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Biochem Block Two
Enzyme Catalysis
13
Biochemistry
Graduate
09/25/2012

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Term
Specific Acid-Base Catalysis
Definition
Involves the constituents of water donation of a proton by the hydronium ion [H3O+], or the acceptance of a proton by the hydroxyl ion [OH-].
Term
General Acid-Base Catalysis
Definition
If the donor molecule is a weak acid or the abstracting molecule a weak base (like a reactive amino acid side chain).
Term
Induced Fit Mechanism
Definition

When some of the energy of binding substrate within the active site is used to generate a conformational change in the shape of the active site.
-In such a mechanism the conformational change distorts the substrate into a more reactive 

shape resembling the transition state. 

Term
Covalent Catalysis
Definition

Results when a covalent enzyme-substrate intermediate is formed during the course of the reaction.  

-Catalysis results if this covalent intermediate is more reactive toward the final acceptor molecule than was the original substrate.
-serine proteases cleave peptide bonds using this mechanism, distinct from carboxypeptidases. 

Term
KD
Definition
[Products]/[Reactants]=[E][S]/[ES]=k-1/k1
Term
Km
Definition

=(k-1+k2)/k1

-[S] which gives 1/2(Vmax)
-when k-1>>k2 then Km~KD
 
-a measure of the affinity of the enzyme for the substrate, the lower the Km the higher the affinity

Term
Competetive Inhibitors
Definition
I binds only to E, not ES
-I increases the apparent Km for S
-as [S] becomes large, I becomes less effective as an inhibitor
-Vmax is unaffected by the inhibitor 
Term
Noncompetetive inhibitors
Definition

I binds to E & to ES

-apparent Km may be unchanged (common), or increased or decreased
-Vmax is decreased
-I interferes with conformational change, but has no effect on S binding.   

Term
Uncompetetive inhibitors
Definition
I binds to ES
-apparent Km is decreased
-Vmax is decreased 
-k2 is lowered
-the substrate binds the enzyme more readily but the catalytic site is not available to react with it.   
Term
Michaelis-Menton Equation
Definition
vo=Vmax[S]/Km+[S]
Vmax is proportional to k2 & [Et
Term
kr Rate Constant
Definition
Rate constant is determined by the free energy of activation, catalysts can reduce that
Term
Carboxypeptidase
Definition
A protease.
-carbonyl polarization & oxyanion stabilization is accomplished by coordination of the oxygen to an active site Zn2+
-an active site glutamate acts as the nucleophile 
Term
Simplifying Assumptions
Definition
1. Initial rate assumption: [S]=the amount of S added
-there is no P & therefore no reverse reaction
2. Steady state assumption: The concentration of [ES] is nearly constant during most of the time P is being formed.  
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