Electron Free Energy Levels and Spectroscopic Character of Dilute Species in Oxidic Solvents: Relating Aqueous to Liquid (and Vitreous) Oxide Solutions

1978 ◽  
pp. 273-288
Author(s):  
C. A. Angell
Keyword(s):  
Free Energy ◽  
Energy Levels

Metabolic and energy correlates of intracellular pH in progressive fatigue of squid (L. brevis) mantle muscle

1996 ◽  
Vol 271 (5) ◽  
pp. R1403-R1414 ◽  
Author(s):  
H. O. Portner ◽  
E. Finke ◽  
P. G. Lee
Keyword(s):  
Free Energy ◽  
Critical Velocity ◽  
Energy Levels ◽  
High Energy ◽  
Swimming Velocity ◽  
High Energy Phosphates ◽  
Energy Status ◽  
Intracellular Acidosis ◽  
Model Calculations

Squid (Lolliguncula brevis) were exercised at increasing swimming speeds to allow us to analyze the correlated changes in intracellular metabolic, acid-base, and energy status of the mantle musculature. Beyond a critical swimming velocity of 1.5 mantle lengths/s, an intracellular acidosis developed that was caused by an initial base loss from the cells, the onset of respiratory acidification, and, predominantly, octopine formation. The acidosis was correlated with decreasing levels of phospho-L-arginine and, thus, supported ATP buffering at the expense of the phosphagen. Monohydrogenphosphate, the actual substrate of glycogen phosphorylase accumulated, enabling glycogen degradation, despite progressive acidosis. In addition to octopine, succinate, and glycerophosphate accumulation, the onset of acidosis characterizes the critical velocity and indicates the transition to a non-steady-state time-limited situation. Accordingly, swimming above the critical velocity caused cellular energy levels (in vivo Gibbs free energy change of ATP hydrolysis) to fall. A minimal value was reached at about -45 kJ/mol. Model calculations demonstrate that changes in free Mg2+ levels only minimally affect ATP free energy, but minimum levels are relevant in maintaining functional concentrations of Mg(2+)-complexed adenylates. Model calculations also reveal that phosphagen breakdown enabled L. brevis to reach swimming speeds about three times higher than the critical velocity. Comparison of two offshore squid species (Loligo pealei and Illex illecebrosus) with the estuarine squid L.brevis indicates that the latter uses a strategy to delay the exploitation of high-energy phosphates and protect energy levels at higher than the minimum levels (-42 kJ/mol) characterizing fatigue in the other species. A more economical use of anaerobic resources and an early reduction in performance may enable L. brevis to tolerate more extreme environmental conditions in shallow estuarine waters and even hypoxic environments and to prevent a fatal depletion of energy stores.

Dangling Bonds in Amorphous Silicon Nitride Alloys: Predictions of the Free Energy Model

1992 ◽  
Vol 284 ◽  
Author(s):  
F. W. Smith ◽  
H. Efstathiadis ◽  
Z. Yin
Keyword(s):  
Free Energy ◽  
Energy Gap ◽  
Energy Levels ◽  
Experimental Studies ◽  
Energy Model ◽  
Paramagnetic Defect ◽  
Amorphous Network ◽  
Energy Of Mixing ◽  
Free Energy Model ◽  
Free Energy Of Mixing

ABSTRACTThe free energy model (FEM) for bonding in a-SixNyHz alloys has been extended to include the contributions of neutral and charged Si and N defects to the free energy of mixing of the amorphous alloy. The FEM predicts that the dominant defects in N-rich alloys are N2o, N2-, and either S3+ or N2+, in contrast to the results of experimental studies that find the dominant neutral, paramagnetic defect to be Si3o. It is concluded that either the observed Si3o defects are not in thermodynamic equilibrium with the amorphous network or the N2o defects have energy levels which lie much higher in the energy gap than currently believed.

