L4 Flashcards
equilibrium constant
K = [AB]/[A] x [B] at equilibrium
AB = product
A, B = reactants
how does concentration of reactants impact if a rxn will proceed
- if low or no A or B - wont proceed; equilibrium tends to shift left
- if high A or B - will proceed; equilibrium tends to shift right
how does concentration of products impact if a rxn will proceed
- if high AB - wont proceed b/c equilibrium shifts left
- if low AB - will proceed, equilibrium shifts to the right
thermodynamic influence on a reaction
negative delta G = spontanrous, requires no energy input (Active transport) - more energy in substrates than in products
positive delta G = not spontaneous, require energy input to proceed (ATP production) - more energy in products than in substrates
if some rxns are spontaneous what keeps them from occurring continuously? - ask tutor slide 8
transition state: unstable, high energy, thermodynamically unfavorable
reactants dont go there, delta G high; they tend to return to lower delta G state
activation energy - a barrier for a spontaneous rxn
enzymes speed up rxns by…
reducing activation energy
enzymes are proteins or riboproteins
Do the work of metabolism: the totality of an organism’s chemical reactions
A metabolic pathway begins with a specific molecule and ends with a product
Each step is catalyzed by a specific enzyme
how do enzymes lower activation energy of reactions?
3D structure of protein has “Active site” that binds substrates
- creates high local concentration of substrates
- holds them in a precise orientation that facilitates bonding
- allows substrates to persist in the transition state
what happens at the active site?
lysozyme cleaves a polysaccharide - degrades sugar polymers
induced fit model (HK) - ask tutor
specific example: Hexose Kinase, an enzyme in glycolysis, initiates reactions that make more ATP in cells
induced fit:
substrate binds enzyme, changing shape of enzyme…
…and the enzyme changes the shape of the bound substrate, putting strain into the substrate
Shape change of the enzyme brings active site amino acids together that together catalyze the rxn
strained swubstrate is susceptible to react at the active site
feedback inhibition
Glucose and ATP (reactants, shown as red hexagon) binds to hexose kinase at
active site.
- Glucose-6-phospate (product, shown as yellow keyhole, labeled molecule X) forms.
- Accumulating G6P binds elsewhere on hexose kinase and reduces its activity.
- Other metabolites (not just the reaction product) can inhibit enzymes.
positive regulation
Phosphofructokinase (PFK): Another enzyme in glycolysis controls a reaction subsequent
to (i.e. downstream of) the one controlled by hexokinase
- Subject to positive regulation
- When ATP levels are low, its degradation product, AMP (green arrowhead, labeled
molecule X), is high - AMP stimulates PFK activity, which can lead to more ATP production.
allosteric regulation of enzymes - ask tutor
both feedback inhibition and positive regulation are examples of this (using other sites besides Active Sites for binding events)
pharmacologic regulation of enzymes
competitive inhibitors bind to the ACTIVE site of an enzyme, competing with the substrate
noncompetitive inhibitors bind to an ALLOSTERIC site of an enzyme, causing a change in shape and making the active site less effective
how do you make a rxn w a positive delta G go?
coupling the rxn w a reaction with a higher negative delta G; net delta G is negative for both. rxns: a spontaneous coupled reaction