Thermodynamics and Kinetics of Glycolytic Reactions. Part II: Influence of Cytosolic Conditions on Thermodynamic State Variables and Kinetic Parameters
Abstract
:1. Introduction
2. Results
2.1. Influence of the Cytosolic Conditions on the Reaction Enthalpy Change
2.2. Influence of the Cytosolic Conditions on the Reaction Kinetics
2.2.1. The Noor Model
2.2.2. The Flux-Force Model
3. Discussion
3.1. Influence of the Cytosolic Conditions on the Reaction Enthalpy Change
3.2. Influence of the Cytosolic Conditions on the Reaction Kinetics
3.2.1. Validation of Kinetic Models
3.2.2. Importance of Cytosolic Conditions
3.2.3. Influence on Reaction 2
3.2.4. Influence on Reaction 9
4. Materials and Methods
4.1. Chemicals
4.2. Sample Preparation
4.3. ITC Measurements of the Phosphoglucose Isomerase Reaction
4.4. ITC Measurements of the Enolase Reaction
4.5. Thermodynamic Calculations
4.6. Kinetic Evaluation
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
Abbreviations
PEG | polyethylene glycol |
BSA | bovine serum albumin |
ITC | isothermal titration calorimetry |
M-M | Michaelis-Menten |
G6P | glucose-6-phosphate |
F6P | fructose-6-phosphate |
2PG | 2-phosphoglycerate |
PEP | phosphoenolpyruvate |
PGI | phosphoglucose isomerase |
Symbols
Symbol | Property | Unit |
r | reaction rate | mol kg−1 s−1 |
substrate concentration | mol kg−1 | |
product concentration | mol kg−1 | |
L | phenomenological coefficient/kinetic parameter | s−1 |
thermodynamic driving force | - | |
Gibbs free energy change of biochemical reaction | J mol−1 | |
standard Gibbs free energy change of biochemical reaction | J mol−1 | |
universal gas constant (8.314 J∙mol−1∙K−1) | J mol−1 K−1 | |
temperature | K | |
activity of component | - | |
concentration of component | mol kg−1 | |
kinetic constant of reaction | s−1 | |
Michaelis constant for substrate/product | mol kg−1 | |
concentration of component at time 0 | mol kg−1 | |
equilibrium concentration of component | mol kg−1 | |
maximum reaction rate | mol kg−1 s−1 | |
Λ | kinetic parameter | s−1 |
Q | heat | J |
reaction enthalpy change of biochemical reaction | J mol−1 | |
standard entropy change of biochemical reaction | J mol−1 K−1 | |
P | heat production rate | W |
m | mass | kg |
equilibrium-molality ratio of biochemical reaction | -/mol kg−1 | |
thermodynamic equilibrium constant of biochemical reaction | - | |
activity-coefficient ratio of biochemical reaction | -/mol kg−1 | |
rational activity coefficient of component on molality base | - | |
relative dielectric constant | - |
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pH | ||
---|---|---|
6 | 9.6 ± 0.2 kJ mol−1 (86 ± 2%) | 13.2 kJ mol−1 (91%) |
7 | 11.1 ± 0.5 kJ mol−1 (100%) | 14.5 kJ mol−1 (100%) |
8 | 10.8 ± 0.3 kJ mol−1 (97 ± 3%) | 14.7 kJ mol−1 (101%) |
Gibbs Free Energy Change (kJ mol−1) | Reaction Enthalpy Change (kJ mol−1) | Entropy Change (J mol−1 K−1) | ||||
---|---|---|---|---|---|---|
Conditions | Reaction 2 | Reaction 9 | Reaction 2 | Reaction 9 From [6] | Reaction 2 | Reaction 9 From [6] |
basic condition | 2.8 ± 0.1 | −13.7 ± 0.1 | 11.1 ± 0.5 | 2.4 ± 0.1 | 26.9 ± 1.7 | 51.8 ± 0.5 |
250 g L−1 PEG 20,000 | 12.8 ± 2.9 | −10.8 ± 0.1 | 7.8 ± 0.3 | 0.7 ± 0.0 | −15.9 ± 1.1 | 34.7 ± 0.8 |
250 g L−1 PEG 6000 | 12.8 ± 2.9 | n.d. | 7.7 ± 0.1 | n.d. | −16.4 ± 0.4 | n.d. |
250 g L−1 BSA | 6.4 ± 0.2 | n.d. | 7.4 ± 1.0 | n.d. | 3.1 ± 3.6 | n.d. |
Conditions | Chemicals | Values | Unit |
---|---|---|---|
Temperature | - | 298.15, 305.15, 310.15 | K |
pH | buffer | 6, 7, 8 | - |
Na+ concentration | NaOH, NaCl | 0.1, 0.15, 0.3 | mol kg−1 |
Mg2+ concentration | MgCl2 | 1, 8, 15 | mmol kg−1 |
Crowding agent concentration | PEG 20,000 PEG 6000 BSA | 0, 113, 182, 250 250 250 | g kg−1 |
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Vogel, K.; Greinert, T.; Reichard, M.; Held, C.; Harms, H.; Maskow, T. Thermodynamics and Kinetics of Glycolytic Reactions. Part II: Influence of Cytosolic Conditions on Thermodynamic State Variables and Kinetic Parameters. Int. J. Mol. Sci. 2020, 21, 7921. https://doi.org/10.3390/ijms21217921
Vogel K, Greinert T, Reichard M, Held C, Harms H, Maskow T. Thermodynamics and Kinetics of Glycolytic Reactions. Part II: Influence of Cytosolic Conditions on Thermodynamic State Variables and Kinetic Parameters. International Journal of Molecular Sciences. 2020; 21(21):7921. https://doi.org/10.3390/ijms21217921
Chicago/Turabian StyleVogel, Kristina, Thorsten Greinert, Monique Reichard, Christoph Held, Hauke Harms, and Thomas Maskow. 2020. "Thermodynamics and Kinetics of Glycolytic Reactions. Part II: Influence of Cytosolic Conditions on Thermodynamic State Variables and Kinetic Parameters" International Journal of Molecular Sciences 21, no. 21: 7921. https://doi.org/10.3390/ijms21217921