1. Thermodynamics and Metabolism _____________change (  ) is a measure of the _______________ _______________ from a reaction  = change in ______________ ___ = change in ______________ A. Thermodynamic Quantities

2. Both entropy and enthalpy contribute to  G (T = degrees Kelvin) ____ = reaction is _____________ in the direction written ______ = reaction is ______________ _________ reaction is at ___________ Relationship among energy, enthalpy and entropy

3. The Standard State (  G o ) Conditions Reaction free-energy depends upon conditions ________________ (  ) - defined reference conditions Standard Temperature = ______(25 o C) Standard Pressure = ______________ Standard Solute Concentration = _____ ____________standard state = _____ Standard ____ concentration = _____ (________) rather than 1.0M (pH = 1.0)

4. B. Equilibrium Constants and Standard Free-Energy Change For the reaction: _______________ At equilibrium: And ____ , so that: 

5. C. Actual Free-Energy Change Determines Spontaneity of Cellular Reactions When a reaction is not at equilibrium, the _______________ _____________________________ _____________________________ (the ratio) ____ = the _______________ ratio Where

6. The Free Energy of ATP ___________________ of metabolic fuels is largely _________________ ______________________________

7. ATP is an “______________”compound A large amount of energy is released in the hydrolysis of the _______________________ of ATP (and UTP, GTP, CTP) All nucleoside phosphates have nearly equal standard free energies of hydrolysis

8. Complexes between ______and ______ Why are phosphoanhydrides high energy compounds? (1) ____________________ among negatively charged oxygens of phosphoanhydrides of ATP (2) ______________________ (ADP and P i ) or (AMP and PP i ) is better than solvation of reactant ATP (3) ______________________ than reactants There are more delocalized electrons on ADP, P i or AMP, PP i than on ATP

9. The Metabolic Roles of ATP ___________________________________ Reactions can be linked by a common _____________________ (B-X) below A-X + BA + B-X B-X + C B + C-X Glutamine synthesis requires ATP energy

10. Phosphoryl-Group Transfer ___________________________ - the ability of a compound to ______________________ ____________________________________ Energy-rich or high-energy compounds have group transfer potentials _________________ ____________________________________ Low-energy compounds have group transfer potentials less than that of ATP

11. Production of ATP by Phosphoryl-Group Transfer ___________________________________ ___________________________________ to form ATP __________________________________ in ________________ pathways ___________________________________ Relative phosphoryl-group-transfer potentials

12. Transfer of phosphoryl group from PEP to ADP Phosphoenolpyruvate (PEP) (a glycolytic intermediate) has a high P-group transfer potential PEP can donate a P to ADP to form ATP ___________________: Energy-rich storage molecules in animal muscle _______________ (PC) and _____________ (PA) are ________________________ Have higher group-transfer potentials than ATP Produced in muscle during times of ample ATP _____________________ when needed via creatine kinase reaction

13. Structures of PC and PA __________-Group Transfer Transfer of the nucleotidyl group from ATP is another common group-transfer reaction ___________________ requires transfer of an ________moiety to acetate ___________________________________

14. Synthesis of acetyl CoA

15. _________ Have High Free Energies of Hydrolysis Thioesters are energy-rich compounds _____________ has a  G o’ = -31 kJ mol -1 _____________ Energy Can Produce GTP

16. __________________________________ from Biological Oxidations Amino acids, monosaccharides and lipids are oxidized in the catabolic pathways ____________________________________ ___________________________________ Oxidation of one molecule must be coupled with the reduction of another molecule A red + B ox A ox + B red Free-Energy Change Is Related to Reduction Potential The ____________________ of a reducing agent is a measure of its thermodynamic ________________ The __________________ is the measured __________________________________ Reference half-cell reaction is for hydrogen: 2H + + 2e - H 2

17. Diagram of an electrochemical cell Electrons flow through external circuit from Zn electrode to the Cu electrode

19. Standard reduction potentials and free energy Relationship between standard free-energy change and the standard reduction potential: n = # electrons transferred F = Faraday constant (96.48 kJ V -1 )  E o’ = E o’ electron acceptor - E o’ electron donor Actual reduction potentials (  ) Under biological conditions, reactants are not present at standard concentrations of 1 M Actual reduction potential (  E) is __________ _________________ of reactants and products

20. __________________________________________ _______________________________________ Most _______ formed in metabolic reactions in aerobic cells is _____________________ ___________________________________ Energy _________________ from ADP, P i Half-reaction for overall oxidation of NADH: Methods for Studying Metabolism Add ______________ to tissues, cells, and follow emergence of intermediates Use sensitive isotopic ______ ( 3 H, 14 C etc) Verify pathway steps in vitro by using ____________________ and substrates Use metabolic ____________ to identify individual steps and sequence of enzymes in a pathway