Biochem Final Flashcards
General acid catalysis
H+ Transfer from acid
Decrease G of transition state
General Base catalysis
H+ Abstraction by base
Decrease G of transition state
Concerted Acid-Base catalysis
Combined; Can occur simultaneously or sequentially.
Acid-base catalysis
pH sensitive
Bovine pancreatic RNase A
RNA hydrolysis
2 His Residue (acid/base)
Covalent (Nucleophilic) Catalysis
Transient formation of catalytic substrate covalent bond.
Features:
Nucleophilic
e- withdraw by enzyme
Example of Covalent Catalysis?
Acetoacetate decarboxylase
Acetoacetate can spontaneously become Acetone + CO2
This happens in Type 1 Diabetics; and people on the keto diet.
Acetate + Lysine
Lysine’s NH2 group causes it to form a Schiff Base (imino group).
What is the best Nucleophile?
Cysteine
Protonated refers to?
Acid
Deprotonated refers to?
Base
Metaloenzymes?
Metal ions Roles in catalysis: Substrate orientation Redox Reactions (e- transfer) Electrostatics--Stabilize or sheild charges
Examples of Metaloenzymes? (CA)
Carbonic Anhydrase
Cofactor: Zn2+
Zn2+, polarizes water to form OH-, and orient it.
Examples of Metaloenzymes? (RR)
Redox Reaction: Chytochrome C (Fe2+) Cytochrome C (Fe2+) ---> Cytochrome C (Fe3+) Shuttles e-'s from Complex 3 to 4
Example of Proximity and Orientation?
Imidazole reacting with p-nitrophenylacetate
Tethering of imidazole increases reaction rate ~25%.