Theory of vibrational relaxation in mixtures of ortho- and para-hydrogen

1981 ◽  
Vol 59 (8) ◽  
pp. 1277-1283 ◽  
Author(s):  
Avygdor Moise ◽  
Huw O. Pritchard
Keyword(s):  
Rate Constants ◽  
Vibrational Relaxation ◽  
Numerical Study ◽  
Relaxation Times ◽  
High Dilutions ◽  
State Rate ◽  
The Mean ◽  
The Individual ◽  
Individual Rate ◽  
Very High

A numerical study of the vibrational relaxation at 500 K of a mixture of ortho-H2 and para-H2 is described. The required state-to-state rate constants were calculated from the quantum results of Rabitz and co-workers, and missing pieces of data were estimated by interpolation.It is concluded that only one relaxation time will be observed in any mixture of ortho-H2 and para-H2 and that (except at very high dilutions in a third inert gas) the relaxation rate constant will be close to the mean of the individual rate constants for relaxation, weighted according to the respective mole fractions of ortho-H2 and para-H2 present in the mixture.We find that the relaxation process can be modelled very accurately as an electrical RC network, whose time constants can be written down quite easily as sums of the appropriate microscopic rate constants, and by using this model, it is a simple matter to explore the conditions required for a mixture of two gases to exhibit two distinct vibrational relaxation times.

scholarly journals Isomerization of an enzyme-coenzyme complex in yeast alcohol dehydrogenase-catalysed reactions

2003 ◽  
Vol 68 (2) ◽  
pp. 77-84 ◽  
Author(s):  
Vladimir Leskovac ◽  
Svetlana Trivic ◽  
Draginja Pericin
Keyword(s):  
Alcohol Dehydrogenase ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Kinetic Mechanism ◽  
Yeast Alcohol Dehydrogenase ◽  
Catalyzed Reactions ◽  
The Individual ◽  
Individual Rate ◽  
Catalyzed Oxidation

In this work, all the rate constants in the kinetic mechanism of the yeast alcohol dehydrogenase-catalyzed oxidation of ethanol by NAD+, at pH 7.0, 25 ?C, have been estimated. The determination of the individual rate constants was achieved by fitting the reaction progress curves to the experimental data, using the procedures of the FITSIM and KINSIM software package of Carl Frieden. This work is the first report in the literature showing the internal equilibrium constants for the isomerization of the enzyme-NAD+ complex in yeast alcohol dehydrogenase-catalyzed reactions.

Study of Speed-Flow Relationships on Individual Freeway Lanes

1997 ◽  
Vol 1591 (1) ◽  
pp. 7-13 ◽  
Author(s):  
V. F. Hurdle ◽  
Mark I. Merlo ◽  
Doug Robertson
Keyword(s):  
Practical Interest ◽  
Linear Functions ◽  
Highway Capacity ◽  
Highway Capacity Manual ◽  
Speed Flow ◽  
High Flows ◽  
The Mean ◽  
The Individual ◽  
The Relationship ◽  
Very High

Many researchers have examined the form of the relationship between speed and flow on freeways. However, these researchers have concentrated on relationships for the freeway as a whole instead of on individual lanes. In this study, the relationship was examined for each of the three lanes at two locations on Highway 401 in metropolitan Toronto. It proved possible to accurately describe the mean speed in each lane with simple linear functions over the range of flows of most practical interest. Cubic functions provided comparable results over a wider range of flows, but it appears unlikely that the very high and very low flows are of sufficient interest to justify the added complexity. When an attempt was made to examine the relationship between speed and flow for the entire roadway, the linear functions were not adequate, but cubic functions performed reasonably well. However, the details of the full roadway curves are quite different from those of the curves described in the 1994 Highway Capacity Manual. In particular, the curves described in the manual are much steeper than the Highway 401 curves at high flows, implying a much more rapid loss of performance as flow approaches capacity than was observed. The full roadway curves are also surprisingly different from the curves for the individual lanes.

scholarly journals The linkage between binding of the C-terminal domain of hirudin and amidase activity in human α-thrombin

1993 ◽  
Vol 289 (2) ◽  
pp. 475-480 ◽  
Author(s):  
R de Cristofaro ◽  
B Rocca ◽  
B Bizzi ◽  
R Landolfi
Keyword(s):  
Rate Constants ◽  
Binding Constant ◽  
Amidase Activity ◽  
Equilibrium Binding ◽  
Viscosity Effects ◽  
The Individual ◽  
Individual Rate ◽  
Hydrolysis Of ◽  
Equilibrium Binding Constant

