-. and bound two equivalents of MgADP with complete conversion into the less-reactive conformation, it was only 45% active with respect to its ability to effect MgATP-dependent electron transfer to the MoFe protein.

scholarly journals Kinetic studies of oxidized nicotinamide–adenine dinucleotide-facilitated reactions of d-glyceraldehyde 3-phosphate dehydrogenase

1974 ◽  
Vol 143 (2) ◽  
pp. 353-363 ◽  
Author(s):  
Patricia J. Harrigan ◽  
David R. Trentham
Keyword(s):  
Nicotinamide Adenine Dinucleotide ◽  
Temperature Jump ◽  
Reaction Pathway ◽  
Kinetic Studies ◽  
Rate Equations ◽  
First Order ◽  
Diffusion Controlled ◽  
Relaxation Temperature ◽  
Pig Muscle ◽  
Kinetics Of

The kinetics of the acylation of d-glyceraldehyde 3-phosphate dehydrogenase from pig muscle by 1,3-diphosphoglycerate in the presence of NAD+ has been analysed by using the relaxation temperature-jump method. At pH7.2 and 8°C the rate of acylation of the NAD+-bound (or holo-) enzyme was 3.3×105m−1·s−1 and the rate of phosphorolysis, the reverse reaction, was 7.5×103m−1·s−1. After a temperature-jump perturbation the equilibrium of NAD+ binding to the acyl-enzyme was re-established more rapidly than that of the acylation. The rate of phosphorolysis of the apoacylenzyme from sturgeon muscle and of aldehyde release from the d-glyceraldehyde 3-phosphate–apoenzyme complex were ≤40m−1·s−1 and ≤12s−1 respectively at pH8.0 and 22°C, which means that both processes are too slow to contribute significantly to the reaction pathway of the reversible NAD+-linked oxidative phosphorylation of d-glyceraldehyde 3-phosphate. Phosphorolysis of both acyl-apoenzyme and acyl-holoenzyme was first-order in Pi up to 100mm-Pi and more. PO43− could be the reactive species of the phosphorolysis of the acyl-holoenzyme, in which case phosphorolysis is a diffusion-controlled reaction, although other kinetically indistinguishable rate equations for the reaction are possible.

scholarly journals THE PHOTOINITIATED ADDITION OF MERCAPTANS TO OLEFINS: III. THE KINETICS OF THE ADDITION OF THIOPHENOL TO STYRENE AND TO 1-OCTENE

1957 ◽  
Vol 35 (7) ◽  
pp. 723-733 ◽  
Author(s):  
R. H. Pallen ◽  
C. Sivertz
Keyword(s):  
Free Radical ◽  
Rate Constants ◽  
Chain Transfer ◽  
Kinetic Studies ◽  
Activation Energies ◽  
Reverse Reaction ◽  
Kinetics Of

Kinetic studies were made of the free radical photoinitiated addition of thiophenol to 1-octene and to styrene in the absence of oxygen. In addition to the usual attack, chain transfer, and termination steps, it is found that a reverse reaction accompanies the attack step, [Formula: see text] The rate constants for the thiophenol–styrene reaction were calculated to be [Formula: see text]kt = 2 × 107 liters.moles−1sec.−1. The over-all activation energies for the two reactions were found to be E (1-octene) = 1.2 kcal., E (styrene) = 2.4 kcal.; suggestions are submitted as to why these activation energies are so low. These reactions are compared with n-butyl mercaptan – olefin reactions.

Laser Raman temperature-jump study of the kinetics of the triiodide equilibrium. Relaxation times in the 10-8 -10-7 second range

1972 ◽  
Vol 94 (5) ◽  
pp. 1554-1559 ◽  
Author(s):  
Douglas H. Turner ◽  
George W. Flynn ◽  
Norman Sutin ◽  
James V. Beitz
Keyword(s):  
Temperature Jump ◽  
Relaxation Times ◽  
Laser Raman ◽  
Kinetics Of
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