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Chapter 14. Enzyme Kinetics

Chapter 14. Enzyme Kinetics Chemical Kinetics Elementary reactions A P (Overall stoichiometry). I1 I2 (Intermediates). Rate equations aA + bB + +zZ P. Rate = k[A]a[B]b [Z]z k: rate constant The order of the reaction (a+b+ +z): Molecularity of the reaction Unimolecular (first order) reactions: A P. Bimolecular (second order) reactions: 2A P or A + B P. Termolecular (third order) reactions Rates of reactions A P (First-order reaction). d[P] d[A]. v= =- = k[A]. dt dt 2A P (Second-order reaction). d[P] d[A]. v= =- = k[A]2. dt dt A + B P (Second-order reaction). d[P] d[A] d[B]. v= =- =- = k[A][B]. dt dt dt Rate constant for the first-order reaction d [A]. v= = k[A]. dt d [A]. = kdt [A]. [ A] d [A] t [A]0 [A] = k 0 dt ln[A] ln[A]0 = kt ln[A] = ln[A]0 kt [A] = [A]0 e kt (t). The reactant concentration decreases exponentially with time Half-life is constant for a first-order reaction ln[A] ln[A]0 = kt [A].

• If an enzyme has a small value of K M,it achieves maximal catalytic efficiency at low substrate concentrations • Measure of the enzyme’s binding affinity for the substrate (The lower K M, the higher affinity) K M = [S] at which v 0 = V max/2. Lineweaver-Burke plot

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