A method derived from the analysis of viscosity effects on the hydrolysis of the amide substrates D-phenylalanylpipecolyl-arginine-p-nitroaniline, tosylglycylprolylarginine-p-nitroanaline and cyclohexylglycylalanylarginine-p-nitroalanine by human alpha-thrombin was developed to dissect the Michaelis-Menten parameters Km and kcat into the individual rate constants of the binding, acylation and deacylation reactions. This method was used to analyse the effect of the C-terminal hirudin (residues 54-65) [hir-(54-65)] domain on the binding and hydrolysis of the three substrates. The results showed that the C-terminal hir-(54-65) fragment affects only the acylation rate, which is increased approx. 1.2-fold for all the substrates. Analysis of the dependence of acylation rate constants on hirudin-fragment concentration, allowed the determination of the equilibrium binding constant of C-terminal hir-(54-65) (Kd approximately 0.7 microM). In addition this peptide was found to competitively inhibit thrombin-fibrinogen interaction with a Ki which is in excellent agreement with the equilibrium constant derived from viscosity experiments. These results demonstrate that binding of hir-(54-65) to the fibrinogen recognition site of thrombin does not affect the equilibrium binding of amide substrates, but induces only a small increase in the acylation rate of the hydrolysis reaction.

Analytic solution of relaxation and dissociation of ozone and sulphur dioxide at low pressures

1981 ◽  
Vol 59 (17) ◽  
pp. 2569-2574 ◽  
Author(s):  
Wendell Forst
Keyword(s):  
Rate Constants ◽  
Sulphur Dioxide ◽  
Vibrational Relaxation ◽  
Analytic Solution ◽  
Thermal Dissociation ◽  
Relaxation Times ◽  
Average Energy ◽  
Collision Rate ◽  
Low Pressures ◽  
Good Agreement

The analytic solution of vibrational relaxation in a low-pressure gas is applied to the thermal dissociation of O3 in helium and of SO2 in argon. Use is made of experimental relaxation times to obtain average energy lost per collision. Calculated weak-collision rate constants are in very good agreement with experiment in the case of SO2, but only in fair agreement in the case of ozone. Several curious aspects of the ozone system, both experimental and theoretical, are discussed.

Growth, Metamorphosis and Energy Conversion in the Larvae of the Prawn, Palaemon Serratus

1969 ◽  
Vol 49 (1) ◽  
pp. 77-96 ◽  
Author(s):  
M. R. Reeve
Keyword(s):  
Energy Conversion ◽  
Larval Growth ◽  
Energy Conversion Efficiency ◽  
Variable Number ◽  
Larval Stages ◽  
Length Increase ◽  
History Of ◽  
The Mean ◽  
The Individual ◽  
Very High

The life-history of the larva of the prawn Palaemon serratus (Pennant) was studied in the laboratory and found to comprise a variable number of stages, dependent on feeding level and other factors. Larval moulting frequency was relatively constant at 3-day intervals, and could be followed in a population by daily examination for exuvia moult-casts. Length increase at each moult progressed arithmetically, and the highest mortalities occurred during metamorphosis. Consumption of Anemia nauplii by each larva rose from 30 to 400 per day. Populations of isolated animals (i.e. when cannibalism was excluded) were inspected daily and the exact number and duration of larval stages determined. Survival through metamorphosis was very high (over 85%) at both high and low feeding levels, although at the latter the larvae passed through more stages with more erratic duration times. At the end of the experiment, when all the larvae had metamorphosed, the mean dry weights at the high and low feeding levels were 7.7 and o.6 mg respectively. Larval stages could not be positively identified morphologically after stage III unless the history of the individual in question was known. It is suggested that the number of larval stages in the sea may also be very variable and difficult to determine.Energy-conversion efficiency was calculated from food uptake measurements and larval growth estimations, and was found to be 50–60% during most of the larval life, falling to 35% when the early post-larvae were taken into account.