scholarly journals Energy flows, metabolism and translation

2011 ◽  
Vol 366 (1580) ◽  
pp. 2949-2958 ◽  
Author(s):  
Robert Pascal ◽  
Laurent Boiteau
Keyword(s):  
Free Energy ◽  
Carbon Metabolism ◽  
Energy Levels ◽  
Self Organization ◽  
Discrete Events ◽  
Covalent Bonds ◽  
Biochemical Processes ◽  
Energy Flows ◽  
Living Organisms ◽  
Complex Chemistry

Thermodynamics provides an essential approach to understanding how living organisms survive in an organized state despite the second law. Exchanges with the environment constantly produce large amounts of entropy compensating for their own organized state. In addition to this constraint on self-organization, the free energy delivered to the system, in terms of potential, is essential to understand how a complex chemistry based on carbon has emerged. Accordingly, the amount of free energy brought about through discrete events must reach the strength needed to induce chemical changes in which covalent bonds are reorganized. The consequence of this constraint was scrutinized in relation to both the development of a carbon metabolism and that of translation. Amino acyl adenylates involved as aminoacylation intermediates of the latter process reach one of the higher free energy levels found in biochemistry, which may be informative on the range in which energy was exchanged in essential early biochemical processes. The consistency of this range with the amount of energy needed to weaken covalent bonds involving carbon may not be accidental but the consequence of the abovementioned thermodynamic constraints. This could be useful in building scenarios for the emergence and early development of translation.

Definitions of free energy levels in biochemical reactions

Nature ◽  
1976 ◽  
Vol 263 (5578) ◽  
pp. 615-618 ◽  
Author(s):  
R. M. SIMMONS ◽  
TERRELL L. HILL
Keyword(s):  
Free Energy ◽  
Energy Levels ◽  
Biochemical Reactions

Hydration of acylimidazoles: tetrahedral intermediates in acylimidazole hydrolysis and nucleophilic attack by imidazole on esters. The question of concerted mechanisms for acyl transfers

1987 ◽  
Vol 65 (8) ◽  
pp. 1951-1969 ◽  
Author(s):  
J. Peter Guthrie ◽  
David C. Pike
Keyword(s):  
Free Energy ◽  
Energy Levels ◽  
Three Dimensional ◽  
Nucleophilic Attack ◽  
Simple Extension ◽  
Energy Relation ◽  
Free Energies ◽  
Free Energy Surface ◽  
Linear Free Energy ◽  
Tetrahedral Intermediates

Heats of hydrolysis have been measured for three acylimidazole acetals. From these results free energies of formation in aqueous solution have been calculated for the acetals and the corresponding tetrahedral intermediates. Having free energies of formation for the tetrahedral intermediates allows a detailed analysis of the energetics of both the unobservable nucleophilic reaction of imidazole with ethyl acetate and also the observable reaction of imidazole with p-nitrophenyl acetate. pKa values of 1-(3-aminopropyl)-imidazole and 1-(2-aminoethyl)-imidazole have been determined to allow calculation of the σ* value for the imidazolyl substituent. The dependence of imidazole pKa values on the electron-withdrawing properties of the 1-substituent was also determined. There is a linear free energy relation between the free energy change for replacement of OH in a carbonyl hydrate by imidazolyl and the sum of the σ* values for the other substituents. The implications of these results for the question of concerted versus stepwise mechanisms for the reactions of imidazole with aryl acetates have been examined. An equilibrium constant has been calculated for the addition of imidazole to p-nitrophenyl acetate. A simple extension of Marcus theory allows the free energy surface for a three-dimensional reaction coordinate diagram to be calculated using the energy levels of the tetrahedral intermediate determined in this work, the energy level of the acylium ion derived from literature data, and intrinsic barriers for the edge reactions. It is shown that the reaction of imidazole with p-nitrophenyl acetate probably follows a concerted path. General conclusions from this theory of concerted reactions are discussed.

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