Bioenergetics -- General Principles • Biological entities obey the laws of thermodynamics. • Accordingly, they can be viewed as systems that use energy transformations to perform various types of work Gibbs Free Energy Useful for predicting whether or not a process is spontaneous. Total Energy Change = Macroscopic + Microscopic Total -- in constant temp/pressure, measured with E (enthalpy) Macroscopic -- energy associated with change in the macroscopic state of matter Microscopic -- change in entropy of system E G TS or G E TS Energy Transformations and Coupling Agents How do energy transformation processes work? Proteins as coupling agents -- devices that link spontaneous and non-spontaneous processes. A mechanical example (and model): At this position E 1 = 0 since M can spontaneously move no further. M G Fulcrum Coupling The Principle of Coupling Illus trate d by a Le ve r Assume this lever is supported L1 = L 2 M 2M L1 L2 Fulcrum d G E1 = M * G * d E2 = 2M * G * d The Concept of Efficiency Conserved (useful) Energy or Power E *100 Available (Total) Energy or Power In the previous example, if we considered the energy available on the right lever arm as the energy used to move the load on the left, then the efficiency of this process was: m* G* d E *100 50% 2m* G* d The Principle of Coupling Illus trate d by a Le ve r Assume this lever is supported L1 = L 2 M 2M L1 L2 Fulcrum d G E1 = M * G * d E2 = 2M * G * d In this case, 50% of the available energy was conserved and the rest was lost. Free Energy Equations Free Energy (G) = Energy available for work, i.e., the work done in going to equilibrium GeneralForm: G nRT ln [state 1] [state 2] G = # units involved * a measure of useful energy (work) per unit Simple diffusion as an example: [state 1] G nRT ln [state 2] E( J) V PV J V R J * K 1 * mols 1 nT nT nT Free Energy in a Diffusion Gradient [side 1] GD n RT ln [side 2] … or, restated: [side 1] GD 2.3* nRT log [side 2] Free Energy and Electrical Charge G nzFE z = charges per particle F = Faraday’s constant -- the amount of charge in coulombs in one mol of electrons E -- electrical potential in joules/coulomb Free Energy from Chemical Reactions aA bBcC dD We can write a description of this reaction at any moment in time as the reaction quotient (QR) or mass-action ratio (q) [C]c *[D]d QR q [A]a *[B]b At equilibrium we say that: Continued [C]c *[D]d K eq QR q [A]a *[B]b Since, by definition, a system at equilibrium can do no work, then any system displaced from equilibrium can do work in either the forward or reverse direction (depending on the direction of displacement from equilibrium.) Thus: GC nRT ln Keq QR or: GC 2.3* nRT log K eq QR Chemical Free Energy Plot Absolute Value of G Review Questions What are diffusive, electrical and chemical work? How could diffusing ions be used to drive some other process? What would be examples of the coupler?