Acid-catalyzed hydrolysis of 2-methylene-1,3-dithiolane. 2. Remarkable effects of β substitution on reversibility of the carbon protonation

1986 ◽  
Vol 64 (6) ◽  
pp. 1116-1123 ◽  
Author(s):  
Tadashi Okuyama ◽  
Masayoshi Toyoda ◽  
Takayuki Fueno
Keyword(s):  
Aqueous Solution ◽  
Rate Constants ◽  
Isotope Exchange ◽  
Relative Stabilities ◽  
The Third ◽  
Initial Carbon ◽  
Acid Catalyzed ◽  
The Individual ◽  
Individual Rate ◽  
Hydrolysis Of

Hydrolyses of 2-ethylidene-(1b), 2-isopropylidene-(1c), and 2-benzylidene-1,3-dithiolane (1d) were kinetically investigated in aqueous solution. All the individual rate constants involved in this three-step reaction were evaluated. Initial carbon protonation is only partially reversible (k2/k−1 = 1.33, 0.68, and 1.02 for 1b, 1c, and 1d, respectively) at higher pH, while the protonation becomes completely reversible below pH 2 where the third step is rate determining. Complete H–D isotope exchange at the β-carbon of 1b and 1d was observed in deuterium media before appreciable hydrolysis took place. It was demonstrated that reversion from the tetrahedral intermediate 3 to 1 occurs extensively during the reaction in the latter acidity range. Relative stabilities and reactivities of the olefinic substrates 1 are discussed.

scholarly journals Temperature response of Rubisco kinetics in Arabidopsis thaliana: thermal breakpoints and implications for reaction mechanisms

2018 ◽  
Author(s):  
Ryan A. Boyd ◽  
Amanda P. Cavanagh ◽  
David S. Kubien ◽  
Asaph B. Cousins
Keyword(s):  
Arabidopsis Thaliana ◽  
Reaction Mechanism ◽  
Kinetic Parameters ◽  
Rate Constants ◽  
Reaction Mechanisms ◽  
Temperature Response ◽  
Concentration Changes ◽  
The Individual ◽  
Temperature Responses ◽  
Individual Rate

ABSTRACTOptimization of Rubisco kinetics could improve photosynthetic efficiency, ultimatly resulting in increased crop yield. However, imprecise knowledge of the reaction mechanism and the individual rate constants limit our ability to optimize the enzyme. Membrane inlet mass spectrometery (MIMS) may offer benefits over traditional methods for determining individual rate constants of the Rubisco reaction mechanism, as it can directly monitor concentration changes in CO2, O2, and their isotopologs during assays. However, a direct comparsion of MIMS to the traditional Radiolabel method of determining Rubisco kinetic parameters has not been made. Here, the temperature responses of Rubisco kinetic parameters from Arabidopsis thaliana were measured using the Radiolabel and MIMS methods. The two methods provided comparable parameters above 25 °C, but temperature responses deviated at low temperature as MIMS derived catalytic rates of carboxylation, oxygenation, and CO2/O2 specificity showed thermal breakpoints. Here we discuss the variability and uncertainty surrounding breakpoints in the Rubisco temperature response and relavance of individual rate constants of the reaction mechanisms to potential breakpoints.

scholarly journals Comparison of Eight Methods for the Estimation of the Image-Derived Input Function in Dynamic [18F]-FDG PET Human Brain Studies

2009 ◽  
Vol 29 (11) ◽  
pp. 1825-1835 ◽  
Author(s):  
Paolo Zanotti-Fregonara ◽  
El Mostafa Fadaili ◽  
Renaud Maroy ◽  
Claude Comtat ◽  
Antoine Souloumiac ◽  
...  
Keyword(s):  
Blood Sample ◽  
Rate Constants ◽  
Fdg Pet ◽  
Input Function ◽  
Blood Samples ◽  
Arterial Blood ◽  
Positron Emission ◽  
Phantom Studies ◽  
The Individual ◽  
Individual Rate

The aim of this study was to compare eight methods for the estimation of the image-derived input function (IDIF) in [18F]-FDG positron emission tomography (PET) dynamic brain studies. The methods were tested on two digital phantoms and on four healthy volunteers. Image-derived input functions obtained with each method were compared with the reference input functions, that is, the activity in the carotid labels of the phantoms and arterial blood samples for the volunteers, in terms of visual inspection, areas under the curve, cerebral metabolic rates of glucose (CMRglc), and individual rate constants. Blood-sample-free methods provided less reliable results as compared with those obtained using the methods that require the use of blood samples. For some of the blood-sample-free methods, CMRglc estimations considerably improved when the IDIF was calibrated with a single blood sample. Only one of the methods tested in this study, and only in phantom studies, allowed a reliable calculation of the individual rate constants. For the estimation of CMRglc values using an IDIF in [18F]-FDG PET brain studies, a reliable absolute blood-sample-free procedure is not available yet.

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