The Molecular Code for Hemoglobin Allostery Revealed by Linking the Thermodynamics and Kinetics of Quaternary Structural Change. 1. Microstate Linear Free Energy Relations†

Biochemistry ◽  
2004 ◽  
Vol 43 (38) ◽  
pp. 12048-12064 ◽  
Author(s):  
Robert A. Goldbeck ◽  
Raymond M. Esquerra ◽  
Jo M. Holt ◽  
Gary K. Ackers ◽  
David S. Kliger
Keyword(s):  
Free Energy ◽  
Structural Change ◽  
Thermodynamics And Kinetics ◽  
Linear Free Energy ◽  
Energy Relations ◽  
Kinetics Of ◽  
Molecular Code

The transmission of polar effects. Part VII. A proton magnetic resonance spectra study of substituted mesitylenes, durenes, anthracenes, and triptycenes

1968 ◽  
Vol 46 (24) ◽  
pp. 3903-3908 ◽  
Author(s):  
Keith Bowden ◽  
J. G. Irving ◽  
M. J. Price
Keyword(s):  
Dielectric Constant ◽  
Free Energy ◽  
Carbon Tetrachloride ◽  
Field Effect ◽  
Proton Magnetic Resonance ◽  
Chemical Shifts ◽  
Linear Free Energy ◽  
Solvent Dependence ◽  
Similar Dependence ◽  
Energy Relations

The chemical shifts of the ring protons in a series of monosubstituted mesitylenes and durenes, and of the 10-protons of a series of 9-substituted triptycenes and anthracenes have been measured in dimethyl sulfoxide, acetone, 2-methoxyethanol, and carbon tetrachloride. The solvent dependence of the substituent chemical shifts has been analyzed by linear free energy relations. The systems all show similar dependence which increases with increasing dielectric constant of the solvent. This does not result from the field effect being transmitted through the medium, but appears to arise from the formation of a hydrogen-bonded interaction between the solvent and the hydrogen of the solute. The substituent chemical shifts appear to arise from contributions from substituent field, resonance, magnetic anisotropy, and solvent effects.

Requirements and interpretation of linear free energy relations

1984 ◽  
Vol 106 (10) ◽  
pp. 2772-2774 ◽  
Author(s):  
Peter E. Doan ◽  
Russell S. Drago
Keyword(s):  
Free Energy ◽  
Linear Free Energy ◽  
Energy Relations

THE TRANSMISSION OF POLAR EFFECTS: PART II. THE KINETICS OF ESTERIFICATION WITH DIAZODIPHENYLMETHANE AND THE IONIZATION OF 3-SUBSTITUTED ACRYLIC ACIDS

1965 ◽  
Vol 43 (12) ◽  
pp. 3354-3363 ◽  
Author(s):  
Keith Bowden
Keyword(s):  
Butyl Alcohol ◽  
Polar Effect ◽  
Rate Coefficients ◽  
Strengthening Effect ◽  
Benzoic Acids ◽  
Linear Free Energy ◽  
Substituted Benzoic Acids ◽  
Energy Relations ◽  
Acrylic Acids ◽  
Kinetics Of

The rate coefficients for the reaction with diazodiphenylmethane in ethanol, t-butyl alcohol, and ethyl acetate at 30° and the pKa values in water at 25° of fourteen 3-substituted acrylic acids have been determined. The effect of substitution is assessed by use of linear free energy relations. A definite incremental acid-strengthening effect solely due to cis-substitution is confirmed. This is not a "bulk" steric effect and is due solely to the orientation of substitution. The polar effect of a substituent is found to be approximately the same from the cis- or trans-position. An attempt is made to test the suggested mechanisms for the transmission of the polar effect. In the reactions studied the transmission of the polar effect in 3-substituted acrylic acid and ortho-substituted benzoic acids is approximately twice that of the meta- or para-substituted benzoic acids. This appears to be reasonably accommodated by a significant field effect.

Linear free energy relations and the hammett equation for substituted pyridine 1-oxides

1967 ◽  
Vol 4 (4) ◽  
pp. 591-597 ◽  
Author(s):  
John H. Nelson ◽  
Roy G. Garvey ◽  
Ronald O. Ragsdale
Keyword(s):  
Free Energy ◽  
Hammett Equation ◽  
Linear Free Energy ◽  
Energy Relations

scholarly journals Thermodynamics and kinetics of the F o F 1 -ATPase: application of the probability isotherm

2016 ◽  
Vol 3 (2) ◽  
pp. 150379 ◽  
Author(s):  
Brian Chapman ◽  
Denis Loiselle
Keyword(s):  
Free Energy ◽  
Numerical Solution ◽  
Atp Synthesis ◽  
Enzyme Activation ◽  
Thermodynamic Efficiency ◽  
Second Law ◽  
Metabolic Rates ◽  
Thermodynamics And Kinetics ◽  
Rotary Mechanism ◽  
Kinetics Of

We use the results of recent publications as vehicles with which to discuss the thermodynamics of the proton-driven mitochondrial F o F 1 -ATP synthase, focusing particularly on the possibility that there may be dissociation between rotatory steps and ATP synthesis/hydrolysis. Such stoichiometric ‘slippage’ has been invoked in the literature to explain observed non-ideal behaviour. Numerical solution of the Rate Isotherm (the kinetic equivalent of the more fundamental Probability Isotherm) suggests that such ‘slippage’ is an unlikely explanation; instead, we suggest that the experimental results may be more consistent with damage to the enzyme caused by its isolation from the biomembrane and its experimental fixation, resulting in non-physiological friction within the enzyme's rotary mechanism. We emphasize the unavoidable constraint of the Second Law as instantiated by the obligatory dissipation of Gibbs Free Energy if the synthase is to operate at anything other than thermodynamic equilibrium. We use further numerical solution of the Rate Isotherm to demonstrate that there is no necessary association of low thermodynamic efficiency with high metabolic rates in a bio-world in which the dominating mechanism of metabolic control is multifactorial enzyme activation.

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