Thermodynamics and Kinetics of Glycolytic Reactions. Part I: Kinetic Modeling Based on Irreversible Thermodynamics and Validation by Calorimetry
Abstract
:1. Introduction
2. Results
2.1. Definitions and Specifications
2.2. Application of Irreversible Thermodynamics for Kinetic Evaluation
2.3. ITC Results
2.4. Kinetic Analyses
3. Discussion
3.1. Thermodynamic Data for Reaction 2
3.2. Validation of Kinetic Models by the New Calorimetric Data
3.3. Temperature Dependency of the Kinetics of Reaction 2
3.4. Temperature Dependency of Reaction 9
4. Materials and Methods
4.1. Chemicals
4.2. Sample Preparation for ITC Measurement
4.3. ITC Measurements
4.3.1. Reaction 2 (Phosphoglucose Isomerase Reaction)
4.3.2. Reaction 9 (Enolase Reaction)
4.4. Determination of Reaction Enthalpy and Equilibrium Constant
4.5. Kinetic Investigations
4.6. Statistics
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
Abbreviations
ITC | isothermal titration calorimetry |
G6P | glucose-6-phosphate |
F6P | fructose-6-phosphate |
2PG | 2-phosphoglycerate |
PEP | phosphoenolpyruvate |
PGI | phosphoglucose isomerase |
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Symbol | Property | Unit |
---|---|---|
A | pre-exponential factor | s−1 |
activity of component | - | |
concentration of component | mol kg−1 | |
concentration of component at time 0 | mol kg−1 | |
equilibrium concentration of component | mol kg−1 | |
product concentration | mol kg−1 | |
substrate concentration | mol kg−1 | |
activation energy | J mol−1 | |
Gibbs energy of biochemical reaction | J mol−1 | |
standard Gibbs energy of biochemical reaction | J mol−1 | |
enthalpy of biochemical reaction | J mol−1 | |
J | flux | mol L−1 s−1 |
thermodynamic equilibrium constant of biochemical reaction | - | |
apparent equilibrium-molality ratio of biochemical reaction | −/mol kg−1 | |
kinetic constant of reaction | s−1 | |
Michaelis constant for substrate/product | mol kg−1 | |
activity-coefficient ratio of biochemical reaction | −/mol kg−1 | |
L | phenomenological coefficient/kinetic parameter | s−1 |
m | mass | kg |
P | heat production rate | W |
Q | heat | J |
universal gas constant (8.314 J mol−1 K−1) | J mol−1 K−1 | |
r | reaction rate | mol L−1 s−1 |
maximum reaction rate | mol L−1 s−1 | |
temperature | K | |
α | correlation factor | mol kg−1 s−1 |
Λ | kinetic parameter | s−1 |
thermodynamic driving force | - | |
rational activity coefficient of component on molality base | - |
Buffer | |
---|---|
HEPES | 9.7 ± 0.3 |
Potassium phosphate | 9.6 ± 0.2 |
MOPS | 11.1 ± 0.5 |
Reaction 2 | Reaction 9 [40] | |||||
---|---|---|---|---|---|---|
Temperature (K) | Q (mJ) | Q (mJ) | ||||
298.15 | 7.63 ± 0.14 | 0.285 | 10.3 ± 0.2 | 8.15 ± 0.72 | 239.4 | 2.4 ± 0.2 |
305.15 | 7.63 ± 0.07 | 0.318 | 10.6 ± 0.1 | 7.85 ± 0.17 | 245.9 | 2.4 ± 0.1 |
310.15 | 7.86 ± 0.33 | 0.343 | 11.1 ± 0.5 | 7.64 ± 0.22 | 251.3 | 2.4 ± 0.1 |
Temperature (K) | Reaction 2 | Reaction 9 | ||
---|---|---|---|---|
(µmol kg−1s−1) | (mmol kg−1) | (ms−1) | (mmol kg−1) | |
298.15 | 7.03 ± 0.58 | 4.35 ± 0.64 | 0.34 ± 0.01 | 10.2 ± 0.92 |
305.15 | 10.30 ± 0.88 | 3.41 ± 0.39 | 0.44 ± 0.13 | 13.8 ± 3.35 |
310.15 | 13.21 ± 1.20 | 3.26 ± 0.09 | 0.57 ± 0.03 | 16.5 ± 0.48 |
Temperature (K) | Reaction 2 | Reaction 9 |
---|---|---|
L Value (s−1) | L Value (s−1) | |
298.15 | 217.18 ± 14.27 | 10.13 ± 0.65 |
305.15 | 358.80 ± 17.29 | 14.57 ± 3.20 |
310.15 | 518.44 ± 43.84 | 20.37 ± 1.03 |
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Vogel, K.; Greinert, T.; Reichard, M.; Held, C.; Harms, H.; Maskow, T. Thermodynamics and Kinetics of Glycolytic Reactions. Part I: Kinetic Modeling Based on Irreversible Thermodynamics and Validation by Calorimetry. Int. J. Mol. Sci. 2020, 21, 8341. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms21218341
Vogel K, Greinert T, Reichard M, Held C, Harms H, Maskow T. Thermodynamics and Kinetics of Glycolytic Reactions. Part I: Kinetic Modeling Based on Irreversible Thermodynamics and Validation by Calorimetry. International Journal of Molecular Sciences. 2020; 21(21):8341. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms21218341
Chicago/Turabian StyleVogel, Kristina, Thorsten Greinert, Monique Reichard, Christoph Held, Hauke Harms, and Thomas Maskow. 2020. "Thermodynamics and Kinetics of Glycolytic Reactions. Part I: Kinetic Modeling Based on Irreversible Thermodynamics and Validation by Calorimetry" International Journal of Molecular Sciences 21, no. 21: 8341. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms21218341